-~ --~T 3~Yf/~sC, j2 ~T4 LOVt' ;4/q/y job rvnr THE WORLD BANK OFFICE OF ENVIRONMENTAL AFFAIRS ENVIRONMENTAL GUIDELINES JUNE 1983 T BLE OF CONTENTS Page FOREW AR . . . . . ...R* * * ** * * * * * ** * * * * * ** * * **.1 1. ALUMINUM INDUSTRY.............DT............................... 1 2. CANE SUGAR INDUSTRY.................. 7 3. CEMENT INDUSTRY.......DUS. 18 4. CHLOR-ALKALI INDUSTRY............. 27 5. DAIRY PRODUCTS INDUSTRYDUS........................... 39 6. DUST EMISSIONSISS................ . ....... ..6 46 7. EFFLUENTS, DISPOSAL OF INDUSTRIAL WASTES....................., 54 8. EFFLUENTS, LIQUID, LAND DISPOSAL & TREATMENT.................. 63 9. ELECTROSTATIC PRECIPITATORS (ESP'S)............................ 65 10. ETHANOL PRODUCTIO.. ............. 66 11. FERTILIZER MANUFATURING WASTES........ 76 12. FISH AND SHELLFISH PROCESSING.......... 86 13. FRUIT AND VEGETABLE PROCESSING................................. 95 14. GEOTHERMAL DEVELOPMENT............ 103 15. GLASS MAN UFACTURING................. 105 16. IRON & STEEL INDUSTRY - GENERAL CONSIDERATIONS................. 116 17. IRON & STEEL INDUSTRY - BLAST FURNACE.......................... 124 18. IRON & STEEL INDUSTRY - BY-PRODUCT COKE OVENS.................. 130 19. IRON & STEEL INDUSTRY - ORE PREPARATION, SINTERING AND........ 137 PELLETIZING 20. IRON & STEEL INDUSTRY - ROLLING AND FINISHING OPERATIONS....... 143 21. IRON & STEEL INDUSTRY - STEEL MAKING PROCESS................... 155 22. LEAD SAMPLING AND ANALYSES............. 169 23. MEAT PROCESSING AND RENDERING........... 177 24. MINING - STRIP SURFACE MINING OPERATIONS....................... 183 (SEDIMENT & EROSION CONTROL - LAND RECLAMATION) 25. MINING - UNDERGROUND (COAL).................................... 189 26. NITROGEN OXIDE EMISSIONS............. .......... ........s 198 27. NITROGEN OXIDE SAMPLING AND ANALYSESNAY...... 204 28. NOISE.211 29. NON-FERROUS METALS INDUSTRY - ALUMINUM......................... 219 30. NON-FERROUS METALS INDUSTRY - COPPER & NICKEL................8 228 31. NON-FERROUS METALS INDUSTRY - LEAD & ZINC...................... 240 32. NON-FERROUS METALS INDUSTRY - SILVER, TUNGSTEN................ 251 COLUMBIUM AND TANTALUM - 33. OFFSHORE HYDROCARBON EXPLORATION AND PRODUCTION PROJECTS....... 263 34. OIL PIPELINES................ 275 35. OIL SHALE OPERATIONSERAT............. 281 36. PALM OIL INDUSTRY.DUS........... 295 37.* PESTICIDE MANUFACTURE - SAFETY AND ECOLOGY..................... 303 38.* PESTICIDES - GUIDELINES FOR USE............................... 306 39. PETROLEUM REFINING...FI............ 312 40. PLATING AND ELECTROPLATING...................................o 323 Page 41. PLYWOOD MANUFACTURING.......................................... 332 42. POULTRY PROCESSING............. 341 43. PULP AND PAPER INDUSTRY....ST...4........................... 348 44.* RODENTICIDESC.................................. ........ 364 45. RUBBER PRODUCTION (CRUMB)...................................... 367 46. SECONDARY ENVIRONMENTAL EFFECTS........... 372 47. SLAUGHTERHOUSES I - INDUSTRIAL WASTE DISPOSAL.................. 374 48. SLAUGHTERHOUSES II - DESIGN ARRANGEMENT..RG....3........ ..... 379 49. SULFUR DIOXIDE EMISSIONS - GENERAL POLLUTION SO2*************** 385 50. SULFUR DIOXIDE SAMPLING AND ANALYSESNA.LYSES. ................ 392 51. LEATEER TANNING AND FINISING........... * 399 52. TEA AND COFFEE PRODUCTION.O.D.TO............................ 408 53. TEXTILE AND SYNTHETIC FIBER INDUSTRIES....oUTRI....ES....... . 413 54. WOOL SCOURING.. ................ 421 * Denotes Environmental and Occupational Health and Safety. FOREWORD JUNE 1983 INDUSTRIAL WASTE CONTROL GUIDELINES As an integral part of its appraisal and supervision functions, the World Bank is required. to evaluate the adequacy and effectiveness of pollution cottrol measures for projects involving industrial operations. These evaluations are concerned not only with effects on environment, but with effects on the occupational health and safety of industrial workers as well. To assist Bank's missions, the Office of Environmental Affairs has developed a series of guidelines covering industries and pollutants most frequently, or considered most likely, to be encountered in the Bank lending programs. Each industry, or major pollutant, which may be. common to a num- ber of industries, is treated separately. Guidelines are designed to pre- sent only an overview of a particular industry or pollutant rather than ex- haustive coverage. Each guideline covers a number of aspects, including: environmen- tal factors, permissible pollutant levels, and principal control methods. If applicable, the guideline includes a discussion of gaseous, liquid and solid waste aspects of the same industry or pollutant. Application of these guidelines must be adjusted to each specific situation. Permissible pollutant levels given, are considered to be a- chievable at reasonable costs by existing treatment and control technolo- gy. Where these performance levels cannot be achieved, the appraisal and/ or supervisory mission should. fully document deviations and reasons for these deviations, be they technical, regulatory or other. Where local reg- ulations regarding permissible pollutant levels differ from those presented in these guidelines, the stricter regulations should prevail. Individual guidelines will be revised periodically by the Office of Environmental Affairs as sufficient new knowledge becomes available to warrant changes. Additional guidelines covering specific industries will be written as required. While these guidelines were prepared primarily for use by Bank staff, their use. by others is wecomed and encouraged. Further information concerning environmental acitivities of the World Bank are available by writing to: Office of Environmental Affairs The World Bank 1818 H Street, N.W. Washington, D.C. 20433 U.S.A. iii -1- THE WORLD BANK JULY 1982 OFFICE OF ENVIONMENAL AFFAIRS GUIDELINES ALUMINUM INUSTRY WASTES 1. Aluminum is considered to be the most abundant metal in the earth's crust. The aluminum industry is international in scope, and its maiufacture, fabrication, and use are currently worldwide. The wastes re- sulting frcn the industry's operations are of significant proportions, and hence their effects must be considered in environmental impact assessments. MANUFACTURING PRCESS 2. The basic material used in the manufacture of aluminum metal -is bauxite ore. Major sources of the mineral are South America, the Caribbean and Australia. Specific sources include Jamaica, Haiti, Costa Rica, Suri- nam, Guyana, French Guiana, Brazil, Ghana, Guinea, Sierra Leone, Cameroon, Sumatra, Java and Borneo. 3. The most camonly used method for the production of aluminum me- tal frcn bauxite ore is the Bayer Process, followed by the Hall-Heroult Process. Thus, aluminum production may be considered a two-step process. 4. In the Bayer Process the bauxite is digested with hot, strong al- kali solution (generally sodium hydroxide) to form a solution of sodium a- luminate, and a nud residue (commonly referred to as "red mud"). The solu- tion is then cooled and the mud residue removed by settling and/or filtra- tion. The hydrated aluminum is calcined to produce alumina (A1203), fol- lowing carbon dioxide injection. 5. The alumina is then reduced electrolytically by the Hall-Heroult Process., to produce aluminum, involving the electrolysis of alumina dissol- ved in a fused salt electrolyte consisting of cryolite (Na3Al F6) with minor additions of other fluoride salts. The process is carried out in a cell (pot) - consisting of a carbon anode, a cathode, and the electrolyte - contained in a carbon-lined steel box. This is followed by alloying and casting into ingots. The ingots are then shaped for final use by casting, rolling, forging and/or extrusion. 6. The industry is currently investigating the possibility of pro- ducing alumina fran alumina-bearing raw materials, as an alternative to the Bayer Process. Recycling is also a source of aluminum metal, with material coming mainly fran new scrap, aluminum cans, and discarded automobile bo- dies. -2- ENVI01MENTAL ASPECTS A - BAUXITE MINING 7. The major environmental concerns in bauxite mining operations are land reclamation, runoff water control, dust control and infrastructure im- pacts. 8. It is generally accepted that in cases of mining and related operations the land should be restored to an equal or more useful state than existed before the start of such operations. Reclamation measures and costs should be carefully asseissed and included in the projected mining costs. 9. Rainwater runoff control can be both difficult and costly under certain conditions. Runoff waters should be carefully considered in terms of suspended solids, pH, dissolved solids, and metals. Dust problems may arise fran the mining, handling, and shipping of bauxite ore. ore opera- tions can also generate unwanted noise from blasting and the use of heavy excavation and transportation equipment. Infrastructure needs can include access roads and facilities, personnel housing, and community services. B - BAUXITE PROCESSING AND REFINING 10. In the processing of bauxite to produce aluminum, the principal environmental concerns include: (1) disposal of the bauxite residue (red mud); (2) dirt losses; (3) emissions from fuel burning; (4) waste liquid and slurry streams, other than bauxite residue; (5) noise; and (6) infra- structure impacts. 11. The amount of bauxite residue can vary from a half to one ton dry weight pez ton of alumina produced; depending upon the type of bauxite and the manner in which it is processed. The mud normally contains 20 to 30 percent of solids. While the chemical caposition can vary widely, a re- presentative sample will generally range as follows: Component % (Dry Basis) Fe2O3 30-60 A1203 10-20 Si02 3-20 Na2O 2-10 CaO 2-8 TiO2 Trace-10 Loss On ignition 10-15 pH 12-12.5 (Sol. Fraction) -3- 12. While a number of disposal methods for these residues have been investigated, some form of dumping is currently considered to be the best method, including (1) land impoundment; (2) ocean dumping by ships, barges,, or pipelines; and (3) seashore reclamation. 13. Land impoundment in a diked impervious area is most frequently used, and is the method to be generally employed for Bank-supported pro- jects. Care must be taken to avoid contamination of ground waters. The settling ponds can remove 30 to 60 percent of the solids. In sane cases, water fram the impoundment area can be returned to the process as make-up water. 14. Sea disposal is practiced in a number of areas. 'At some sites in the Mediterranean, the residue -is discharged via pipelines into underwater canyons at depths of over 2,000 meters. In Japan sea dumping is permitted, but only to areas and by methods specified by government regulations, with disposal areas being located over 300 kilometers from shore. Use of bauxite residue for seashore reclamation is permitted in Japan on a limited basis, but has been found to be very costly. 15. For Bank-sponsored projects sea disposal may be used in special cases only, under carefully controlled conditions, and with the assurance that there will be no harmful effects on sea life. 16. The handling of bauxite from its transportation source through storage and processing can generate significant fugitive dust emissions, as can the handling of aluminum from processing to shipping. Although both bauxite and aluminum are inert materials, their escape into the atmosphere can create a nuisance problem. Exhaust gases from aluminum calcination may also be a source of undesirable dust emissions. Abandoned bauxite impound- ment areas can also lead to appreciable dust generation if allowed to be- come entirely dry. 17. Fuel burning for steam generation and aluminum calcination can produce emissions of sulfur dioxide and oxides of nitrogen. Stacks for these facilities should be designed to meet applicable ambient air quality standards. 18. Infrastructure effects may extend some distance from the plant site itself. Consideration should be given to access roads, bauxite un- loading and aluminum shipping facilities, water supplies, power needs, housing for the work force, and community facilities. C - ALUMINA REDUCTION 19. The emissions resulting fran the primary reduction process are both gaseous and particulate in character. The gaseous portions consist mainly of hydrogen fluoride (HF), with traces of other fluoride compounds. The particulate material is chemically ill defined, but does contain sub- stantial quantities of fluoride. The proportion of gaseous to par'iculate fluorides will vary considerably, depending upon the type of cell being operated. -4- 20. While fluorides are the principal substance of concern, attention must be given to other potential waste problems. Scrap carbon, used pot linings, and precipitator dusts snould also be considered. The use of wet scrubber systems may require liquid waste treatment. STANDARDS AND CONTROLS 21. The contaminants of principal concern in the production of alumi- num mtals-are the flourides, in various forms. Standards defining allow- able levels have been established in various countries. On the basis of these and of the currently available technology, the Bank has established limits which are to be adhered to for its projects involving this type of industrial development. These limitations are as followS: A. Bauxite Mining 1. There is to be no disposal of mine tailings to waterways or to the sea, except under very special circumstances and very carefully controlled conditions. 2. A reclamation program is to be established for handling mine tailings. The project sponsor is to submit a proposed plan of action, which will be evaluated as part of the project appraisal. 3. The reclamation program is to be initiated within three (3) years of the start of project perations. B. Bauxite Processing and Refining There is to be no disposal of red mud into either the waterways or into the sea. C. Primary Aluminum Smelting 1. Liquid Effluents Kg. per Mg* Contaminant Al. Produced Fluorides (Total) 0.05 TSS - . 0.01 pH 6 to 9 2. Gas Effluents Stack heights and stack releases should be such that air con- centration both inside and outside the plant will conform to the following limits: * 1Mg= 1 megagram = 1 metric ton. -5- a. Annual Mean Fluorides (as HF) 10 pg/n3 Fluorides (Insol.) 30 Pjg/n3 b. Eighty-Hour Peak Fluorides (as HF) 100 pq/r3 Fluorides (Insol.) 300 ugn/m3 c. Total Enissions Total fluoride discharge is to be no greater than 1 Kg. per Mg of aluminum producted, and the discharge of total particulate is to be no greater than 5 Kg. per Mg of aluminun produced. In applying these standards it is essential that currently recognized and accepted methods of analysis be used to measure concentrations of the contaminants of interest. Standard methodology is generally available, and ray be found in the literature. -6- BIBLIOGRAPHY 1. "The Aluminum Industry and the Environment." UNEP Industry Sector Seminars, Aluminum Meeting, Paris, 6 to 8 October 1975. Papers and Documents. (1975). 2. "Environmental Aspects of the Alminum Industry-An Overview." UNEP' Industry Programme. Paris (May 1977). 3. "Environmental Recommendations for Siting and Operation of New Primary Aluminum Industry Facilities.". International Primary Aluminum Institute. London (1977). 4. "Environmental Considerations of Selected Energy Conserving Man- ufacturing Process Options." Alumina/Aluminum Report. U.S. En- vironmental Protection Agency. Doc. EPA 600/7-76-034 h. Wash- ington (December 1976). 5. "Air Pollution Control in the Primary Aluminum Industry." Sing- master & Breyer. New York (1973). 6. "Development Document for Proposed Effluent Limitations Guidelines and New Source Performance Standards for the Bauxite Refining Sub- category of the Aluminum Segment of the Nonferrous Metals Manufactur- ing Point Source Category." U.S. Environmental Protection Agency. Doc, EPA 440/1-74/019-c (March 1974). 7. "Development Document for Proposed Effluent Limitations Guidelines and New Source Performance Standards for the Primary Aluminum Smelt- ing Subcategory of the Nonferrous Metals Manufacturing Point Source Category." Doc. EPA -440/1-74-019-d (March 1974). 8. "Development Document for Effluent Limitations Guidelines and New Source Performance Standards for the Secondary Aluminum Smelting Sub- category of the Aluminum Segment of the Nonferrous Metals Manufactur- ing Point Source Category." Doc. EPA-440/1-74-019-e (March 1974). 9. Bauxite, Alumina and the Environment (ISSN. 0378-9993. UNEP, Industry and Environment Office. July/ August/Septem.ber, 1981.. Vol. 4 No. 3 17 Rue Margueritte, 75017, Paris, France. -7- THE WORLD BANK July 1982 OFFICE OF ENVIRONMENTAL AFFAIRS GUIDELINES CANE SUGAR INDUSTRY 1. Cn the basis of general manufacturing practices, cane sugar production falls into one or the other of two groupings - raw cane sugar processing and canie sugar refining. These represent separate major steps in the process and are frequently carried out at separate locations. For the purposes of these guidelines each grouping will be discussed separately under each of the principal headings. Although in a few cases raw cane and refined sugar are produced in the same plant, the two types are, treated separately since physically separate production facilities are generally utilized. ,There are substantial differences in the processes, as well as in the quality and quantity of waste effluentz. 2. In each case organics al,d solids are the pollutant of significance. Pollution loadings are generally expressed in terms of biochemical oxygen demand (BOD5) and total suspended solids (TSS). The hydrogen ion concentration (ph) is also important in measuring pollutional effects of these wastes. MANUFACTURING PROCESSES Raw Cane Sugar Processing 3. Sugar cane is a giant perennial grass, containing varying amounts of sucrose in fhe juice of the mature plant. The exact sucrose concentration depends upon the variety of cane, agricultural practices, and other factors. The harvested cane will typically contain 15 percent fiber and 85 percent juice, by weight. In turn, the juice will average 80 percent water, 12 percent sucrose, and 8 percent invert sugars and impurities. 4. The harvesting and loading of sugar cane on transport vehicles may be accomplished either manually or mechanically, depending upon the availability antd cost of labor. The methods used will appreciably affect the amounts of dirt, trash and mud entering a mill. High loads of these materials are undesirable from both the processing and waste water handling viewpoints, and are generally. higher where mechanical harvesting and loading are utilized. 5. The manufacturing process consists of cane washing and cleaning, milling or extraction of the juice from the stalk, clarification, filtration, evaporation and crystallization. Washing is generally employed when mechanical harvesting and loading are used. After cleaning, the cane is cut into chips, shredded and fed into a series of mills for crushing and extraction of 40 to 50 percent of the juice. The cane fiber from the final mill, known as "bagasse", is usually fed to a boiler and used to produce steam. -8- 6. The juice from the mills contains large amounts of impurities. Screening removes the coarser shreds, which are returned to the mills. Lime, heat and a small amount of phosphate are used to remove much of the remaining impurities through precipitation, settling and decantation in continuous clariliers. Following clarification the juice is divided into the clarified and precipitated mud portions. Rotary vacuum or other types of filters are used to thicken the precipitated materials and recover a part of the juice. The liquid from the clarification system is about 85 percent water and 15 percent soluble solids. Before crystallization, the solution is reduced by evaporation to obtain a syrup containing about 60 percent soluble solids. 7. The -concentrated juice from the evaporation is crystalllized, gently agitated and discharged to high-speed centrifuges to separate the crystal from the syrup. Crystals remaining in the centrifuge are washed with hot water to remove remaining syrup and the crystalline sugar trans- ferred to storage for subsequent shipping of futher processing. 8. A typical process flow diagram is presente,. in Figure 1. Cane Sugar Refining 9. The raw material for refining consists of the crystalline sugar produced by the raw cane factories. The raw sugar contains a film of mo- lasses, as well as various impurities such a bagasse particles, organics, inorganic salts and microorganisms. The refining process involves the re- moval of most of this film and the associated impurities. The steps gener- ally followed include affination and melting, clarification, decoloriza- tion, evaporation, crystallization and finishing. A typical process flow diagram is presented in Figure 2. Processes will vary in detail from refi- nery to refinery. Such differences are particularly evident in ccolora- tion methods, where the mediun may consist of bone char, granular activated carbon, powered -activated carbon, vegetable carbon, ion-exchange resins or other materials. 10. In some cases a refinery may produce liquid sugar only, or both liquid and crystalline sugar. For liquid sugar the affination, decoloriza- tion, and evaporation steps are usually the same. After evaporation, the sugar solution is filtered, cooled and stored in the liquid form .for later distribution. A typical process for liquid sugar refining is presented in Figure 3. SOURCES AND CHARACTERISTICS OF WASTES Raw Cane Sugar Processing 11. In raw cane sugar processing, water is used for cane washing, cooling of vapors from barometric condensers, slurrying of filter cakes, boiler bottom ash and boiler fly ash, boiler makeup, maceration, floor wash and clean up and miscellaneous cooling. Botler Feed Water COMPIENISATE SITO.SE Dilution of Molassei Electricity Steam Bagasse Imbibition Washing Discharge Turbogenerators Bearing Cooling Steam Turbines Water--Cooled Condenser -. and Recycled or Water From Discharged Barometric Legs Mechanical 14111 Drive Cane Leveler Cane Wash Imbibition Water / / /.\ Juice Rtcycle CrirCrusher ,----- --- F Knives .:.- Screenings a o c d Cane Wash Water Filter to Discharge or Recycle Juice To Clarification Figure 1 - Typical Process Flow Diagram for Raw Cane Sugar Production - 10 - Raw Sugar Hot Water MAGMA 7AFFINATION. MINGLER CENTRIFUGALS MELTER CLARIFICATION Mingling Syrup FILTRATION ~ONPRESSURE . Cake FILTRATION Disposal Scum and . I - Cake Disposal DECOLORIZATION EVAPO VACUUM PANS Final *--- CENTRIFUGATION Molasses GRANULATION PACKAGING . OR STORAGE Figure 2 - Typical Process Flow Diagram for Refined Crystalline Sugar Production Raw Sugar AFFINATION Steam 1Water MELTING Wae SWEET WATER CL.ARIFICATN FILTRATION GRANULAR CARBON ION EXCHANGE Water EVAPOKEIO ¡y. HOT WATER EVORAT ION Carbon FILTRATION Diatomaceous Earth INVE RSION Refined Sugar Figure 3. - Typical Process Flow Diagram for Refined Liquid Sugar Production - 12 - 12. Water use will vary considerably between plants, due to differ- ences in water conservation and recirculation practices. The quantitites of waste water generated in a plant may not correspond to the total water intake because of moisture content of -sugar cane, amounting to 70 to 75 percent; a portion of the fresh water added in the process enters into the filter cake and bagasse; and a portion of the fresh water is lost through evaporation. 13. Waste water production will be affected by (1) the condition of the cane upon arrival at the factory in terms of the mud and trash content; (2) harvesting technique, whether by hand, mechanically, or a combinaiton of the two; (3) the availability of land for waste water treatment of dis- posal; (4) length of processing season; (5) climatic variations; (6) size of plant; (7) nature of soil; (8) process variations; (9) nature of water supplies. 14. The-character of the total waste water discharges will depend not only upon the characteristics of the component streams, but also upon the extent of in-plant waste reduction practices. The principal sources are the filer mud, barometric condenser cooling waters, and cane wash water. Some pollution is added by numerous small streams originating in the pro- cess. In general, purely hazardous.or toxic pollutants (such as heavy met- als and pesticides) will not be found in wastes discharged from cane sugar factories. 15. While a number of parameters may be considered in evaluating the effects of these wastes, it has been found that three are of principal sig- nificance: (1) BOD5, for measuring the organic oxygen-consuming materials; (2) TSS for measuring the loading of suspended materials which could inter- fere with water supply andd other legitimate stream use; and (3) pH for as- sessing the acidity of alkalinity of the wastes. Cane Sugar Refining 16. . As in the case of raw cane sugar plants, water use will vary widely due to differences in processes, water reuse, conservation tech- niques, and other aspects. Water supplies are usually taken from two sour- ces. One will be a low quality water, generally from a nearby surface sup- ply, for condenser cooling. The other will be a high quality water, such as from a municipal source, for process, washing and related purposes. Water intake for a crystalline refinery is about double that for a liquid sugar refinery. 17. Waste water discharges may originate from condensers, filter backwash, truck and equipment washing, floor drains, boiler fed blowdown, and miscellaneous cooling. 18. Although waste water volumes and quality from refineries will vary widely, the sources may be generally grouped as follows: - 13 - (1) Crystalline refinery using bone- char for decolorization - principally char wash water and barometric condenser cooling water. (2) Crystalline refinery using carb.n for decolorization - principally barometric condenser cooling water, process waste, ion-exchange regeneration solution, and carbon slurries. (3) Liquid refinery utilizing affination and remelt - similar to a carbon crystalline refinery but with a lower barometric condenser cooling water flow. (4) Liquid refinery not using affination, remelt and vacuum pans - similar to number' (3) but with a lower barometric condenser cooling water flow. (5) Combination crystalline and liquid refiner, by separate process-discharge is a combination of numbers (2) and (3). 19. The parameters of principal pollutional significance for cane sugar refining wastes are BOD5, TSS and pH. On an individual basis, chemi- cal oxygen demand (COD), temperature, sucrose, alkalinity, total coliforms, fecal coliforms, total dissolved solids, and nutrients may be of signifi- cance. Based on available evidence cane sugar refining wastes are not known to contain hazardous or toxic substances. EFFLUENT LIMITATIONS 20. As has been previously stated, for both raw sugar processing and cane sugar refining plants, the BOD5, TSS and pH are the pollution para- meters of principal concern, and should therefore receive principal consid- eration by appraisal and supervision missions. The effluent limitations. presented below are considered to be economically achievable- by the use of best available technology for.new plants. Raw Sugar Cane Processing 21. The quality and quantity of plant discharges will be influenced by several factors. Such factors include raw materials, harvesting tech- niques, length of grinding season, climatic 'variations, growing cycle, to- pography, precipitation, irrigation prctices, and other relevant aspects. 22. Generally the most significant factor influencing operations and waste water characteristics will be the mud, dirt, and trash content of the cane upon arrival at the factory. Harvesting techniques--whether mechan- ical, hand, or a combination of the two-will determine the amounts of these materials entering the plant.. The levels of undesirable materials will affect processing operations in terms of : the presence or absence of cane washing and the quality of spent cane wash water; the efficiency of sucrose production; and the amounts, of filter muds and bagasse produced. Factories processing hand harvested cane generally do not utilize cane washing, and thus should more readily produce a high quality effluent. -14- 23. Table 1. lists the permissible effluent concentrations for maximum daily average discharges, expressed in terms of kilograms of pollutant per megagram of field cane.* Field cane is defined as the cane crop as harvested, including field trash and other extraneous materials. 24. As an approximation for relating pollutant discarges to output of finished product, experience indicates that on the average 1 megagram net cane will produce 75 kg. of raw cane sugar. Field cane may contain from zero to as high as 50 percent field trash* and extraneous materials, depending upon the location, harvesting methods, and other local factors. Net cane is defined as field cane minus the weight of extraneous materials. Table 1. - Effluent Limitations for Raw Sugar Can Procesing Plants. Harvesting BOD5 TSS Method Max. Daily Max. Daily pH Mech. or com- bined hand/mech. 0.20 0.48 6 - 9 Hand 0 0 6 - 9 Cane Sugar Refining 25. For purposes of applying effluent standardds, cane sugar refineries are grouped according .to whether producing crystalline or liquid sugar. Current limitations to be applied to Bank projects are given in Table 2, expressed as kilograms of pollutant per megagram of melted sugar. 26 As an approximation for relating pollutant discharges to finished product, experience has shown that on the average 100 kg of raw cane sugar will yield about 93 kg of crystalline sugar, at 960 Brix. Degrees Brix is defined as the percentage of sucrose, by weight, in a pure sugar solution. * 1 megagram = 1 metric ton 1 Mg = 1 MT 15- Table 2 Effluent Limitations for Crystalline and Liquid Sugar Refining Plants 1/ Category BOD5 TSS 2/ Max. Daily Max. Daily ,pH Crystalline 0.18 0.11 6 to 9 Liquid 0.30 0.09 6 to 9 CONTROL AND TREATMENT 27. Flows resulting from the production of sugar, spanning from the harvesting of cane to the refined product, are amenable to a number of techniques for reducing or eliminating waste discharges. This includes both in-plant and end-of-pipe procedures. Raw Cane Sugar Processing 28. Treatment and disposal at cane sugar factories may range from essentially no treatment to complete land retention (by irrigation or other means) for eliminating all discharges to surface waters. In-house measures could include development of new harvesting methods for reduction or elimination of cane wash waters; dry hauling or impoundment of filter muds and bottom ash; recirculation or reduction of various cooling water flows; and improved plant housekeeping practices. 29, Existing end-of-pipe technology is considered rudimentary. The procedures currently employed include: (1) impoundment of all contaminated waters; (2) recirculation of can wash waters; (3) dry hauling or complete cotainment of ashes and filter mud slurries; (4) recirculation of condenser waters or use for irrigation; (5) screening and disposal of leafy trash; and (6) elimination of excess bagasse discharges. 1/ Assumes cooling and recyling of barometric condenser cooling water. 2/ For combined crystalline - liquid refineries applicable limitation may be determined by taking weighted average of crystalline to liquid pro- duction. 30. A number of potential end-of-pipe technologies are currently un- der investigation, including: (1) biological treatment (stablization ponds, activated sludge and others); (2) the use of tube settlers and other means for removing solids without the use of coagulants; (3) modification of cane washing systems to reduce soil loadings in the waste waters; and (4) the use of polymers to accelerate settling of waste water discharges. Cane Sugar Refining 31. Current technology for the control and treatment of cane sugar refining waste waters consists principally of process control (i.e. recyc- ling and reuse of water, prevention of sucrose entrainment in barometric condenser cooling water, and recovery of sweet waters), impoundment (land retention), and disposal of process waters to municipal sewerage systems. In-plant control measures are important in the total pollution control ef- fort. A principal purpose of these measures is to prevent sugar losses, which may be looked upon as profit losses by the refiner and as organic pollutant contributions by the environmentalist. 32. In addition to reducing sugar losses, other measures would in- clude effective dry-handling techniques for sludges and filter cakes, maxi- mum recovery and reuse of various process streams, and improved housekeep- ing. 33. A number of end-of-pipe techniques are available, ranging from preliminary to advance waste treatment systems. These would include (1) flow equalization; (2) chemical treatment (pH adjustment, chlorination); (3) primary treatment (settling, sedimentation, and clarification); (4) bi- ological treatment (activated sludge, trickling filters, stabilization ponds and lagoons); (5) advance waste treatment (carbon adsorption, micro- screening, reverse osmosis); and (6) ultimate disposal (evaporation la- goons, spray irrigation). .34. When land disposal of waste water is practiced, contamination of ground water resources must be prevented, whether.such disposal is by see- page beds or by deep well injection. - 17 - BIBLIOGRAPHY 1. Made, G.P. "Cane Sugar Handbook". 10th Ed. John Wiley & Sons, New York, (1977). 2. "Development Document for Interim Final Effluent Limitations Guidelines and Proposed New Source Performance Standards for the Raw Cane Sugar Processing Segment of the Sugar Processing Point Source -Category", U. S. Environmental Protection Agency, Doc. EPA 440/1-75/044 (February 1975). 3. "Development Document for Effluent Limitations Guidelines and New Source Performance Standards for the Cane Sugar Refining Segment of the Sugar Processing Point Source Category". U. S. Environmental Protection Agency. Doc. EPA 440/1-74/002-c (March 1974). 4. "Sugar Manual". Hawaii Sugar Planters Association. Honolulu (1972). 5. "A System Approach to Effluent Abatement by Hawaii's Sugar Cane In- dustry". In Proceedings Fourth National Symposium on Food Processing Wastes. Doc. EPA 660/2-73-031, U. S. Environmental Protection Agency. Washington, (December 1973). 6. "Consumptive Use of Water by Sugar Cane in Hawaii", University of Hawaii, Water Resources Research Center, Technical Report No. 37 (1978) 7. Biaggi, N. "The Sugar Industry-in Puerto Rico and Its Relation to the Industrial Waste Problem". J. Water Pollution Control Federation. 40, 8 (August 1968). 8. Miller, J. R. "Treatment of Effluent from Raw Sugar Factories". In proceedings of the International Society of Sugar Cane Technologists, (1969). - 18 - THE WORLD BANK MARCH 1983 OFFICE OF ENVIROtMNTAL AFFAIRS CEMENANUFACTURING GUIDELINES FOR DISPOSAL OF WASTE 1. Cement manufacturing plants vary widely in volume and conposit- ion of pollutants discharged. Differences arise fran process variations, in-plant practices, bousekeeping, and other factors. 2. Three basic steps are normally utilized in cement manufacture: (1) raw material grinding and blending, (2) clinker, production, and (3) finish grinding. 3. Paw materials include lime (calcium oxide), silica, aluminum, and iron. Litne, the largest single ingredient normally canes fran limestone, cement rock, oyster shell, marl, or chalk - all of these sources consist prinarily of calcium carbonate. Other raw materials are introduced as sand, clay, shale, iron ore, and blast furnace slag. These materials may be added initially, with feed. to the process, or further in the process se- quence such as in the clinker grinding stage. 4. Two types of processes are available, naninally termed "wet" or "dry". In the wet process, raw materials are ground, mixed with water and the slurry fed to the kiln. With the dry process raw materials are dried before or during grinding. Dry ground materials are fed to the kiln. 5. The kiln is a long cylindrically shaped oven, internally lined with refractory brick. It rotates slowly on a axis slightly inclined fran the horizontal. The slight axis inclination allows kiln contents to drop forward as the kiln rotates. High temp erature combustion gas produced at the lower end of the kiln flows upward, counter current to solid material noving down the kiln. Coal, gas, or oil my be used to generate this con- bustion gas. Most kilns are equipped to fire more than one type fuel. As material moves down the kiln, its temperature increases to about 14008 C, at which point it fuses to form hard, small pieces termed "clinker". Upon leaving the kiln, clinker. is rapidly air cooled, combined with a small amount of gypsum* and ground into fine powder. Ground cement is further and shipped to market either in bulk or bags. * Gypsum level of the final cement product, regulates cement setting time at the site of its use. -19- 6. Flow sheets for typical wet and dry manufacturing processes are shown in Figure 1. 7. Cement plants are categorized as "leaching" and "non-leaching". Kiln dust leaching systems are used in leaching plants to avoid loss of high alkali dusts. Dry dust is mixed with water to rake a slurry about 10% solids. In the slurry, alkali frxn the dust dissolves into the water. phase. The slurry then flows to a clarifier. Clarifier underflow, - con- taining 40 to 60 % solids returns to the kiln, while overflow is discharg- ed. Clarifier overflow is the nost severe source of water pollution for the cement industry. An alternative for reducing this problem is to use low alkali raw materials. SOURCES OF WASTE 8. Cement manufacture can result in pollution of air, water, and land resources. Air 9. Air pollution can originate at several operations in cement manu- facture. These sources and their associated emissions are as follows: Sources Enissions Raw Materials - Particulates (dust) Grinding, Handling Kiln Operations Particulates (dust), OD, and Clinker Cooling SOxr NOx, Hydrocarbons, Aldehydes, Ketones Product Grinding, Particulates (dust) Handling, Packaging, Shipping 10. A major source of particulate natter (or dust) at nost cement plants is the kiln. Kiln rotation and high-velocity flow of combustion gases entrain large quantities of dust (as much as 10 to 20 % of the kiln feed) out the feed inlet of the kiln. Water 11. Highest levels of water pollution occur when water is allowed to contact collected kiln dusts. Three nost significant sources where this contact may occur are: (1) the leaching operation (most important) which renoves soluble alkali and recovers solid insoluble portions for reuse, and - 20 - Raw Materials . Crushing Wet Process Dry Process Proportioning and ixin ofProporticning .din-Water and Mixing of Raw Materials Itaw Materials in Slurry Tanki Grinding Water .Grinding Homogenizing Homogenizing and Blending UandBlending Evaporation [-Ki.Lln * DUST Ki ln Clinker CoolerClne i-inish Grinding and _ Gypsum Addition Cement Cooler Storage Bagging Shipping Figure 1 - Flow Sheer for Typical Wet and Dry Cement Manufacturing Processes. -21- discharges overflow (leachate) as waste, (2) disposal of enti:e wet dust slurry with no recovezy or reuse (slurry is fed to a pond, solids settle and overflow is discharged), and (3) aqueous effluents frcn wet scrubbers are used to wash dusts from kiln gas emissions. 12. Process cooling is the major use for water in dry process cement manufacture (drying equipment and air COmpressor operation, and cooling of kiln bearings, burner pipes, etc.). Therefore, dry process water effluents should not normally be contaminated unless poor water management is prac- ticed. Slurry water used to feed raw materials into the kiln for the wet process evaporates (dissipates in the air as vapor) so it does not become a water effluent discharge. 13. Auxiliary activities such as electric power generation (with a steam boiler), slurry tank cleaning, washing of bulk bauling trucks, cool- ing tower blow-down, and raw material washing are wastewater sources, but normally of minor significance. Land 14. Kiln dust, raw materials, clinker, coal, and other substances are frequently stored in piles on plant property. Unless proper measures are taken, rainfall may pe iate through these piles, dissolve (or leach) soluble pollutants and carry hem with the sutface runoff waters. Also water polluted in this manner can migrate through the subsurface layers be- neath the material storage piles and contaminate groundwater sources. CHARACTERIZATION OF WASTES 15. Dust renoved from kiln gases is primarily a mixture of raw ma- terial, and clinker particles. These gases also contain alkalies (from the raw materials) and fuel which volatilized in the kiln. While raw material alkalies are insoluble in their natural state, high kiln temperatures, chemically modifies the alkali conponent of its mineralogical matrix so that alkali becomes both volatile at high temperatures and water soluble at lcw temperatures. 16. Plants which produce low alkali cement and use high alkali raw materials do not recyle dust to the kiln. Disposal of this dust is a seri- ous plant problem. In. addition to dust, cement plant emissions also con- tain significant quantities of CO, SOx, (sulfur oxides)' and NOx, (nitrogen oxides), as well as lesser quantities of hydrocarbons, aldehydes, and ke- tones. 17. The seven most significant parameters for evaluating water pollu- tion of cement industry effluents are: pH, total dissolved solids, total suspended solids, alkalinity, potassium, sulfate, and temperature. Average values for these parameters which are in water effluents created by scrub- bing kiln dusts are shown in Table 1. - 22 - Table 1 - Average Values of Pollution Parameters for Leaching and Non-Leaching Plants. Paraneter Leaching Non-leaching pH (m units) 9.9 8.2 TDS 6.6 ng/M4 (a) 0.27 ng/Mg TSS 0.9 " 0 t Alkalinity 1.38 " 0.09 " Potassium Salts 3.3 " 0.08 " Sulfates 6.7 " 0 Tenperatures +3.00C +3.0C increase (b) (a) Milligrams per regagram of product. (b) Typical temperature rise in cooling water discharges. 18. Surface water runoff fran rain ay be contaminated with dust ac- cunulated at the plant site. Runoff fran dust piles, coal piles, and raw material 'storage ay also add to this problem. The pollution potential of runoff waters fron these sources are highly variable. Coal pile runoffs, for example, may frequently show pH values of 4.0 or less. EFFLUENT LIMITATION 19. Permissible levels of gaseous, liquid, and solid waste discharges for both leaching and non-leaching plants are given below. If these cannot be net, appraisal or supervisory missions nust thoroughly document any var- iation and reasons for not meeting these. limitations. Air Pollutants 20. Air pollutants originate in kiln gases, clinker cooler exhaust gases, and (to a nuch lesser extent) in the boiler flue gas. Stack gases should be analysed for 507, Nx, and particulates. If coal that contains mercury is used for kiln heating, flue gas should also be analyzed for mer- cury. Ambient air pollution levels will depend not only on pollution con- centrations in the effluent, but also on stack height, local atmospheric conditions and local terrain. - 23 - 21. The following pollutant limits for the most important emissions are to be adhered to in all but unusual circumstances: SO2 - At Grourid .Level Inside Plant Fence Annual Arith. Mean: 100 ug/m3 Mtx. 24-hr Peak 1000 pg/m3 Outside Plant Fence Annual Arith. Mean: 100/ ug/m3 Max. 24-hr Peak 500 ug/m3 Particulates (dry basis) fran kiln 150 g/Mg. Feed fran clinker cooler 50 g/Mg Feed ground level outside plant fence 80 pg/m3 Stack discharge* 50 mg/m3 Liquid Pollutants 22. Based on currently available technology, liquid effluent disposal should be within the following limitations: * This limit may replace combined kiln and clinker cooler discharge if it appears more acceptable. All Plants - No cooling water discharge. If recycling is not feasible, cooling waters way be discharged provided its temperature rise is not over 3* C. -- No water discharge to slurry waste dusts. - No discharge of slurry spills or slurry tank wash water. - Maintain pH level of effluent discharge between 6.0 and 9.0. Non-Leaching Plants - Suspended solids under 5g/mg Product. - Total dissolved solids no greater than levels in water incoming to the plant. Leaching Plants - Suspended solids less than 150 g/Mg Product. - Total dissolved solids less than 1.5 Kg/Mg Product. TDS may be adjusted to reflect composition of raw materials. -24- Material Storage Piles No rainfall allowed to percolate through piles and runoff in uncontrolled fashion. Equipent Washing, Road Washing, Etc. - Not over 150. g/Mg Product during equipment cleaning operations, or during periods of rainfall. Solid Wastes/Material Storage 23. Kiln dust, coal, and other materials piles should be so arranged as to avoid any arbitrary rainfall runoff. Where such runoff cannot be avoided, the effluent should be channelled, centrally collected, and sub- jected to sedimentation and any other necessary measures for reducing or eliminating pollution. . Also, if any rainwaters can migrate under storage piles to contaminate a groundwater resource, storage areas may have to be lined. CONTROL AND TREMMENT OF WASTES 24. Kiln operation is the major source of dust and gaseous pollu- tants. Larger dust particles can be renoved by cyclones or other mechani- cal devices. Small dust particules can be renoved by electrostatic precip- itators, bag filters, or wet scrubbers. In most cases, collected dust is recycled to the process for reuse as raw material. Dusts from other sec- tions of cement production are generally renoved through local exhaust sys- tems combined with some form of mechanical collection. 25. Both wet process and dry process plants achieve essentially com- plete waste water reuse with available technology, except in certain dust contact operations. In all wet process plants, except those leaching col- lected dust, effluents fran ancillary operations (plant clean-up, truck washing, cooling, etc.) can be used to prepare slurry feed to the kiln. This water evaporates in the kiln, any organic matter is burned off, any nonvolatile inorganic material remains with the product, thus, no water ef- fluent is produced. Cooling towers or ponds may be necessary to recycle excess water. 26. Use of waste waters for feeding the kiln is not possible in dry process plants. Here, however,, virtually ccmplete recycling of liquid ef- fluents is possible if cooling towers or ponds are used. The only dis- charge is normally a small volume of cooling tower "blow-down" or bleed water that is required to prevent buildup of dissolved solids in the recirculating water. In some cases, these small volumes can be evaporated. Cooling streams can be segregated and steps taken to prevent dust entry into cooling water systems. -25- 27. For leaching plants, the water is necessarily exposed to contam-i- nants and recycling is generally rot feasible. Principal pollution param- eters of leaching basin -effluents are pH, alkalinity, suspended solids, and total dissolved solids (primarily potassium and sulfate). Treatment is ef- fected by neutralization and carbonation. Although removal of dissolved solids is generally not practiced for leachate streams, results indicate that evaporation, precipitation, ion exchange, reverse osmosis, and elec- trodialysis, individually or in combination, can be quite effective. 28. Laboratory analyses for any liquid effluent should include pH. total dissolved solids, total suspended solids, alkalinity, potassium, salts, sulfate, and temperature rise. 29. Solid naterials, including wastes, are generally stored in piles on plant property. These can be contained or treated .(diking, latex spray- ing, etc.) to prevent rain runoff into adjacent waters. Diked areas should be of sufficiennt size to contain an average 24-hour rainfall. ENERGY CONSIDERATIONS 30. Application of these guidelines and control mechanism should ensure optimm utilization of raw materials and result in some reduction of energy requirements. Major factors in minimizing energy consumption will be the plant design and operation. 31. Fuel requirements of a cement plant should vary from 6.23 to 6.91 gigajoules per negagram of product* for the wet process and from 3.14 to 4.0 gigajoules/megagram of product for the dry process. Fuel consumption for new plants should be at the lower limit, and it should fall below the upper limit for existing plants. Conformance to these limits should minimize any impact on the environment. Where fuel consumption for a new plant is estimated to be at or near the higher value, the reasons must be fully explained by the appraisal mission. * One gigajoule = one billion joules. One gigajoule/megagram = 238.9 calories/gm - 26 - BIBLIOGPAPHY 1. "Information Sources on the Cement and Concrete Industry". UNIDO Guides to Information Sources, No. 2. United Nations Industrial Development Organization. New York (1977). 2. "Emission Measurement Techniques for Particulate Matter from Power Plants, Cement Manufacturing and the Iron and Steel Industry". Or- ganization for Ecoinmic Cooperation and Development. Paris (1975). 3. Development Document for Effluent Limitations, Guidelines and New Source Performance Standards for the Cement Manufacturing Point Source Category". U.S. Environmental Protection Agency. Doc. No. EPA/440/1- 74-005-a. 4. "Papadakis, M. and M. Venuat. "Industrie de la Chaux, du Ciment, et du Platre", from Collection "Les Industries, Leurs Productions, Leurs Nuisances". Industrie-2. DUNOD. Paris (1970). - 27 - THE WORLD BANK FEBRUARY 1983 OFFICE OF ENVIROMNTAL AFFAIRS CHLOR-ALKALI PLNTS (CHLORINE AND CAUSTIC SODA) 1. Chlorine and caustic soda. (NaOH) production constitute important segments of the inorganic diemicals industry. The largest world producers of chlorine include Canada, France, the Federal Republic of Germany, Italy, the United Kingdom, and the United States. Annual production by_individual countries for 1979 varied fron 0.87 to 11 million metric tons. 2. Except for the United Kingdom the sare countries, along with Ro- Mmnia and Russia, are the largest world producers of caustic soda. For 1979, the annual production varied from 0.7 to 11.3 million metric tons in the individual countries,. as 100 percent NaOH. 3., Chlorine and and its co-product, caustic soda, are used in large quantities in the production of plastics, organic and inorganic chemicals, in the pulp and paper industry, in water supply and wastewater treatment, and in several other industrial processes. MANUFATUING PPCESSES: 4. Chlorine and caustic soda are produced alrcst entirely frcm the electrolysis of a sodium or potassium chloride solution (brines) by one of two major processes - the mercury cell or the diaphragm cell. These two processes differ in cell design and in the quality and quantity of wastes - generated. Other processes, such as the membrane process, have been devel- oped through the pilot plant stage but operating data are not currently available. To avoid any discharges of nercury to the environment, new World Bank projects involving chlor-alkali plants should not utilize the mercury cell process. 5. In the purification of the brine, the sodium chloride solution (brine or salt dissolved in water) is treated with sodium carbonate and sodium hydroxide to precipitate inpurities such as calcium, magnesium, and iron. The precipitated hydroxides and carbonates are then settled in a clarifier and the underflow, referred to as brine nud, goes to a lagoon or to filtration. 6. Brine muds from mercury cell plants usually contain small amcunts of mercury, because of recycling of the spent brine from the cells. Before transfer to the cells, treated brine is evaporated if necessary to rexmve the excess water and -then pH-adjusted. Spent or depleted brine from the cells is acidified and dechlorinated (using vacuum and/or air stripping) before being saturated with salt and recycled. -28- Mercury Cell Process 7. The mercury cell consists of two sections: the electrolyzer and the decomposer or denuder. A general process flow diagram is shown in Fig- ure 1. The electrolyzer consists of an elongated steel trough slightly in- clined fran the horizontal. Mercury flows in a thin layer at the bottom, acting as the cathode of the cell, and the brine flows concurrently on top of the mercury. Parallel graphite or metal anode plates are suspended frcm the cover of the cell. Electric current flowing through the cell decom- poses the brine, liberating chlorine at the anode and sodium metal at the cathode. The metallic sodium forms -an amalgam with the mercury. The amal- gam from the electrolyzer flows to a denuder. The spent brine is recycled to the brine purification process. 8. In the denuder, the sodium-mercury amalgam is the anode and the cathode is iron or graphite. De-mineralized water is added, and this re- acts with the amalgam to fotm hydrogen and caustic soda. The mercury is returned to the electrolyzer. The hydrogen gas can be vented or cooled by refrigeration to remove water vapor before sale or before use as a fuel. 9. The chlorine from the cell is cooled to remove water and other impurities. The condensate is usually steam stripped and then either re- turned to the brine system or discharged as a waste. The chlorine gas, after cooling, is further dried by scrubbing with sulfuric acid. The di- luted acid is regenerated for reuse, sold, or used for pH control. The chlorine gas is then compressed and liquified. 10. The liquefying procedure results in a residual mixture of noncon- densable gases known as tail or sniff gases. This residue is usually scrubbed with caustic or lime, generating a hypochlorite solution, whida is deconposed, used on site, sold, or discharged as a waste. 11. The caustic soda formed at the denuder has a concentration of 50 percent NaOH. Sane of the impurities present in the solution can be re- moved or reduced by the addition of certain chemicals, followed by filtra- tion of the caustic. In most cases the caustic is sent to storage or evap- orated if a more concentrated product is required. Diaphragm Cell Process 12. The process flow diagram for the diaphragm cell process is pre- sented in Figure 2. In this process, the treated brine solution is elec- trolyzed to form chlorine, hydrogen and sodium hydroxide. The cell con- tains an asbestos diaphragm separating the anode frcm the cathode. Chlo- rine is liberated at the anode, while hydrogen and hydroxyl ions are pro- duced at the cathode. The negatively charged hydroxyl ions (anions) will react with the positively charged sodium ions (cations) to form caustic. In the past graphite, with lead to provide the electrical contact and sup- port, was generally used for the anode. ' In recent years the graphite anodes have been replaced by titanium anodes, having a platinum or ruth- enium oxide coating. The advantages of the metal anodes include increased , " 1 � i � ' " • . . . . � 11vnnOCeu ' , ' . • • п� ; � � . С111,0 IUf. • . РUаlГ1СП MERL'URY UM;NVeCa _ i GM►C ; • DN11K '�" JU1111•cAN ,. 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ЧлтГ11 .,,} CEl.L l1U1p1HE ' • 11t то 1 h saOluм • • , Чоисагплст , • • ичОЧохl0е ссоынс . . � • ЛULUTION • MATY.R • � . .. • МлТС11 • ' ' BULГAT[ gA1. RECYCI.�, • . 1К�Е • • � 1:VAГQ1lЛТОR gAПOHETRIC COOLER . C111ANINATLD ЧлтВR CONDEHS1гTE • , ' ' . CANDBN5c8 • , - . . GALT �(�дгlС - ORYER 1► иLАК 6U4ГURiC ACID .., . , ' • • et•моvль • н."о слиsтl ro лт►иsРИсив ' (LIHEj � ' COOLINC SOOIUM 11N0 иАТ�R 6fЮIUH • •` тиея " HrnnoxtOE coмraessoa sсЧивеСа' пУРасиw Rlre•1в то usE ' w ,• s�ьurloH � бowтioN 6ALCS. oR иА9Т[ • , О . � - � • . . � , ui�+r.к1MN • ' . '. то илчтг: пеенlссп- тлl� слs . иАт••н • ' ЧЛТ1:П • FILTCR Ат1оN LIOUEFIБII • • ' � БУSтЕН <,�лF9, Ornrunлc�l sr1�.1s Ник:огплст u1an0 илsiиис , кл;ciuMsnl РАскистис сооьlгю сИгмгlЧе � СТС, илТСВ Ч�' •R • OCPOSlT]OH . TU U51. � • • • оП 8�1LЕу 1'0 6A4BG у'о ил;7•Е • + • ТО HЛSTk . о11 USif �USCO SОНГ. PLANTB ONLY . н ' UE1'сЧ09 lU'оН Р1 �NT 11EBIGN , . • ' . . 1 • ' 1. • • . i � .. „ . Figure 2- General process flow dlagram for production of chl�rine/caustic by '` , diaphragm ce11s. (From Document ЕРА 440/1-79/007) •, 31 power efficiencies, longer anode life,, and a reduction in potential pollu- tant load of lead and chlorinated organics. Cathodes are generally made of m.ital - In the Hooker "S" cell, for example, the cathode is made of crimped steel wire directly covered with asbestos. When in use, the cath- ode unit is conpletely submergered. The asbestos covering then functions as the diaphragn. separating the anode fran the cathode. 13. The chlorine gas is processed in the same way as in the mercury cell process, and produces the same residuals. The hydrogen gas can be vented or cooled to remove the water vapor, and either marketed or used as a, fuel - 14. The resulting caustic (or sodium hydroxide) has a concentration of about 14 percent NaOH and a sodium chlori.de content running as high as 17 percent. The caustic is usually filtered to remove sorm of the impuri- ties and then evaporated to 50 percent NaOH in rmltipl!-- effect evaporat- ors. The vapor resulting from the last of the evaporators is condensed in barometric condensers,, by contact with cooling water, or in surface conden- sers using non-contact cooling water. Sodium chloride remains as a solid salt,, and this is returned to the brine system. Further purification of the caustic is sometimes necessary for certain applications (such as rayon production). Extraction or adsorption techniques are effective in removing small amounts of impurities. TAMSTE SOURCES AND CHAPACTERISITICS Ai-r Emissions 15. Er issions from miercury and diaphragm cell plazits include chlori ne gas, carbcn dioxide, carbcn monoxide, and hydrogen. Gaseous chlorine is present in the gas from liquefaction, from vents in tank cars and tax0% con- tainers during loading and unloading, and frcm storage taxLks and process transfer tanks. Othe-- emissions include miercury vapor from mercury cathode cells and chlorine from compressor seals, header seals, and the air blowing of depleted brine in mercury cell plants. Liquid Effluents - Mercury Cell Process 16. Brine mud,, produced from purification of the brine.. usually con- tains magnesium, calcium, iron and other trace metals such as titanium, molybdenum, chromium, vanadium, and tungsten. Calcium and iron are removed as oxides. Small amounts of mercury also are found in the nud, frcm the recycling of the unconverted brine to the purification unit after dechlori- nation. 17. Ce" room wastes include leaks, spills, area wash down, and cell wash waters. The volume depends tTm housekeeping practices, and my vary from 0.01 to 1.5 cubic meters per metric tcn of chlorine produced. This is the major stream requiring treatment because-of the high levels of mercury present. If graphite anodes are used.. the wastes may also contain lead and chlorinated organics. -32- 18. Condensation from the cell gas is contaminated with chlorine. In most cases the condensates are recycled to the process after chlorine re- covery. Both contact and non-contact water are utilized for chlorine cool- ing and for removal of water vapor. Concentrated sulfuric. acid is used in the. dryer to remove residual water from the chlorine gas after first stage cooling. The acid is used until it is reduced in concentration to 50 to 70 percent. Then it is regenerated, used for pH control in a treatment system, or marketed. 19. The tail gas containing the uncondensed chlorine gas from the liquefaction stage, along with some air and other gases, is scrubbed with sodium/calcium hydroxide to form sodium/calcium hypochlorite solution. Additional hypochlorite solution is produced when the equipment is purged for maintenance. The hypochlorite can be used on site in another process, sold, or treated before discharge. Tail gas scrubber discharges will vary from 0.04 to 0.58 cubic meters per metric ton of chlorine produced. 20. The 50 percent caustic produced at the denuder is filtered to re- move salt and other inpurities. The filters are backwashed periodically as needed. The backwash water can be discharged to treatment, or filtered with the filtrate which is recycled to the brine system. The filtered solids may either be *disposed of to land or reprocessed for recovery of mercury. 21. Ccoling of the hydrogen results in a condensate, which can either be sent to treatment facilities or to mercury recovery and returned to the denuder. 22. In summary, the total waste flow from mercury cell plants is re- ported to average 2.1 cubic meters per metric ton of chlorine produced. This does not include brine nud waters, which are reused instead of dis- charged and hence do not affect total flow. 23. The pollution parameters of importance in the mercury cell plants are total suspended solids (TSS), mercury, and hydrogen ion concentrations (pH). Other toxic metals which nay be present, besides mercury, include arsenic, antimony, cadmium, chromium, copper, lead, nickel, silver, thallium and zinc. The principal sources of these metals are considered to be the raw salt or brine and the corrosion reactions between chlorine and the materials in the process equipment. Other than mercury, the levels of the other toxic metals found in the wastes are not considered to be significant. Liquid Effluents - Diaphragm Cell Process 24. Brine purification produces the brine mid as a waste, consisting of precipitated hydroxides and carbonates of calcium, magnesium, iron, and other metals . The muds are filtered or settled in lagoons, with the filtrate or overfklow either discharged or recycled to the brine systems. The filtrate volume will average about 0.42 cubic meter per metric ton of chlorine produced. - 33 - 25. Cell room wastes include leaks, spills, area washdown and cell wash waters. The cell wash waters contain high levels of asbestos. Where graphite anodes are used in the cells, the wastes may also contain signifi- cant quantities of lead. Waste flows from cell roon operations will vary widely, and will average about 0.38 cubic meters per metric ton of chlorine produced fram metal anode plants. Graphite anode plants will average 1.2 cubic neters per metric ton of chlorine produced. 26. Condensation fram the indirect cooling of cell gas is contami- nated with chlorine. The chlorine is removed and/or recovered frcm the liquid stream before discharge or recycle. Flows will average 0.49 cubic meter for metal anode plants and 0.78 cubic meter per metric ton of chlo- rine produced for graphite anode plant. 27. Concentrated sulfuric acid is used to dry the chlorine gas after the first cooling stage. When the concentration is, reduced to 50 to 70 percent, the spent acid is regenerated, sold, or used for pH control, as is the case-in mercury cell plants. 28. Uncondensed chlorine gas from the liquefaction stage is scrubbed with sodium or calcium hydroxide to produce the corresponding hypochlo- rite. The hypochlorite can be used in other processes, sold, or discharged with or without treatment. Waste flows from this source average 0.17 for metal anode plants and 0.11 for graphite anode plants, in terms of cubic meters per metric ton of chlorine produced. 29. Backwashing of filters used to clarify the caustic product ray produce significant quantities of wastewaters. These are wholly or par- tially recycled to the process. Caustic filter badkwashing is necessary to remove sodium sulfate at graphite anode plants, since the accumulation of sulfate ions can interfere with cell performance. 30. Hydrogen gas cooling produces a stream which is usually dis- charged. The volume of flow is very small and not considered to be of sig- nificance. 31. . Where vapors from caustic evaporators are water-cooled, a signif- icant amount of wastewater can be generated in "once through" installa- tions. Recirculation of the cooling water will greatly reduce this dis- charge, but will require a cooling step and a blowdown discharge. Average wastewater flows from the individual units in the diaphragm cell process are given in Table 1. The total plant flow in any specific case will de- pend upon the practices (such as recirculation, by-product recovery, etc.) employed at the particular plant. 32. The pollution parameters of significance include total suspended solids (TSS), hydrogen-ion concentration (pH), chromium, copper, lead, nic- kel and zinc. Asbestos, used for the diaphragm separating the anode from the cathode, is a major toxic pollutant also fourd in these process waste- waters. However, due to the lack of a standardized analytical procedure there is as yet no general agreement on acceptable limitations. As a rough approximation, a concentration of 300,000 fibers per liter is considered to be an acceptable limit at this time. Other toxic metals may also be pre- sent in these wastes but the levels are generally not considered to be of significance. -34- Table 1. Average Wastewater Flows fran Diaphgram Cell Plants. Fla-m3 per Metric Ton Chlorine Source Metal Anode Graphite Anode Plant Plant Cell room wastes and cell wash 0.38. 1.2 Chlorine Condensate. 0.49 0.78 Spent Sulfuric Acid 0.01 NA* Tail Gas Scrubber 0.17 0.11 Caustic Filter Wash NA* 5.4 Brine Filter Backwash NA* 0.45 Caustic Cooling Blowdown 0.86 NA* Brine Mud 0.42 NA* * NA = Not Available - 35 - Solid Wastes 33. The major sources of solid wastes in chlorine plants, for both the diaphragm and mercury cell processes, are the brine muds. The solids concentration in the filter backwashing can vary from 2 to 20 percent, and range in volume from 0.04 to 1.5 cubic meters per metric ton of chlorine produced. Solids are also present in the caustic filter washdown and the cell room wastes. In a diaphragm cell plant, the waters will contain sig- nificant quantities of asbestos, originating from washdowns and cell repair or cleaning. Total mercury loss from mercury cell operations averages 7.5 grams of Hg per ton of chlorine liquefied. Some portion of this can be ex- pected to be present in the solid wastes discharged fran the plant. EFFLUET LIMITATIONS Air Emissions 34. Air emissions, when discharged to the atmosphere should be main- tained within the following limitations: Carbon Monoxide (CO) Max. 8-hr. Aver. 10 jug/m3 Max. 1-hr. Aver. 40 pg/rm3 Carbon Dioxide (C9)20 mg/m3 Chlorine Gas (as Cl-) Max. 30-idi. Aver. 0.3 mg/m3 Max. 24-hr. Aver. 0.1 ng/m3 Sodium Hydroxide (Na OH) Max. 15 minutes 4 mg/m3 Mercury (Hg) Per ton of chlorine produced: 3 grams Liquid Effluents 35. Liquid effluents from plants using the mercury cell process, are to be usintained within the following limits: Max. Max. 24 hr. Aver. 30 day Aver. Kg per Metric Ton of Chlorine Product. TSS 0.64 0.32 Mercury 2.8 x 10-4 1.4 x 10-4 pH 6 to 9 units 6 to 9 units - 36 - 36. For plants using the diaphragm cell process, effluents should meet the following limitations: Max. Max. 24-hr. Aver. 30-day Aver. Kg. per Metric Ton of Chlorine Product. TSS 1.1 0.51 Chromium 2.3 x 10 8.8 x 10-4 Copper 1.1 x 10-2 4.4 x 10-3 Lead 2.6 x 10-2 1.0 x 10-2 Nickel 1.1 x 10-2 4.4 x 10-3 Zinc 1.1 x 10-2 4.4 x 10-3 pH 6 to 9 Units 6 to 9 Units CONTROL AND TREAIMM OF WASTES' Air Emissions 37. Airborne emissions can be kept within required air quality limi- tations through the use of cyclones, scrubbers, strippers, and other meth- ods. In manuy instances, the gases may be recovered and reused cr marketed as saleable products. Liquid Effluents 38. Management and bousekeeping practices should receive first con- sideration in establishing measures for reducing or eliminating wastewater discharges, and these could include control of water usage, recovery of useful or saleable by-products, and process nodifications. 39. The brine treatment and cell roam areas should be equipped with fiberglass gratings to collect all spills and leaks. Mercury bearing wastes should receive sulfide precipitation, followed by pressure filtra- tion.. This will also renove the other heavy metals which may be present in the stream. The precipitated mercury waste may be stored in a lined pond, transferred to a secure landfill, or processed for recovery of the mer- cury. The filtrate from the sulfide filtration is recycled back to the process. Where further treatment is needed the filtered effluent can be passed through granular activated carbon beds for removal of residual metal sulfides and metallic mercury. 40. At diaphragm cell plants, the prevailing practice is either to control asbestos wastes by settling or filtEering cell wash wastewaters or to neutralize and settle effluents before discharge. Recycling of treated streans is comon, although not always the case. Plants using graphite an- odes treat lead-bearing wastes by chemical precipitation and settling or filtration before discharge. - 37 - 41. The -control of toxic organic compounds varies greatly between plants. For exariple, in a plant where the end use of the chlorine is the manufacture of a chlorinated product, the bulk of the chlorinated organic inpurities are not removed. 42. Where a more purified chlorine product is required, the organics are accumulated in the reboiler of the chlorine scrubber. The residues are batch-treated for separation and recovery of the organic phase materials, which are then sold as feedstock for the manufacture of related products. The aqueous phase may be stripped for removal of additional organics and chlorine, and then recycled or discharged 43. The use of mtal rather than graphite anodes increases cell power efficiency and greatly reduces the pollutant loading of lead and toxic or- ganics. 44. By changing from contact to noncontact cooling of the vapors from caustic soda concentration, or by recirculating barametric condenser water, the amount of wastewater generated qan be considerably reduced. 45. Raw diaphragm materials are being developed, whidh can apprecia- bly reduce pcwer consumption and rinimize or eliminate asbestos dischar- ges. The rodified diaphragms include polymer rodified asbestos rretbranes, polymer merbranes and ion exchange membranes. 46. The use of high pressure and refrigeration for chlorine recovery will reduce the chlorine content of tail gases. Before venting of the tail gas to the atiosphere, the common practice is to scrub it with caustic soda and produce a hypochlorite solution. The hypochlorite can be sold, used on site, or discharged. Solid Wastes 47. The solids contained in the brine muds, as well as those result- ing from other parts of the plant cperations, should first be examined for possible by-product recovery, either on site or elseWhere. When on site disposal is required, these residues may be transferred to ponds, drying beds, or durped in land fills. Since isuch residues may contain mercury or other toxic substances, extreme care should be taken to avoid runoff or drainage into surface waters or seepage into ground waters. Disposal grounds may need to be sealed and provided with surrounding walls to pre- vent both seepage and surface runoff. ENERGY CONSIDERATIONS 48. In the electrolytic chlor-alkali production process the energy requirements will be very large. The process requires an average of 21.6 giga-joules of energy per metric ton of chlorine produced (1 giga-joule equals 1 billion joules). 49. This energy will be in the fonn of electric power, which may either be brought in from outside sources or generated on-site. Where power is brought in from outside sources via a grid system, the available - 38 - energy varies from 30 to 45 percent of the energy content of the fuels used to generate the electricity. If the power is generated at the chemical plant site the available energy can be increased to a range of 60 to 80 percent by, for example, the use of pass-out steam for other factory opera- tions such as distillation or drying. 50. The above energy requirements do not include the energy required by the equipment used for treatment and disposal of plant wastes. These requirements will vary according to the treatment and disposal techniques adopted, and rust therefore be determined on a case-by-case basis. BIBLICGRAPHY 1. UN Economic and Social Council. "Air Pollution Problems of the Inor- ganic Chemicals Industry". Proceedings of Seminar held in Geneva, Switzerland, 1-6 November 1976. Doc. ENV/SEM. 7/3, CHEM/SEM. 5/3. (22 July 1977). 2. Economic Cormission for Europe "Annual Review of the Chemical Industry 1979". Doc. ECE/CHEM/34. United Nations. New York (1980) 3. Jarrault, P. "Limitations des Emissions de Polluants et Qualite de L'Air. Valeurs Reglementaires dans les Principaux Pays Industrial- ises". Institut Francais de L'Energie. Paris (1978). 4. U.S. Environmental Protection Agency. "Compilation of Air Pollutant Emission Factors". Second Edition. Doc. AP-42. Washington (March 1975). 5. U.S. Environmental Protection Agency "Development Document for Effluent Limitations Guidelines and Standards for the Inorganic Chemicals Manu- facturing Point Source Category" (Proposed). Document EPA 440/1-79/007. Washington (June 1980). 6. U.S. Environmental Protecion Agency. "Treatability Studies for the In- organic Chemicals Manufacturing Point Source Category". Document EPA 440/1-80/103. Washington (July 1980). 7. APHA, AWWrA, WPCF. "Standard Methods for the Examination of Water and Wastewater". 15th Edition. American Public Health Association. New- York (1980). 8. Shreve, R.N. "Selected Process Industries". McGraw-Hill Book Co. New York (1950). 9. The Chemical Society. "Conservation of Resources". A Symposium held at the University of Glasgow, 5th-9th, April, 1976. Special Publica- tion No. 27. London (1976). -39- THE WORLD BANK FEBRUARY 1983 OFFICE OF ENVIROMENTAL AFFAIRS GUIDEAINES DAIRY PRODUCTS INDUSTRY 1. The dairy products industrial operations are difficult to treat 'because of wide variations between individual plants in raw material in- .puts, processes used, varieties of products manufactured, volumes of wastes generated as affected primarily by internal plant practice and other fact- ors. These guidelines will present general information on typical plant operations, which may then be applied and/or adapted to specific projects. INDUSTRIAL PROCESSES 2. Dairy products plants may be categorized by specific product out- put. Categories and products generally included in each category are shown in Table 1. 3. Plants may perform a combination of these product operations, al- though there are plants which have only one or two process categories. Typical manufacturing processes for these products can be found in the sug- gested references cited below. 4. For example, processing of fluid milk includes clarifying, cream separation, pasteurizing, homogenizing and possibly deodorizing. For but- ter production, a culture of bacteria is added to cream, the mixture is "ripened" and agitated under oDntrolled temperatures until butter and but- termilk are separated. 5. Cheese is produced through addition of a "starter" to whole milk or skim milk under controlled temperature conditions. An acid or enzyme is added to this mixture to form lactic acid which, in turn, results in curd formation . Curd is separated, washed, and subjected to various additional processes, depending upon the type of cheese being made. SOURCES OF WASTES 6. Dairy industry effluents are. primarily all liquid. Main sources of wastes result from: a) Washing and cleaning of tank trucks, cans, piping and other equipment. b) Spills fram leaks, overflows, equipment malfunctions, careless bandling and other similar causes. - 40 - Table 1 - General Categories and Products for Dairy Processing Plant Operations Category Products Receiving Station Raw Milk Fluid Products Market milk (ranging from 3.5% to fat-free), flavored milk .- .(chocolate and other) and cream (of various fat concentrations, plain and whipped). Cultured Products Cultured skim milk ("cultured buttermilk") yoghurt, sour cream and dips of various types. Butter Churned and continuous-process butter. Natural and Processed Cheese All types of cheese foods except cottage cheese and cultured cream cheese. Cottage Cheese Cottage cheese and cultured cream cheese. Ice Cream, Frozen Desserts, Ice cream, ice milk, sherbert, Novelties and other Dairy water ices, stick confections, Desserts frozen novelty products, frozen mellorine., puddings, other dairy-based desserts. Ice Cream Mix Fluid mix for ice cream and other frozen products. Condensed Milk Condensed whole milk, condensed skim milk, sweetened condensed milk and condensed buttermilk. Dry Milk Dry whole milk, dry skim milk, and dry buttermilk. Condensed Whey Condensed sweet whey and condensed acid whey. Dry Whey Dry sweet whey and dry acid whey. Note: While some plants carry out operations in only one of these categories (single-product plants) most plants produce a combination of two or more of the above categories. -41- c) Processing losses sudh as evaporator entrainment bottle and case washer discharges, container breakage and product change-over in filling machines. d) Wastage of spoiled products, returned products, or by-products such as whey. e) Detergents and other compounds used in working and sanitizing solutions that are discharged as wastes. f) Entrainment of lubricants from conveyors, stackers and other equipment. g) Routine operation of toilets, washrooms and eating facilities. h) Waste materials that may be contained in incoming raw water which ultimately goes to waste. 7. The greatest amount of waste originates from the first five sour- ces listed above and is directly related to various dairy products handled at the plant. Typical contributions of waste aterials to the total final waste load, as estimated for a fluid milk plant in terms of 5-day biodhemi- cal oxygen deinand (BOD5), are shown in Table 2. Table 2 - Estimated Waste Contribution, as BOD5, By Source - Fluid Milk Plant. Waste Source (as BD5) Per6ent Milk, milk products and other edible products 94 Cleaning products 3 Sanitizers Very Small Lubricants Very Small Sanitary and domestic wastes 3 (employees) Total 100- -42- CHARACTEPSTIC OF WASTES 8. Several water quality parameters may be used to assess the pollu- tion potential of wastes from processing of dairy products. Three parame- ters are considered most significant: 5-day biochemical oxygen demand (BOD5), total suspended solids (TSS), and hydrogen ion concentrations (pH). Parameters of lesser significance include, chemical oxygen demand (COD), temperature, phosphorous as phosphates, nitrogen as ammonia and ni- trates, and chlorides. 9. Wastes are largely organic in nature. The mijor pollution effect is to decrease dissolved oxygen in receiving waters. The BOD5 test is most useful as a measure of this potential to decrease dissolved oxygen. 10. Suspended solids will adversely affect turbidity of receiving waters, as well as causing a build-up of bottom deposits. This is particu- larly objectionable when solids are organic in nature, as is the case for dairy wastes. Bottom deposits of organic sludge may exert a heavy oxygen demand on receiving waters. Anaerobic decomposition may produce hydrogen sulfide or other intermediate products which can cause noxious odor prob- leus and can be toxic to aquatic life. 11. A pH outside the acceptable range may have an adverse direct im- pact on the receing waters or may have secondary effects such as increasing the solubility of heavy metals. There may also be increased toxicity to aquatic life, inceased corrosiveness of water supplies, increased costs of water treatment, rendering of waters unfit for certain processes such as food and beverage canning or bottling, and other similar effects. Though individual waste streams may exhibit unusually high or low pH values, the combined discharge from a plant generally results in a final effluent with- in acceptable ranges of this parameter. I EFFLUNT LIMITATIONS 12. Table 3 presents permissible levels of biochemical oxygen demand, total dissolved solids and pH. These levels are to be met by individual discharges frcm the product category indicated. Loadings apply to single- product plants only. Limitations for the final effluent of a multi-product plant should be determined from these, using a weighted average based on the contribution and reduction to be affected by each of the categories conprising plant operations. 13. Where a plant discharges to a municipal sewage collection and treatment system, effluent limitations are governed by local regulations . Depending upon character and volume of the industrial wastes, sore pre- treatment may be required to render them acceptable to the municipal sys- tem. 14. In determining plant effluent loadings and applying these stand- ards, it is essential that currently well recognized and accepted labora- tory analytical techniques be utilized. Detailed procedures may be found in the literature. - 43 - Table 3 - Final Effluent Limitations for Dairy P o ucts Industry - By Individual Product Category Effluent Limitation(a) Individual Product BOD b) TSS(b) pH Receiving Station 0.010 0.014 6 to 9 Fluid Products 0.076 0.096 Cultured Products 0.076 0.096 Butter 0.426 0.534 Natural and Processed Cheese 0.970 1.210 Cottage Cheese 0.168 0.210 Ice Cream lix 0.068 0.084 Ice Cream 0.264 0.330 Condensed Milk 0.190 0.236 Dry 1ilk 0.156 0.194 Condensed Whey(c) 0.060 0.076 Dry Whey 0.150 0.190 (a) For new sources (b) As Kg/Mg of Finished Product.* (c) At 40% solids * Mg - megagram 1 Mg 1 metric ton -44- CONTROL AND TRFATMENT OF WASTES 15. Control and reduction of waste discharges can be achieved through (1) in-plant control and management; (2) end-of-pipe treatment; and (3) discharge to municipal systems. In nost cases a combination of two of these is utilized. 16. In-plant control and management techniques should always be ap- plied, regardless of final disposal of plant effluents. Final discharges will be reduced in strength and/or volumes, thus reducing loading on treat- ment systems. 17. Internal measures most commonly used include: (1) a ccmprehen- sive waste nonitoring system to provide a basis for effective waste manag- ment; (2) an equipment maintenance program to minimize product losses; (3) a product and process scheduling system to assure optimum equipment utili- zation; (4) a product quality control program to prevent loss of products to waste streams; (5) development of uses for waste products; and (6) con- stant improvement of processes, equipment and systems. 18. The major concern in treatment of dairy wastes is to reduce the concentration of oxygen-demanding materials, and thus make wastes generally amenable to one form or another of biological treatment. More commonly ap- plied techniques include activated sludge, trickling filters, aeration la- goons, stabilization ponds, spray irrigation, ridge and furrow irrigation, and anaerobic digestion. In general practice, wastes are treated by a com- bination of these techniques, depending upon volumes, strengths, effluent standards, and other conditions. 19. Probably the nost difficult problem in disposal of, dairy wastes is whey handling. In many cases, whey supply exceeds that which can be marketed for useful purposes. Whey is difficult to treat by usual biologi- cal techniques. The most ccmnon methods for disposal include (1) livestock feeding; (2) spray irrigation; (3) discharge to nu.Lnicipal systems where feasible; and (4) concentrating and drying. 20. Depending upon the volume and strength of the wastes and capabil- ity of the nunicipal treatment system, dairy wastes may be discharged to public sewers. The dairy waste load may need to be equalized either through individual holding facilities or through incidental storage in municipal sewers, in order to av6id shock loads on the municipal treatment plant. Effective in-plant control measures will reduce the strength and volume of the effluents. Where the dairy waste constitutes a significant portion of the total volume reaching the nunicipal plant, the whey should be segregated to avoid possibly upsetting the municipal treatment system. -45- BIBLIOGRAPHY 1. "Develonent Document for Effluent Linmitations Guidelines and New Source Performance Standards for the Dairy Product Processing Point Source Category". U.S. Environmental Protection Agency. Doc. EPA 440/1-74-021-a. Washington. (May 1974). 2. Nemerow, N.L. "Liquid Waste of Industry - Theories, Practices, and Treatment". Addison-Wesley Publishing Conpany, Inc. Reading, Mass. (1971). 3. Finch, J. "Gdidelines for the Control of Industrial Wastes - Dairy Wastes". World Health Organization. Doc. WHO/WD/71.7. Geneva (1971) 4. Jones, H.R. "Pollution Control in the Dairy Industry". Noyes Data Corporation. Park Ridge, N.J. and London, England (1974). - 46 - THE WORLD BANK APRIL 1983 OFFICE OF ENVIRONMENTAL AFFAIRS DUST EMISSIONS GENERAL POLLUTION GUIDELINES Introduction 1. Two series of dust guidelines are presented: one for the work- place and one for the environment beyond the plant fence. 2. Dust concentration LeveLs inside industrial or agroindustrial plants are threshold Limit vaLues (TLV) for workers exposed eight hours a day, and forty hours per week. For this reason, a plant should be designed and operated to provide actual dust Levels weLL below the TLV. 3. Concentration LeveLs given for environment (beyond pLant bound- aries) couLd probably be exceeded a few times per year without experiencing permanent adverse affects. . 4. The Office of Environmental Affairs (OEA) wiLL revise these guideLines when additional knowLedge from inside- or outside the-Bank-Group warrants changes. Definition and Properties of Dust 5. Dust or particulate matter consists of fineLy divided soLids, so smaLL in size as to be capable of remaining suspended by the atmosphere for Long periods of time. The Lower size Limit for particuLates is the transi- tion size to Larger gas moLecuLes (about 0.1 um or Less), whereas the upper particuLate size Limit is about 500 pm. When the upper size Limit is ex- ceeded, gravity wiLL remove a particLe from the air so rapidLy, that it cannot constitute a breathing hazard. IndustriaL, agroindustriaL, trans- portation and domestic activities aLL can release particulates into the air. This dust may or may not be mixed with other gaseous or Liquid contaminants. 6. The five main factors which infLuence the interaction between dust and the human body are: (a) PhysicaL characteristics (size, shape, hardness) (b) ChemicaL composition (c) Concentration in the atmosphere (d) Duration of exposure (e) IndividuaL susceptibi Lity 7. Size of dust particLe: Dust retention by human Lungs varies with particLe size as shown by the foLLowing table (from the US Bureau of Mines): -47- ParticLe Diameter Approximate Retention in (micrometers, ,um) human Lungs (percent) Between 6 - 10 20% 5 25% 42% 13 50% 2 70% 1 70% 0.5 50% Lung retention drops rapidLy beLow 0.2 pm, because dust particLes of this size tend to act as .gas moLecuLes and wiLL be exhaLed as readiLy as they are inhaLed. This is a general rule that wiLL vary with particle shape and specific gravity. 8. Chemical composition: Dust deposited in the Lungs may cause pneumoconiosis (pneumo = Lung; koni = dust; osis = disease) which can be disabling or non-disabling depending on whether or not the dust is physio- LogicaLLy active. Most forms of disabling pneumoconiosis are caused by crystaLLine siLica or quartz (WO2). Amorphous siLica and siLicates (ex- cept asbestos) do not cause disabling diseases. 9. Concentration and exposure time: Dosage is the product of dust concentration and exposure time. The TLV table presented beLow- for -m-ineraL dusts in industrial plants, represents in fact dosages for an 8-hour work- day. This means that if a particuLar dust has a 5 mg/m3 concentration for an 8-hour workday (Dosage = 5 X 8 or 40) with a 10 mg/m3 concentration, a worker couLd onLy stay in the facility for a 4-hour workday to receive the same dosage (Dosage = 10 X 4 or 40). 10. The bottom portion of the TabLe Lists a series of factors to de- termine aLLowabLe dust concentration Levels for workdays differing from 8- hours. Thus in the exampLe used above, if one established in the upper table a 5 mg/m3 TLV for an 8-hour workday and was interested in the aLLow- able concentration for a 4-hour workday, he wouLd use the Lower table to determine the appropriate correction factor of 2. Then, multipLy the upper table vaLues by the correction factor in order to estabLish the aLLowabLe 4-hour workday concentration. (5 mg/m3 X 2 = 10 mg/m3 for a 4-hour work- day). 11. Individual susceptibiLity: Genetic factors not yet fuLLy under- stood make some individuals more resistant than others. Environmental fac- tors can change this resistance. Heavy smokers or workers exposed to chem- ical irritants wiLL LikeLy deveLop pneumoconiosis at an earLier stage. -48- SampLing and Measuring Dust 12. AccurateLy determining dust concentrations in the air remains a problem. One must remember that totaL dust is much Less important than re- spirable dust. The sampLing instrument should thus dupLicate insofar as possible, retention characteristics of the human Lung. A number of such instruments have been developed. The best known are the British MRE (Mines Research EstabLishment) and the American personal sampLer. Their retention characteristics are compared with the human Lung in TabLe 1. There is a good correLation between these two instruments. The MRE sampLer coLLects 1.88 times more than the personal sampLer. As these instruments wiLL coL- * Lect onLy a few miLLigrams of dust over an eight hour period an accurate and sensitive baLance is necessary to weigh the coLLected particLes. The preceding discussion shows why it is imperative to provide the sampLing in- strument name and its retention characteristics with any anaLytical results. OccupationaL GuideLines 13. Occupational guidelines given in the foLLowing table are extrac- ted from Occupational Safety and Health Administration (US Department of Labor) and from the bookLet "TLV" pubLished by the American Conference on GovernmentaL IndustriaL Hygienists (1977). As discussed earlier, entries * in this tabLe are TLV values for 8-hours exposure. ActuaLLy, any facility shouLd be designed and operated to give LeveLs. weLL below .these vaLues (no more than one-haLf the TLV is recommended). 14. When figures are presented in miLLions of particLes per cubic foot (mppcf) they were determined by measurements on impinger sampLes counted by Light field techniques. VegetabLe Dust 15. If these dusts contain Less than 1% Si02 the inert dust TLV vaLue applies. If they contain more than 1% Si02 the quartz TLV applies. Many of these dusts produce aLLergic reactions either from their own antigen content or from moLd or fungi dusts that grow during storage. Vegetable dusts can create three kinds of hazards: respiratory effects, skin and eye effects and fires and explosions. - 49 - Table 1. 10 0 i Pulmonary Deposition 80-\ 2 Personal Sampler (cyclone) 0 3 MRE Samplcr 60 -2 40 - 20 - 0 2 4 6 8 l0o, 12 Pace Dlameter (micrometers) .Source: U.S. Burezu of Mi1nes. S=mpling an-d Evpluating Respirable Coal1Mine Dust: A Training Mý'anual. U.S. Bureau of Min',-es, nomainCircular No. 8503, Februar-y 19'il, p. 3. Adapted from Fig-ure 1. OL.. - 50 - TLV FOR DUSTS Based on 8-Hour Workday Substance mppcf mg/m_ ,Silica (SiO7) CrystaLLine Quartz RespirabLe *1,4 300 10 %SiO2 + 10 %Si02 + 2 Total Dust 30 %Si02 + 2 CristobaLite Use one haLf of the Thidymite vaLues caLcuLated for totaL dust TripoLi (Respirable) *4 10 + 2 %Si.02+2 Fused SiLica Use quartz formuLa 'Amorphous RespirabLe *4 1 (< 5/um) (including diatomaceous earth) TotaL 3 (aLL sizes) SiLicates (< 1% quartz) Asbestos (aLL forms) *3 2 fibers (> 5um)/cc Graphite (naturaL) 15 Mica 20 -- MineraL WooL Fiber -- 10 PerLite 30 -- PortLand Cement 30 -- Soapstone 20 -- TaLc (Non-Asbestiform) 20 -- TaLc (Fibrous) Use asbestos vaLue TremoLite Use asbestos vaLue CoaL Dusts Bituminous RespirabLe fraction <5% Si02 * 2.4 RespirabLe fraction >5% 5i02 * 10 %Si02 + 2 Inert or Nuisance Dusts (2) Respirable *4 15 5 TotaL 50 15 - 51 - TLV CORRECTION FACTORS FOR WORKDAYS DIFFERING FROM 8 HOURS Workday Hours TLV Correction Factor 1 8.0 2 4.0 4 2.0 8 (Base Case) 1.0 10 0.8 15 0.53 20 0.4 Notes: (1) Both concentration and % 5i02 to be determined from dust fraction passing a size selector with the foLLowing charac- teristics. Aerodynamic Diameter (pm) % Dust Passing (unit density sphere) Through the SeLector < 2 90 2.5 75 3.5 50 5.0 25 10.0 0 (2) Should contain Less than 1.0% quartz; if quartz content is greater use quartz formuLa. (3) As determined by the membrane fiLter method, at 400-450 X mag- nification (4 mm objective) with phase contrast iLLumination. (4) Respirable dust as defined by the British MedicaL Research CounciL criteria, and as sampLed by a device producing equivalent results (MRE sampLer). - 52 - EnvironmentaL Guidelines 16. The U.S. Department of Health, Education and Welfare estimates adverse human heaLth effects begin when ambient Levels of dust exceed 80 pg/m3, whereas adverse effects on materials and vegetation can begin with 'dust Levels as Low as 60 pg/m3. These estimates formed the basis of the foLLowing EPA dust guidelines (issued in July 1974). (a) 75 pg/m3 -- annual geometric mean (b) 260 ,Pg/m3 -- maximum 24 hour concentration, no more than once a year. To make these guideLines easier to use, EPA. (at the same time) aLso pro- vided a guideLine for stack discharges: 50 mg/m3 (dry). As a comparison, the USSR guideline is 150 pg/m3 (maximum 24 hour concentration). The pre- ceding figures are applicable to totaL inert dust (< 1% Si02) containing no carcinogenic compounds. Large variations from one project to another exist in terms of requirements for dust controL. These variations are due to the physicaL and chemical characteristics of dusts between projects,' climate (dry or rainy, calm or windy), and other factors of Location. Therefore it is difficuLt to offer universaL guide- Lines for dust controL. As a ruLe, the foLLowing LeveLs should not be ex- ceeded: Stack Emissions: When background LeveLs of dust are high, dust emissions from the stack shouLd not be greater than 100 mg/m3 Ambient Levels: AnnuaL geometric mean 100 ,ug/m3 Maximum 24-hour concentration 500/ug/m3 If the dust under consideration is affecting vegetation, the annuaL mean and 24-hour concentration figures shouLd be adjusted downwards. SampLing and AnaLysis 17. OnLy anaLyticaL resuLts which give both sampLing method and meth- od of analysis are meaningful. The most reLiable sample is "respirabLe dust". If it is not possible to coLLect a "respirable dust" sampLe, the totaL dust sampLe shouLd be evaLuated. Whatever sample type is selected, the name of the sampLing instrument and its retention characteristic should be given. Weighing a sampLe (if possible) is the most accurate method of anaLysis. Precautions shouLd be taken to weigh onLy dry dust from which aLL moisture (humidity) has been removed. ParticLe counting is less accu- rate than weighing, but nonetheLess is acceptabLe for any siLcate except asbestos. If particle counting is the only avaiLabLe means for asbestos, it shouLd onLy be done for fibers Longer than 5 um. -53- Control 18. The appraisaL mission should receive assurances that the project wiLL meet the guideLines and that necessary equipment and trained personneL wiLL be avaiLable to sampLe, analyze, and take any necessary corrective measures. FoLLow-up missions should check analysis results in comparison to the guidelines. If results are higher than guideline va'Lues, mission members shouLd ask for reasons and discuss possibLe corrective measures. LegisLation 19. If existing Legislation in the project country incorporates dust standards or guidelines stricter than IBRD's guidelines, country standards prevaiL. 20. If, on the other hand, existing LegisLation in the project coun- try is Less restrictive than IBRD guidelines, the appraisaL mission should present reasons why it is expected that plant personneL and the neighboring exposed popuLation and its environment wiLL be as weLL protected as if the guideLines were foLLowed. - 54 - THE WORLD BANK CCTOBER 1982 OFFICE OF ENVIROIMENTAL AFFAIRS GENERAL GUIDELINES DISPOSAL OF INDUSTRIAL EFFUJENTS 1. These guidelines are intended for general application to disposal of effluents and pollutants for most industrial sources. Although general in nature, they should be applied to the total environment whether the ef- fluents are in the gaseous, liquid or solid state. These guidelines may be applied where particular data is not otherwise available, or as a supple- ment for those specific industries where guidelines have been developed by the Bank. 2. Polluticn may be defined as the addition, fram either natural or man-made sources, of any foreign substances to the air, water or land in such quantities as to render such medium unsuitable for specific or estab- lished uses. An industry may frequently produce wastes that affect rore than one of these media. Thus, the Appraisal or Supervision Mission must consider the total range of disposal operations in order to properly evalu- ate effluent treatment and control measures. Toxic properties are of prime concern in evaluating effects of industrial pollution. Table 1 presents a surmary of waste toxicity frcm a number of industries. 3. Pollution may also result fram noise and heat, which are measur- able in term of intensity and effect but have no physical, chemical or bi- ological composition. 4. This guide is concerned primarily with the effects of pollution on the environment. However, consideration should also be given to the ef- fects of specific contaminants on personnel at the industrial work place. SOURCES AND CHARACTER OF WASTES 5. Effluents are frequently complex, heterogeneous mixtures of sev- eral substances or materials. Gaseous effluents may include particulates (solids) or aerosols (liquids); liquid effluents may include dissolved solids or gases, as well as suspended solids; and solid wastes often con- tain one or several liquids. Gaseous Effluents 6. Airborne pollutants originating at stationary sources whether or not diluted with air, are generally exhausted through a stack. From the stack they will disperse into the atnsphere and eventually return to ground level. Ground level concentrations may be estimated on the basis of the stack height and diameter at stack muth, gas velocity or flow, and temperature. For new installations some of this information will need to be derived from performance at existing installations. - 55 - TABLE 1 - Some Hazardous Wastes Produced by Industry(a) Toxic Waste Produced Industry Solvents Metals Gases Org. Inorg. Mining X X X Textiles X X Paper Prod. Etc. X X Alkalai & Chlorine X Cyclic Internediates X X X X X Organic Chemicals X X X X X Inorg. Chemicals X X X X Plastics X X X Drugs X X X Soaps & Cleaners X Paints, etc. X X X Agri. Chemicals X X X Explosives X X Petr. & Coal Products X X X X X Leather Tanning X X X Asbestos Products X X Blast Furn. & Steel X X X X Non-Ferrous Metals X X (a) Fran "A Study of Hazardous Waste Materials, Hazardous Effects and Disposal Methods", Vol. 1, Report PB 221-465. Booz-Allen Applied Research, Inc. Available from National Technical Information Service, Inc., Springfield, Va. (1973). 56- 7. Gaseous effluents most frequently result fran combustion proces- ses. They may also be either by-products of chemical reactions or suspend- ed particulates resulting fran mechanical operations such as grinding. Principal inpurities of combustion gases generally include sulfur dioxide (SO2) particulates (flying ash or carbon), nitrogen oxides (NOx), carbon dioxide (CO), and mercury compounds from combustion of certain coals. 8. Chemical products released to the atmosphere are too numerous to mention, and depend upon the particular industry considered. As examples, hydrofluoric acid and fluoride compounds evolve from production of both aluminum and phosphoric acid; arsine a particularly lethal arsenic com- pound, (AsH3) can result from the burning of- pyrites or blends in a reduc- ing atmosphere. 9. Quarrying and mining operations can discharge dust or particulate matter into the atmosphere, as can plants producing steel, cement, and fer- tilizers. While dusts may create environmental problems, it is important to note that they may also create serious occupational hazards if the work place has been poorly designed or is not properly operated. The human health problem is of primary importance in these situations. Liquid Effluents 10. Apart from normal human wastes discharges, other liquid effluents from industrial plants consist principally of cooling water and waste by- products dissolved or suspended in water originating from the process or other sources. In many cases the gaseous effluents are stripped of par- ticulate matter by wet scrubbers which, in turn, discharge to plant sewers. 11. Cooling water, as the nomenclature implies, is used to cool pro- cess materials. It is generally uncontaminated in flowing through the plant, except for an increase in temperature and for containing chromates used to protect surfaces from corrosion. When cooling water is combined with other waste streams, the total effluent will contain these other con- taminants. 12. Liquid effluents will generally be at temperatures higher than those in receiving waters . Therefore, care must be exercised to keep the temperature differences as small as possible to avoid harmful effects on aquatic plant and animal species living' in the receiving waters. 13. As a general guideline for Bank projects, effluent temperatures should not be more than 30 C higher than that of the receiving waters. Where the receiving water temperatures are at 28* C or less, the effluent temperature may be a maximum of 50 C above that of the receiving waters. In cases where maintaining these differentials causes excessive increases in project costs or undue harm to fisheries or other aquatic life, the max- im=u allowable temperature may be determined from the following equation: Tmax = OT + URLT-OT 3 -57 - Where: Tmax = Maximum allowable stream temperature after mixing OT = Optimum temperature for species affected URLT = Ultimate recipient lethal temperature for species affected. 14. An important but frequently overlooked source of liquid pollution is the. accidental or deliberate discharge of hazardous materials. Toxic materials have been known to reach adjacent waterways during plant start-up periods because of accidents or inadequate preparation. Village wells and surface supplies have been contaminated from careless disposal of ion-exchange unit backwash discharges. Where toxic materials are used or produced in the industrial operations, measures for prevention of accidental spills should be established and fully described by appraisal and supervision missions. Solid Wastes 15. Land may become polluted or rendered otherwise unsuitable for specific uses through addition of waste materials. Among the more common substances are (1) paper, cartons, plastics, and other packing materials; (2) rubble frcm demolition and other discarded building materials; (3) stripped soil, exposed erodable soil and tailings from mining operations; (4) slag heaps frcm smelting operations; (5) pulp, pits, culls, vines and other organic residuals from canning operations; and (6) organic sludges from pulp and paper mills, textile plants and other industrial operations. 16. Land disposal may include spray irrigation, lard farming, sanitary landfull, deep well disposal and "secure" burial. 17. Proper location and operation of disposal sites are principal factors in handling solid wastes. A general unsightliness, noxious odor caused by deconposing organic residues, and breeding of disease carriers, can result fram improperly operated areas. 18. Dust may also create a problem at dump sites that are completely dry. These sites should be kept to a minimum or eliminated, depending upon their composition and the environment surrounding the disposal site. MANAGEMENT OF WASTES 19. Measurement of effluents, both as to quantity and quality is basic to a waste management program. Acceptable and recognized techniques are readily available for this purpose. The management program will in- volve sampling and analysis of effluents, flow measurements, application of established standards, and control of discharges through treatment or other means. Standardized laboratory techniques should be utilized to assure data acceptability. - 58 - Sampling and Analytical Procedures 20. Monitoring of air contaminants may be accomplished through emis- sion source testing or atmospheric monitoring. Industrial processes may involve frequent cyclic changes. Therefore source monitoring must be care- fully timed so that measurements are nade when the process is operating in typical fashion. Fluctuations of peak loadings must be determined. All waste source variables should be defined so that samples will represent typical process conditions. 21. Atmospheric monitoring requires establishment of an air monitor- ing network. Incation of the sampling stations should be based on the use to be made of the data, such as (1) source-oriented monitoring for enforce- ment purposes; (2) zones of highest projected pollution concentrations; (3) background data needs prior to industrial development* (4) high population density areas; and (5) background data needs where industrial development is not imrninent. 22. Analytical methods for air contaminants are described in the lit- erature. Methods are generally classified as chemical or physical, and cover dustfall, suspended particulate matter, gaseous substances and organ- ic pollutants. 23. Wastewater sampling points should be such that flow conditions in the discharge stream will have achieved a homogeneous mixture. The efflu- ent discharge velocity at the sampling point should be high enough to assure collecticn of a well-mixed representative sample. 24. Flow measurements are an integral part of any wastewater monitor- ing program. Selection of a method will depend upon the facilities avail- able, the degree of precision required, and the conditions under which the wastes are discharged (batch operations, operating periods, etc.). The weight of contaminants discharged to a receiving stream can be calculated from both the flow rate and the measured concentration of contaminants de- rived from the analytical data. 25. Techniques for the qualitative, analysis of wastewaters fall into four categories; chemical, physical, biological and biochemical. Specific analyses will depend upon the nature of the industrial operation and other factors determined on a case-by-case basis. 26. All significant waste streams, including single or conbined flows, which are present or planned, should be described in terms of flow rate (volumetric) and their chemical, physical, and biological characteris- tics. If partial or full treatment of the waste stream is being or will be provided, a full description should be furnished by the missions. -59- 27. Solid wastes from industry often pose special problems such as non-degradability (plastics) and toxicity (chemical residues). In estab- lishing disposal methods, solid wastes should be classified and rated as to their effects such as (1) human toxicity; (2) groundwater contamination; (3) biodegradability; and (4) nobility. Chemical, physical, and biological methods, as described above, are normally used to analyze air and water effluents from solid waste disposal areas. 28. Quantities of solid wastes are measured in terms of both volume- and weight. Leachates are measured by collecting all drainage frcm the disposal area, and passing it through a device for flow measurement and sample collection. Units of Measurement 29. In order to permit conparison of data between projects it is es- sential that, insofar as possible, the same units be used in reporting en- vironmental data. With the rapid movement towards universal use of metric units throughout the scientific and technical communities, Bank missions should confine themselves to that system. 30. More commonly-used metric units are as follows: Gaseous Effluents: Micrograms per Normal cubic meter pg/3m3 (normal)* Milligrams per Normal cubic meter pg/m3 (norrmal) Grams per Normal cubic meter g/m3 (normal) Liquid Effluents: Milligrams per liter rg/L Micrograms per liter pg/L Solid Effluents: Milligrams per kilogram of mg/kg solid waste (dry basis) Flows: Liters per second L/s Cubic meters per hour m3/h Pressure: Kilograms per square centimeter kg/cm2 Newtons per square centimeter N/cm2 Temperature: Degrees Centigrade *C * Normal Conditions: O0 C, 101.3 kPa (760 mm Hg) kPa - kilo Pascals - 60 - Application of Standards 31. "Standards" are be defined as levels at which specific materials may be safely discharged to the environment. "Standards", "regulation", and "norm" are terms frequently applied very loosely in appraising a plant's performance. A strict definition may differ between countries, or *even between regions in the same country. Therefore, appraisal and super- vision missions should clearly define standards used in rating effluent disposal performance. Data for both standards used and a plant's perform- ance should be expressed in units of contaminant per unit of production of raw material input. Effluent Controls 32. Reducticn of waste effluents to meet applicable discharge stand- ards can be acconplished by in-plant measures (process changes, good house- keeping, etc.), treatment systems, or some combination. 33. Measures for reducing gaseous effluent contaminants include (1) operational improvements; (2) increasing stack height; (3) removal of gases by adsorption, absorption, catalytic conversion, or other methods; and (4) particulate removal systems such as filters, sedimentation, centrifugal separators, electrostatic precipitators, wet scrubbers or other equipment. 34. Techniques applicable for liquid effluent disposal include in- plant measures and process changes, discharge to mnicipal treatment systems, or on-site treatment facilities designed to reduce specific con- taminants. 'When releasing liquid effluents, precautions nust be taken to avoid contamination of adjaceant aquifers, particularly in the case of deep-well injection. Thorough tests, using tracer dyes or other nethods, should be conducted at each specific location where it is planned to use this method. 35. Handling and disposal of solid wastes nust give attention to the land at the disposal site, as well as the effect of disposal methods on air and water resources. Sites should be designed and operated to prevent, or minimize or properly channel runoff. Runoff collection and settling have been effective for this purpose. Latex films covering waste piles have al- so been effective. Unprotected waste piles are subject to leaching which may result in acidic or alkaline effluents percolating to streams or aqui- fers used for water supply. 36. Appraisal missions should make certain that engineering designs for the project have incorporated necessary treatment equipment and con- trols to achieve predetermined acceptable levels of effluent quality. The mission should also make certain that equipment cost is included in pro- ject funding, and is properly scheduled for procurement and delivery. Plans should also be developed for the training or employment of personnel to efficiently use the equipment. The sampling and analysis program should be critically reviewed to assure comlete coverage of industrial opera- tions, including night shifts and weekends. - 61 - 37. Supervision missions should ascertain that pollution control equipment has been installed, that it is being efficiently operated, and that adequate monitoring is being provided to assure continuing conformance with control requirements. 38. In all cases, proposed or actual handling of waste materials and final effluents should be coupletely described. This is particularly im- portant with large projects involving several contractors. Where treatment elements are being planned and designed by different organizations or agen- cies, it must be ascertained that these elements are compatible with each -other and will result in an overall system that.reduces plant discharges to acceptable levels. ENERGY CONSIDERATIONS 39. Energy needs for the individual plant must be considered. The fuel requirements for optimum operation of a plant have been determined for a number of industries: Fuel consumption for new plants should readily meet the established levels or ranges. Failure to meet these limitations should be fully explained by the Bank's missions. BIBLIOGRAPHY 1. "Environmental Considerations for the Industrial Development Sector". The World Bank, Washington. (August 1978). 2. "Treatment of Industrial Effluents". Ed. by A.G. Callely, C.F. Forster, and D.A. Stafford. John Wiley & Sons, New York. (1976). 3. Powers, P.W. "Hdw to Dispose of Toxic Substances and Industrial Wastes". Nayes Data Corporation. Park Ridge, N.J. and London. (1976). 4. "Land Application of Residual Materials". Selected Papers-Engineering Foundation Conference, September 26 - October 1, 1976. Pub. by American Society of Civil Engineers, New York. (1978). 5. "Manual on Urban Air Quality Management". European.Series No. 1. World Health Organization, Regional Office for Europe, Copenhagen. (1976) 6. Nemerow, N.L. "Liquid Wastes of Industry - Theories, Practices, and Treatment". Addison-Wesley Publishing Co., Reading, Massachusetts. (1971) 7. "Air Quality Control - Naional Issues, Standards and C-oals". National Associaticn of Manufacturers, Washington. (1975) 8. "Analysis of Raw, Potable and Waste Water". U.K. Department of the Environment, HMSO, London. (1972) - 62 - 9. "Standard Methods for the Examination of Water and Wastewater" 14th Edition. American Public Health Association, New York. (1975) 10. "Standard Methods for the Water Quality Examination for the Member Countries of the Council for Mutual Economic Assistance". Ministry of Forestry and Water Management, in cooperation with the Hydraulic Research Institute, Prague. (1976) 11. Martin, W. & Stern, A.C. "The Collection, Tabulation, Codification, and Analysis of the World's Air Quality Management Standards". Vol. I. ESE Publication No. 380. University North Carolina, Chapel Hill. (October 1974) 12. "Water Quality Criteria - 1972". U.S. Ehvironmental Protection Agency, Washington. (March 1973) 13. "Quality Criteria for Water". U.S. Environmental Protection Agency, Washington. (July 1976) - 63 - TE WORLD BANK AUGUST 1979 OFFICE OF ENVIRONMTAL AFFAIRS 1NDUSTRIAL LIQUID EFFLUENT LAND DISPOSAL AND LAND TREATMET 1. When land is available and concentrations of toxicants are low enough, land disposal is the simplest technical and the most economical way to dispose of liquid effluents. 2. If the effluent is suitable, it can be used for land treatment including irrigation and soil desalination. Land DisDosal 3. In this technique, the affluent is spread on a piece of land for a few hours, then on a second piece for the same amount of time, and so on until it is possible to come back to the first when the water has been absorbed and the biological oxidation completed. 4. It is difficult to give figures in a general guideline. The area required depends on the type of soil, its thickness and on the characteristics of the industrial wastes. It is advisable to err on the conservative side . . when estimating the land necessary and this estimation should be.left to specialists. 5. All agro industries liquid effluents (i.e. slaughter houses, dairies, sugar plants etc.) can probably be disposed of on land as most of the impurities can be subjected to biological oxidation. 6. The US EPA estimates that land disposal is 20% more economical than the usual techniques. When the effluent contains nitrogen and/or phosphorus, land disposal is an easy way to prevent eutrophication of a lake or a river. Land Treatment 7. Certain industrial effluents can be beneficial if used on the land. A few industries produce water as a by-product (i.e. urea). When this water is pure or, as in the case of urea, only slightly contaminated with beneficial products like ao and urea, it can be used in irrigation. Because of the continuous supply.'"I, crops can increase from one per year to two or three. 1/ The yearly plant turn around can be done during monsoon time and/or crop harvesting. -64- 8. Cooling water used in process industries can also be used for irrigation if chromates are replaced by phosphates as corrosion inhibitors and if the free chlorine is kept to a low value. 9. This raises the question of considering the industrial effluents one by one instead of mid"ng them in,a pond or lagoon and then deciding on the treatment. Some effluents can be used without treatment, others with some very slight treatment and these two could then be disposed of on the land or even used in irrigation, the rest mst be treated and discharged in a waterway or in the sea. 10. The advantages of land treatment affects not only the economics of the project but also of the agriculture in the region. For this reason land treatment should be considered as the first option in any industrial project. BIBLIOGRAPHY 1. A History of Land Application as a Treatment Alternative. United States Environmental Protection Agency,April 1979- 430/9- 79-012, Washington D.C. 20460. 2. EPA Design Manual for Land Treatment (in preparation). - 65 - TEE WORLD BANK JANUARY 1981 OFFICE OF NVIRONMENTAL AFFAIRS ELECTROSTATIC PRECIPITATORS (ESP's) GIDELINES 1. Electrostatic Precipitators (ESP's) are one of the best ways to collect dust from gaseous effluents. Several industries use them extensively; among them, cement, mining, steel and non-ferrous metals. They act by ionizing the dust particles in the gas stream. The particle is then pulled towards an electrode by the electrostatic field then removed from the electrode and collected. ES? Design 2. The design takes into account the following factors: gas flow and composition dust concentration in raw gas dust concentration exit ES? All other conditions being equal, the dust amount in the gas exit ESP will determine the characteristics of the precipitators (electrode total surface). 3. If, instead of a 100 mg/m3 concentration we want 50 mg/m3 exit ESP, we will have to practically double the electrode total surface and, at the same time, the equipment price. 4. From the preceding, it is easy to see that the most important technical guarantee is the dust concentration exit ESP. Defining ESP performance by the ratio of dust removed over total dust should be avoided as this depends on the dust concentration inlet equipment. 5. The US and West German standard is now 50 mg/Nm3 in the stack. World Bank Guidelines 6. The World Bank guideline will be 100 mg/m3 in the stack. The concen- tration 150 mg/m3 can be accepted if the plant is in a rural area, and if dust concentration at ground level is within World Bank guidelines inside the plant fence and 260 ,pg (microgram)/im3 maxim= outside the plant fence. 7. Up to 1980 the ESP for LDCs were designed usually for 300 mg/m3. This has created problems particularly in conjunction with low level stacks. The decrease to 100 mg/m3 will also have the added benefit of decreasing the shut down time and the maintenance cost on the extracting fan. At 300 mg/m3 in a power station using normal coal (10% ash), the fan has to be shut down every 3 to 4 months to rebalance or replace some blades. - 66 - THE WORLD BANK APRIL 1983 OFFICE OF ENVIRONMENTAL AFFAIRS ETHANOL PRODUCTION ENVIRONMENTAL GUIDELINES 1. EthanoL, an organic chemicaL, is commonLy used as an industrial soLvent, in medicine, and in the manufacture of alcohoLic beverages. It can be used as a fueL, but is costLier than hydrocarbon fueLs. 2. - EthanoL (ethyL alcohol) can be produced by fermentation from any of three main types of biomass raw stocks: (a) sugar bearing materiaLs (such as sugarcane, moLasses, and sweet sorghum); (b) starches (such as cassava, corn, babassu mesocarp, and potatoes); and (c) ceLLuLoses (such as wood and agricuLturaL residues). 3. Production of ethanoL from these materials first requires con- version of the carbohydrate into soLubLe sugars (except when sugar bearing materiaLs are used), then fermentation of the sugars into ethanoL, and fin- aLLy separation of ethanoL from water and other fermentation by-products by distiLLation. RAW MATERIALS 4. Sugarcane is considered to be the most suitable raw materiaL. It not only requires the simpLest conversion method but its processing also generates a waste product caLLed bagasse. Bagasse is generaLLy dried and used as a fueL for generating steam and power needed for crushing, fermen- tation, and distiLLation operations. One ton of sugarcane having an average sugar content of 12.5 percent produces about 70 Liters of ethanoL by'direct fermentation of the juice. Sugarcane gives one of the highest ethanoL yieLds per hectare of crop Land, and is currently the most commonLy used raw materiaL worLdwide. 5. Cane moLasses, a by-product resulting from the extraction of sugar from cane and known as blackstrap moLasses, has been the most widely used raw materiaL. Production of one ton of sugar yields 190 'Liters of mo- Lasses, containing 50 to 55 percent fermentabLe sugar. A ton of moLasses (consisting mainLy of sucrose, gLucose, and fructose) wiLL yieLd about 280 Liters of ethanoL. Sugar production from beets wiLL also yieLd moLasses which couLd be used as a source for ethanoL. 6. Main starch materiaLs of interest as ethanoL sources are cassava (aLso caLLed mandioca) and corn. Cassava is a root wideLy grown as a sub- sistence crop in a number of developing countries. Under proper condit- ions, cassava yieLds can reach 20 tons per hectare. One ton of cassava yields about 180 Liters of ethanoL. Use of cassava produces no suitabLe residuaL energy source. - 67 - 7. HistoricaLLy, corn has been used principaLLy for fermentation in whiskey production, and as a minor source of industriaL alcohoL. Consider- able work is currently underway to produce ethanoL for use as a gasoline bLend. Corn yields average 6 tons per hectare, and a ton of corn yieLds about 368 Liters of ethanoL. Corn-based ethanoL plants do not produce any residuaL fueL suitabLe as an energy source. 8. Wood and agricultural crop residues are the principal ceLLuLosic materials used. EthanoL production from this source is more complex and Larger in scaLe than that from sugar and starches. No commerciaL scaL processes, suitable for use in deveLoping countries, are currently avaiL- abLe. Considerable development work is presentLy being carried out in many countries, and this may become an important biomass source at some future time. Since this source is not commerciaLLy proven, it wiLL not be dis- cussed further in this document. MANUFACTURING PROCESSES 9. In a plant using sugarcane as the raw material, cane is washed, crushed, and then fiLtered to separate ceLLuLose (or bagasse) from the sug- ar juice. The juice is concentrated and steriLized. This is foLLowed by yeast fermentation of the juice in a batch system. Yeast is removed by centrifuging, treated (to grow additional yeast), and recycLed to the fer- mentation system. Bagasse is dried and burned to generate steam and power to meet in-plant requirements. 10. ConventionaL ethanoL technoLogy uses batch fermentation with com- mon strains of yeast to produce a solution containing 8 to 10 percent aLco- hoL after 24 to 72 hours fermenting. A concentration of 8 to 10 percent ethanoL is the maximum achievabLe in batch systems. 11. Fermented mash (caLLed "beer") is sent to a stripping column. Here, two separate streams are made, the ethanoL product stream (with a trace of water) and a waste stream, caLLed stiLLage. The stiLLage con- tains most of the water and the fermentation soLids. It must be properLy discarded to avoid environmentaL poLLution. 12. The stream containing the ethanoL is distiLLed in a muLtistage coLumn to a concentration of about 94 percent ethanoL. Anhydrous ethanoL, having 99.8 percent purity, is produced in a third distiLLation coLumn, by adding benzene and further distiLLing. Benzene is separated from the aLco- hoL and recycLed. 13. If the end product is to be hydrous or straight aLcohoL, contain- ing 94 percent ethanoL, the third distiLLation step is not used, thus redu- cing steam requirements and eLiminating the need for benzene. 14. The basic process for other sugar materiaLs is the same as des- cribed above. The size of fermentation and distiLLation units might be different, depending upon raw materiaLs used and resuLting materiaLs baL- ance. For these sugar materiaLs, fermentation takes 4 to 5 times Longer than in the case of sugarcane. - 68 - 15. Operations in a starch based ethanoL plant are aLso similar, ex- cept that mash preparation is required prior to fermentation. Cassava roots, (containing 25 to 30 percent starch) are frequently used. First, they are washed, peeLed, and Liquified in a cooker. Liquified starch is broken down into fermentable sugar by adding two enzymes: amyLase and gLuco amyLase. Once fermentable sugar is formed, processing is identical to that for sugarcane, beginning at the fermentation step. 16. Cassava roots contain essentiaLLy no ceLLuLose. No bagasse is formed and energy r1equirements must be supLied from externaL sources. 17. Other starch bearing materials use practicaLLy the same process- ing procedures as cassava, aLthough preparation faciLities must be designed for the particular crop being used. 18. A process fLow diagram for sugarcane and starch-based pLants is presented in Figure 1. 19. TechnoLogy for production of ethanoL from biomass has not changed greatLy in recent years. However, with the increasing interest in the use of aLcohoL as a fueL, severaL efforts are underway. 20. Continuous fermentation, though not yet commerciaLLy developed, can yieLd Liquor with up to 12 percent alcohoL content. AdditionaL micro- bioLogical research is in progress to improve yeast strains to yieLd higher alcohoL concentrations during fermentation. This technoLogy is expected to reduce energy requirements for distiLLation and simuLtaneousLy reduce stiL- Lage volume as weLL. 21. Use of agriculturaL wastes for feedstock or fueL purposes and the development of new or improved crops as raw materiaLs are aLso receiving some attention. A major constraint in utiLizing cassava and corn is the need for externaL fueL sources. Certain agriculturaL waste products couLd be made suitable for fueL purposes by modifying current boiLer designs. WASTE SOURCES AND CHARACTERISTICS 22. EthanoL production produces a number of waste products having an impact on the environment. No extremely toxic waste streams are associated with the biomass conversion technoLogies. OccasionaLLy some heavy metaLs may be found, but this is rare. 23. Sources of air emissions for a particular ethanoL facility wiLL depend upon the feedstock used. The utiLization of grains rather than sug- ar feedstocks wiLL generate particuLate emissions during unLoading, Load- ing, conveying, rough grinding, screening, cLeaning, and fine miLLing the stock. 24. GeneraLLy, air emissions originate from fermenter vents as weLL as the condenser vents on distiLLation coLumns. Fugitive voLatiLe organic compound emissions aLso occur at valves, pumps, flanges, open-ended Lines, and storage tanks, throughout the plant. s CAssAA7 jE6P71 PASTE PiREPARATNON AND SIOnAGE WAAER ENZYME51 EN21M1I* WAILM VAPO LFACION AND WAWLIE- ~i R-- -- cnttN - n] II L t INGS C14t1 1. i l WATE 1At PIIELIt101FAC1IIIN STIEAM FInMENTAT ION AND FI TRATION DISIULLATION ¥EAST ANHIV0MOUS PR[ I FMINtAM4hN -EtitMcIAiIN ...t.L- oIIct PriRnOU14s URAZIL Figure 1. Process Flow Diagram Sugarcane and Starch Based Plants. - 70 - 25. Carbon dioxide is produced during fermentation. Due to high re- covery costs, the gas is usuaLLy vented to the atmosphere. Trace amounts of ethanoL may occasionaLLy escape with the carbon dioxide. Trace amounts of benzene may also escape from the dehydration/benzene recovery process, in both the gaseous and Liquid wastes. Benzene discharges are not consid- ered harmful so Long as they are Limited to trace amounts. Such dischar- ges shouLd be regularly monitored since benzene is a known carcinogen and is highLy explosive. Regular equipment maintenance and proper housekeeping procedures wiLL generaLLy provide adequate controL. 26. FuseL oiLs produced as one of the fractions in the distiLLation column, consist mainLy of amyL or isoamyL aLcohoLs and glyceroL. About 5 kilograms of fuseL oiLs are produced per 1000 Liters of ethanoL. This vaL- uable by-product is either soLd to outside markets or bLended with the eth- anoL as a fueL denaturant. (A denaturant is an additive which, once com- bined, is very difficult to separate and makes the mixture unfit for human consumption). MoLasses fermentation yields about 1.1 Liters of fuseL oiL per 1000 kiLograms of feedstock. With corn the yieLd amounts to about 3 percent of the alcohoL produced. 27. StiLLage consists of non-fermentabLe materiaL, and can be removed at various points in the production process. The most commonLy used meth- od, resulting in minimum ethanoL Loss, is to withdraw it from the bottom of the stiLL during or after distiLLation (thus the term stiLLage). This waste can have a biochemical oxygen demand (BOD5) as high as 40,000 mg/ Liter and contain about 10 percent of solid material. StiLLage contains some fertilizer nutrients made up of about 1 percent nitrogen, 0.2 percent phosphate, and 1.5 percent potash. 28. Yeast grows rapidly in the fermentation step, and the excess is generaLLy recovered, purified, and recircuLated into the system. Yeast re- covery wiLL amount to about 72 grams per Liter of ethanoL produced. 29. If steam and power for conventional sugarcane base operations are generated from burning bagasse, particuLate emissions may resuLt. Were sugarcane is not the biomass source, fossiL fueLs are generaLLy used and, dependent upon the choice of fueL, emissions of suLfur oxides, nitrogen ox- ides and particulates may result. 30. CooLing tower bLowdowns are another waste source. This stream (having high concentrations of dissolved inorganic materiaL) wiLL be high in soLids but Low in B0D5. Feedstock pLant and equipment washes constitute another signifiant waste stream, and can acount for up to 20 percent of the totaL BOD5 Loading. 31. FLy ash, coaL dust, and grain dust are the primary soLid wastes resulting from fermentation process using coaL as a source of fueL. - 71 - EFFLUENT LIMITATIONS 32. Many of the waste materials resulting from ethanoL production yield valuable by-products, or are suitable for other uses. For other poL- Lutants,as discussed below, treatment methods are available for eLiminating or reducing their discharges to the environment. 33. Where disposaL to the environment is unavoidable, effLuent dis- charge Levels are to be reduced to the foLLowing: Air Emissions SuLfur Dioxide (as S02): Ann. Arith. Mean 100 jag/m3 Max. 24-hr. Peak 1000lyg/m3 Nitrogen Oxides (as NO2): Ann. Arith. Mean 100 /g/m3 Particulates: Ann. Geom. Mean 75 ug/m3 Max. 24-hr. (once 260 ug/m3 per year) Benzene 1 ppm Liquid Wastes 5-Day BOD : 30 to 60 mg/L Suspended SoLids : 30 to 60 mg/L pH : 6 to 9 Units WASTE CONTROL TECHNOLOGY 34. Emissions from the various steps in the process can be reduced to acceptable LeveLs by use of conventional mechanicaL coLLectors or wet scrubbers. This wiLL remove or drasticaLLy reduce both the particuLates and gases. A Liquid waste, containing the particuLates as suspended soLids, wiLL be produced and wiLL require disposal. 35. Carbon dioxide is recoverabLe, and it may be economicaL to do so if a market is readiLy avaiLaLbe. It can be used in the manufacture of carbonated beverages, fire extinguishers, dry-ice production, food process- ing, and the chemicaL industry. Some 70 to 80 percent of the carbon diox- ide is recoverable. The gas contains a few impurities (such as aLdehydes and aLcohoLs) and these do cause odors. They can be readiLy removed by ab- sorption or adsorption. 36. FuseL oiL is a combination of higher aLcohoLs, its composition depending upon the crop used to supply the sugar base. It can be used as a feedstock in chemicaL production and as a soLvent. It may aLso be burned as a fueL. In Large scale fermentation it is removabLe in an extra column, fractioned, and marketed as a by-product. Removal is not practical in a smaLL scaLe pLant. - 72 - 37. StiLLage constitutes by far the major Liquid waste requiring dis- posaL. It is high in both BOD and suspended soLids (in the range of 30,000 to 40,0000 mg/Liter), and volumes wiLL be in the range of 10 to 15 times the voLume of the ethanoL produced. The waste has found wide usage in many countries as animaL feed, fertiLizer, and for crop irrigation. 38. Starch crop fermentation stiLLage contains non-fermentabLe solids in suspension-and in solution. The waste can be applied directly to the Land as a fertiLizer, but the amounts must be carefuLLy monitored, because of their acidity and odor. The coarser solids can be separated, dried, and bLended with the dried soLubLe materiaL. These are normaLLy referred to as distiLLers dark grains (DDG) or, when combined with the dried soLubLe ma- teriaL, as distiLLers dried grains with solids (DDGS). The nutritionaL value of these products for animaLs wiLL vary according to the feedstock and production process used. 39. StiLLage products from beverage distiLLeries are generaLLy aLL used for animaL feed. The bourbon whiskey industry is the main source, with corn being the principaL feedstock. Wheat and rye stiLLages are aLso used for this purpose. In addition to suppLying protein and energy, such feeds aLso act to stimuLate digestive processes in ruminants. DistiLLers feeds have been found to be of benefit to chickens, turkeys, beef and dairy cattLe, caLves, sheep, swine, and warm-water fish. 40. Residue from moLasses fermentation is aLso used as an animaL feed, but mainLy for dairy cattLe. It is aLso used as an antidusting agent in feed mixing and handLing. The residue contains potash salts, nitrogen compounds, and phosphates and hence can be used as a fertiLizer. As a fer- tiLizer, it can be applied directly to.the soiL as a Liquid, but costs and Logistics tend to Limit its use to areas cLose to the fermentation faciLi- ties. Excessive use can create a number of problems, such as proliferation of insect pests. 41. Under normaL operations the stiLLage, after removaL, is separated into solids and Liquids (thin stiLLage). After initiaL screening and pro- cessing through a dewatering press the soLids wiLL stiLL contain about 65 percent water, and are known as wet stiLLage. This may be fed directLy to Livestock. One head of cattle wiLL consume the stiLLage produced from pro- duction of about 3.8 Liters of ethanoL. Further drying is necessary if Long-distance transportation or Long-term storage is required. The dried materiaL must be protected from insects and rodents. 42. The thin stiLLage of fermented grains aLso contains vaLuabLe pro- teins and carbohydrates, but it is difficuLt to dry any further. It is acidic and may be applied directly to the soiL through irrigation systems. It may also be anaerobicaLLy fermented to produce methane. 43. Where stiLLage wastes are not used for by-product recovery or other beneficiaL use, they shouLd not be dicharged to surface waters with- out treatment. If volumes are smaLL in reLation to the capacity of an availabLe pubLicLy owned sewage treatment plant, the wastes may be dis- charged to pubLic sewers. - 73 - 44. If Large volumes are to be handLed, then treatment should be pro- vided at the plant site. The nature of this waste is such that treatment methods normaLLy used for domestic sewage may be applied. Secondary treat- ment, such as activated sLudge or trickLing fiLters, may be used after some form of pretreatment to remove the high concentrations of organic materials and solids. The BOD5 and suspended soLids should be reduced to the 300 mg/Liter range before secondary treatment. Again depending on voLumes, settLing ponds or Lagoons may aLso be used, particuLarLy if the operation is seasonal and based on the availabiLity of crops. Care must be taken to avoid damaging ground waters. 45. The Liquid waste from the wet scrubbers shouLd receive treatment before discharge to the environment. Since the principal contaminant is in the form of suspended solids, the discharge can go to settLing or evapora- tion ponds. 46. The principal solid wastes wiLL be the sLudges resuLting from in- plant waste treatment facilities and the settLed solids from any ponds op- erated at the site. Consideration should be given to possibLe recovery of vaLuable by-products from the solids which are generated. Otherwise the solids shouLd be removed and dumped on controLLed (such as diked) areas in the plant. Means shouLd be provided for preventing rain runoff into nearby surface or ground waters. 47. Ocean disposaL of wastes is to be avoided whenever possibLe. However, when no other options are available and it becomes a method of Last resort, expert services shouLd be engaged to design the system. This is a highLy specialized field, in which onLy a few designers have had ex- tensive experience. 48. Initial planning for an ocean outfaLL should include a comprehen- sive survey of the proposed ocean discharge area to determine the foLLow- ing, as a minimum: (a) Currents - direction, magnitude, frequency, variation with depth, relation to tide, water dispLacements, etc.; (b) Densities -.variation with depth, as determined from saLinity and temperature data and standard tabLes; (c) Submarine topography, geoLogy, and bottom materiaLs; (d) Marine bioLogy; and (e) Turbidity, dissoLved oxygen, and other physicaL and chemi- caL characteristics. 49. The data derived from this survey shouLd be the basis for design of the outfaLL and diffusion system. Wastes discharged into the ocean are subject to three stages of diffusion or mixing: - 74 - (a) InitiaL jet mixing, which is infLuenced by jet strength, currents, and density differences; (b) DeveLopment of a homogeneous diffusion field; and (c) TurbuLent diffusion of the entire waste field due to naturaL oceanic turbuLence. 50. The factors infLuencing these stages wiLL incLude: (a) OutLet design. For optimum diLution the jets shouLd dis- charge horizontaLLy with no initiaL upward veLocity; (b) Number of outLets. A multipLe outLet diffuser wiLL dis- charge over a Large area and provide more effective diLution and dispersion. ALL other factors being equal, the singLe outLet unit wiLL generaLLy require a Longer distance and greater depths to the point of discharge; (c) Diffuser velocity. The veLocity in aLL parts of the diffuser shouLd be sufficient to prevent deposition of residuaL particLes. For settled wastes a veLocity in the range of 0.61 to 1 meter per second is considered a minimum; (d) FLow distribution. The outfLow between the various diffuser outLets shouLd be fairLy uniform. Where this may be difficuLt, as in the case of a sLoping sea bottom, the distribution shouLd be fairLy uniform at Least for the Low and medium flows anticipated; and (e) Prevention of seawater intrusion. Seawater entering the pipe becomes stagnant, and wiLL tend to trap grit and other settLeabLe materiaLs, causing reduction of hydrauLic capacity. BIBLIOGRAPHY 1. PauL, J.K. (Ed.) "EthyL ALcohoL Production and Use as a Motor FueL". Noyes Data Corporation. Park Ridge, New Jersey. (1979). 2. The WorLd Bank. "ALcohoL Production from Biomass in the Developing Countries". Washington (November 1980). 3. "ALcohoL FueLs from Biomass". In "Energy TechnoLogies and the En- vironment". U.S. Department of Energy. Doc. DOE/EP-0026. Washing- ton (June 1981). 4. SeLtzer, Richard E. "Economic Impact of Effluent ReguLations on the Rum Industry (Puerto Rico and U.S. Virgin Islands)". Prepared for U.S. EnvironmentaL Protection Agency by Development PLanning and Re- search Associates, Inc. Manhattan, Kansas 66502 (March 1979). - 75 - 5. Houghton-ALico, Doann "ALcohoL FueLs-Policies, Production, and PotentiaL". Westview Press. BouLder, CoLorado 80301. (1982). 6. "Study of Rum DistiLLery Waste Treatment and By-Product Recovery Technologies". SCS Engineers. Long Beach, CaLfornia 90807. (1979). - 76 - CTHE WORLD BANK MARCH 1983 OFFICE OF ENVIRONMENTAL AFFAIRS GUIDELINES FERTILIZER MANUFACTURING WASTES 1. Fertilizer use has increased sharply in recent years. By 1973, total world consumption of N-P-K (nitrogen-phosphorous-potassium) fertiliz- ers bad reached 77 million metric tons, having doubled over the pzeceding eight years. Largest tonnage increases were in &eveloped countries of Europe and North America, but greatest percentage increases were in lesser developed regions of Asia, Africa and Latin America. 2. While formulation of fertilizers, as well as other manufacturing aspects will vary between plants and countries, there are many common pro- duction elements in which affect both discharge of waste effluents and sub- sequent environmental effects. MANUFACTURING PROCESSES 3. Fertilizer plants produce two types of product - nonmixed (or straight) and mixed. Nonmixed fertilizers contain only a single major nu- trient, while mixed fertilizers contain two or more primary nutrients. For purposes of these guidelines the industry will be further subdivided as follows: Nonmixed Fertilizers Nitrogen Based -Ammonia --Urea - -Amnium Nitrate Phosphate Based --Phosphoric Acid --Normal Superphosphate --Triple Superphosphate Mixed Fertilizers Ammonium Phosphate and N-P-K's 4. Nitrogen fertilizer manufacture includes four basic process plants: ammonia, urea, nitrate, and nitric acid. - 77 - 5. Ammonia is the basic nitrogen fertilizer constituent, and is pro- duced by reaction of hydrogen with nitrogen. Urea, another major nitrogen source, is produced by reaction of ammonia with carbon dioxide to form am- monium carbamate, which in turn is dehydrated to form urea. Urea plants usually share a common site with like-size ammonia plants, so that the lat- ter not only supplies ammonia but also high purity carbon dioxide needed to produce urea. 6.' Amonium nitrate is produced by reaction of ammonia with nitric acid. The resulting- product is a. solution, which can be sold as a liquid or further processed into a dry product. In some cases the final dry form will be prills (or pellets). In other cases the final product will be crystals. 7. Nitric acid is produced in many plants for use in ranufacturing nitrogen fertilizers such as ammonium nitrate. Nitric acid is generally made by partial oxidation of amm onia with air, followed by further oxida- tion and absorption in water to produce a 55 to 65 percent solution. 8. Phosphate fertilizer facilities are usually separated geographic- ally from nitrogen facilities, and therefore are discussed separately in these guidelines. The manufacturing process is comprised of eight separate components: sulfuric acid production, phosphate rock grinding, wet process phosphoric acid production, phosphoric acid concentration, phosphoric acid clarification, and preparation of: normal superphosphate, triple superphos- phate, and armnonium phosphate, respectively. 9. The basic components are sulfuric acid production and wet process phosphoric acid production. Sulfuric acid is the essential raw material in producing phosphoric acid and normal superphosphate. It is now usually manufactured by the Contact Process, using elemental sulfur, air, and water. 10. Raw materials used in producing phosphoric acid are ground phos- phate rock, sulfuric acid, and water. Other acids, such as nitric and hy- drochloric, may also be used. The resulting phosphoric acid solution is concentrated by evaporation, clarified for removal of precipitated solids (consisting mainly of iron and aluminum phosphates, soluble gypsum, and fluorosilicates) and then distributed to markets. 11. Normal superphosphate is produced by mixing 65,to 75 percent sul- furic acid, ground phosphate rock, and water. Following mixing and initial settling of 1 to 4 hours, the mixture is transferred to storage for 3 to 8 weeks to allow complete chemical reaction between the acid and the rock. The basic chemical reaction is as follows: Ca3(PO4)2 + 2H2S04 + 5H20 2 CaSO4.2H20 +,Ca(H2PO4)2.H20 (Normal Superphoshate) - 78 - 12. Triple superphosphate (TSP) is produced by corrbining phosphate rock, phosphoric acid, and water. Two types of TSP are manufactured, using the same raw materials: Run-of-Pile (ROP) and Granular Triple Superphos- phate (GTSP). 13. The ROP phate, except that phosphoric acid is used instead of sulfuric acid. Mix- ing of the phosphoric acid and phosphate rock is done in a cone mixer. This produces a slurry, which rapidly becomes plastic and solidifies. So- lidified material passes through a rotary mechanical cutter, which breaks it up and discharges to storage piles for curing. Following 2 to 4 weeks of curing, the product (triple superphosphate) is taken from storage, sized and Bhipped to markets. The solidification process may release obnoxious gases which can create air pollution problems. 14. The GTSP process utilizes a lower concentration of phosphoric acid, different proportions of the same ingredients, and other changes from the ROP process. The product is a hard, uniform, pelletized granule made in equipment which permits easy collection and treatment of dusts and nox- ious fumes. 15. Aronium.phosphate fertilizers are produced in two major formula- tions: ronoammnium phosphate (MAP) and diamnonium phosphates (DAP). These vary in the amount of nitrogen and phosphate present. The two pri- mary raw materials, in either case, are anrnia and wet process phosphoric acid. Sulfuric acid is sometimes used in certain MAP formulations. The final granular product is dried, cooled, and shipped. Small sized granules are separated and used as recycle material. 16. Luring the past several years there has been a trend towards com- pound fertilizers. While these have always been popular in the United States, their use has grown considerably in Western Europe and Japan. These coumpounds (sometimes referred to as mixed fertilizers) are produced by mixing inorganic acids, various solutions, double nutrient fertilizers, and certain types of straight fertilizers mixed in accordance with require- ed N-P-K ratios. Another form of compound fertilizers, called blend ferti- lizers, are produced by simple combination of granular dry straight and inixed fertilizers, again, in accordance with the N-P-K ratio required, SOURCES AND CHARACTERISTICS OF WASTES 17. Fertilizer industry wastes can affect air, water, and land re- sources of an environment. Pollution problems arise from low process effi- ciency, disposal of unwanted by-products, contaminants in flue dusts and .gases, contaminants in process condensates, and accidental spills or losses. 18. In production of nitrogen fertilizers, no air pollution results from amnonia and urea manufacture. Overhead vapors from neutralizers in the reaction of armonia with nitric acid to form crystal armoni=n nitrate which ay lead to an air pollution problem. However it can frequently be handled by cyclones or baghouses. Concentrator and prill tcwer exhausts can contain ammonium nitrate particles and ray also result in an air pollu- tion troblem. -79- 19. Liquid wastes from the nitrogen fertilizer industry can originate from wastewater treatment plant effluents (filtration, clarification, soft- ening, deionization), closed loop cooling tower blowdown, boiler.blowdown, compressor -blowdown, process condensates, spills or leaks, and nonpoint source discharges. Nonpoint polluted water sources ay originate from air- borne armonia dissolving into falling rain or snow, or prill dusts or other materials lying on the plant grounds, dissolving into rainwater as it runs off various surfaces in the vicinity of the fertilizer plant. 20. Since air pollution p-.blens for a nitrogen fertilizer complex are considered minor in nature, to air pollution parameters are applied. Major wastes are liquid in nature and are measured in terms of ammonia ni- trogen, organic nitrogen, nitrate nitrogen, and hydrogen-ion concentration (pH). 21. Phosphate fertilizer plants generate considerable amounts of dust in grinding phosphate rock. Fluorine (as SiF4) ay evolve in the acidula- tion process (changing phosphates in phosphate rock from an insoluble to a soluble state). Air pollution problems are caused by ROP production. While dust and obnoxious fumes result,from GTSP production these are read-- ily collected and treated. 22. Liquid effluents include water treatment plant wastes, cooling tower and boiler blowdowns, make-up water, spills and leaks, surface run- off, and gypsum pond water. Cooling is- generally by indirect mans, and cooling waters are not contaminated. In the United States the majority of phosphate fertilizer plants impound and recirculate all water which has direct contact with process gas or liquid streams. Uses include barometric condensers, gypsum sluicing, gas scrubbing, and heat exchangers. This con- taminated water is normally not discharged from the plant complex. 23. Fluoride emissions are the principal air pollution concern in phosphate fertilizer plants. Hence this is the only air pollutant for which effluent limitations are provided in this guideline. Primary param- eters for liquid wastes are phosphorous, fluorides, suspended solids, and TpH. 24. For all fertilizer plants, solid materials may be found in stor- age piles, settled dust, and similar forms. As rain water falls upon these dust sources, dusts may be swept into the rainwater runoff. This will in- crease both the dissolved and suspended solids levels in these runloff waters. EFLUENT LIMITATIONS 25. Effluent limitations are given below for nitrogen, phosphate, and mixed fertilizer plants. The permissible levels are based on best current- ly available demonstrated control technology. 26. For all plants, where applicable,' the ambient air quality levels should not exceed those given in Table 1, to assure public health protec- tion. -80- Nitrogen Fertilizer Plants 27. Except for ammonia, as given in Table 1, air emissions from ni- trogen fertilizer plants are usually of minor inportance under proper op- erating conditions. Therefore, no other limitations are included for gase- ous effluents fran this type of plant. Limitations for liquid effluents from nitrogen plants, as presented in Table 2. Where applicable, gaseous nitric acid effluent limitations are the same as those for phosphate ferti- lizer plants, as shown in Table 3. Table 1 - Arbient Air Quality Limitations a/ Pollutant Period Limitation ug/m3. b/ Particulates Ann. Geom. Mean 75 Max. 24-Hours 260 Sulfur Oxides: Inside plant fence Ann. Arith. Mean 100 Max. 24-Hour peak 1000 Outside plant fence Ann. Arith. Mean 100 Max. 24-Hour peak 500 Carbon Mbnoxide Max. 8-Hour 10,000 Max. 1-Hour .40,000 Photochem. Oxidants Max. 1-Hour 160 Hydrocarbons Max. 3-Hour 160 Nitrogen Oxides Ann. Arith. Mean 100 Atmonia Max. 8-Hour 72,000 a/ From "Expert Group Meeting on Minimizing Pollution From Fertilizer Plants". Helsinki, 26-31 August 1974. UUIDO. Vienna (1974). b/ ug/m3: Microgram/cubic reter. - 81 - Table 2 - Liquid Effluent Limitations for Nitrogen Fertilizer Plants Liitation - Kg/Mg Type of Plant Parameter of Product Daily Ratio Anonia An=onia as N 0.11 Urea Non-prilled Amnonia as N 0.065 Prilled " 0.065 Non-prilled Organic N as N 0.24 Prilled 0.7 Armonium Nitrate Non-prilled Aumnia as N 0.05 Prilled " 0.10 Non-prilled Nitrate as N 0.025 Prilled 0.05 All Plants pH (no units) 6 to 9 -82- Phosphate .fr>artilizer Plants 28. Limits on gaseous emissions from phosphate fertilizer plants are presented in Table 3. Iable 3 -- Gaseous Emission Limits for Phosphate Fertilizer Plants Process Parameter. Limitation Nitric Acid Nitrogen Oxides (NOx) 1.5 kg/Mg Product Visible Emissions 10% Opacity a/ Sulfuric Acid Sulfur Dioxide (SO2) 2.0 kg/Mg Product as 100% Acid Acid Mist 0.075 kg/Mg Product as 100% Acid Visible Emissions 10% Opacity a/ Wet Process Phos- Fluorides (as F) 10 gm/Mg Equiv. b/ phoric Acid I P2 05 Feed Superphosphate Fluorides (as F) 5 gm/Mg Equiv. P2 05 Feed Triple Superphosphate- Fluorides (as F) 5 gm/Mg Equiv. ROP and Granular P2 05 Feed Visible Emissions 20% Opacity a1 Triple Superphosphate- Fluorides (as F) 0.25 gm/hr/M ton Gran. Equiv. P2 05 Stored Storage Facility a/ "Opacity" is defined as the degree to which emissions reduce the transmission of light and obscure the view of an object in the background. b/ g = gram 1 megagram = 1 metric ton 1 Mg = 1 metric ton - 83 - 29. Process waste liquid effluents should not be discharged. Iupoundment design should be adequate to hold all waste streams and all runoff expected frm the maximum 10-year, 24-hour rainstorm for the area. In any calendar month when precipitation exceeds evaporation, a volume of waste flow equivalent to the difference between the two ny be discharged, but subject to the following limitations: Max. ]Daily Parameter ng/L a/ Phosphorous - as P 70 Fluorides - as F 30 Total Susp. Non- filterable Solids 50 pH (no units) 6 - 9 a/ milligram/liter Mixed Fertilizer Plants 30. For a mixed fertilizer plant, fluorides in gaseous emissions (measured as F) are limited to 30 g/Mg of Equivalent P2 05 Feed. No liquid effluents are to be discharged. WASTE CONTROL AND TREATMENT 31. Process control and in-plant procedures can be effective in minimizing pollution effects from fertilizer plants. Careful application of such measures can result in significant economic benefits for plant operators. Specific measures taken for protecting the environment must be based on the raw material, processes, climate conditions, and other factors applicable to individual plants. - 84 - 32. For nitrogen fertilizer plants, ammonia stripping has been found effective for removing ammonia in process condensates, and boiler and cooling tower blowdowns at anmonia, urea, and ammonium nitrate plants. The stripping medium may be -either air or steam, depending upon the use to be made of the overhead vapors, local air pollution regulations, and other factors. At urea plants hydrolysis has been used to convert urea in waste streams back to amonia and carbon dioxide. 33. Recently a nmber of investigations have been nade into removing nitrate from wastewater by the use of biological action in aerated ponds or basins. Ion exchange units have also been used successfully to remove amnonia and nitrates from waste waters. At ammonium nitrate plants condensates contain anmonia, ammonium nitrate, and some oxides of nitrogen, and these all require treatment before discharge. These condensates have been used as absorber feed in the nitric acid plant. Thus creating an internal use of the waste stream which results in recovery of both ammonia and nitrate. Oils and greases can also present problems in nitrogen fertilizer complexes, but application of available technology can reduce these pollutants to less than 25 mg/liter. 34. For phosphate fertilizer plants, technology exists for reducing contaminants present in waste effluents. Air pollution of SO2 from sulfur- ic acid plants can be reduced by use of the "double-contact" process or am- monia scrubbing. Tail gas from nitric acid plants, containing oxides of nitrogen (NOx), can be handled by extended absorption or catalytic reduct- ion. In general, gaseous eniissions as a group can be reduced by the use of absorber towers. They are either collected as dusts or water scrubbed. 35. Although there should be no discharge of liquid effluents from phosphate fertilizer plants, rainfall conditions may be such as to require treatment of discharges on certain occasions. Frequently reductions in pollutant concentrations can be effected on separate process streams. Critical points where neasures can be applied include: (1) cooling water blowdown and accidental leakage from sulfuric acid coils; (2) drainage from waste by-product gypsum piles; and (3) seepage from gypsum ponds. 36. Because of differences in production of N-P-K fertilizers, re- sulting pollution problems will vary widely. Usually cyclones and filter bags will reduce dust emissions in dry-process plants. In other cases scrubbers will be the preferred alternative and these, in turn, will re- quire further pollution control procedures for the resulting liquid ef flu- ent. - 85 - BIBLIOGRAPHY 1. "Minimizing Pollution from Fertilizer Plants". Report of an Expert Group Meeting, Helsinki, 26-31 August 1974. UN Industrial Development Organization. Vienna (1974). 2. Hignett, T.P., "Recent Developments in Fertilizer Production Technology and Economics, with Special Reference to An=monia and Compound Fertiliz- ers". ASPAC Food and Fertilizer Technology Center. Taiwan (August 1974). 3. Finneran, J.A. "Guide to Building an Ammnia Fertilizer Complex". UN Industrial Development Organization. Vienna (1969). 4. "World Guide to Pollution Control in the Fertilizer Industry". British Sulphur Corporation. London (1975). 5. "Development Document for Effluent Limitations Guidelines and New Source Performance Standards for the Basic Fertilizer Chemicals Segment of the Fertilizer Manufacturing Point Source Category". U.S. Environ- mental Protection Agency. Washington. Doc. EPA-440/1-74-011-a (March 1974). 6. "Development Document for Effluent Limitations Guidelines and New Source Performance Standards for the Formulated Fertilizer Segment of the Fertilizer Manufacturing Point Source Category". U.S. Environ- mental Protection Agency. Washington, Doc. EPA/1-75-042-a (January 1975). 7. "Standards of Performance for New Stationary Sources". U.S. Environmental Protection Agency. Washington (August 1, 1976). -86- THE WORLD BANK OCTOBER 1982 OFFICE OF ENVIRONITAL AFFAIRS GUIDEINES FISH AND SHELLFISH PROCESSING 1. There is a wide variety of finfish and shellfish which could be processed at projects involving Bark financing. Therefore, it is not pos- sible to prepare a guideline covering all forms that may be encountered. This document will deal only with ocean fish and marine life, and will con- fine itself to a representative group of species, thereby providing informa- tion considered typical of and applicable to processing, canning, and pre- serving of fish and shellfish. 2. Specific species to which these guidelines may be applied in- clude, but are not limited to, salmon, herring (sometimes as sardines in the immature state), ocean perch, mackerel, halibut, cod, sole, tuna, clams, oysters, scallops, crab and shrimp. PROCESSING OPERATIONS 3. Harvesting utilizes a wide range of old and new technologies for supplying the basic raw material. Techniques fall into one of four general methods; netting, trapping, dredging, and line fishing. Airplane spotting and other systems are sometimes used for locating the fish. Once harvested and aboard the vessel, the catch is either taken directly to a processing plant or is iced and frozen on board for later delivery. 4. At the receiving point, the catch is unloaded, weighed, and transported by conveyor or suitable containers to the work area. It may be processed imrediately or transferred to cold storage. Pre-processing pre- pares the catch for the later cperations. It nay consist of washing of dredged crabs, thawing of frozen fish, beheading shrimp at sea, and other operations prior to butchering. Wastes from butchering and evisceration are usually dry-captured or screened fran the waste stream and processed as a fishery by-product. 5. Except for those portions intended for the fresh fish and seafood markets, some form of cooking or pre-cooking is usually practiced in order to prepare the caInndity for the picking and cleaning operation. Precook- ing or blanching facilitates removal of skin, bone, shell, gills, and other parts which nust be separated before marketing. In same cases steam con- densate fram this operation is collected and further processed as a by-pro- duct. For example, the condensate or stick water from the tuna precook. Stick water is water which has been in close contact with the fish, and contains large amounts of entrained organics. - 87 - 6. End product is prepared in its final form by picking or cleaning to separate edible fram non-edible portions. Non-edible portions resulting fran this procedure are usually collected and saved for by-product process- ing. The cleaning operation may be manual, mechanical, or a combination of the two. With fresh fish or fresh shell-fish, the neat product is packed into suitable containers and held under refrigeration until shipment . to consumer outlets. If the final product is to be held for extended periods before consunption, then freezing, canning, pasteurization, refrigeration, or same combination of these is used for preservation to prevent spoilage. 7. Fish and shellfish, and their waste products, are frequently used for production of such industrial cocodities as fish meal, concentrated protein solubles, oils, liquid fertilizers, fish food pellets, kelp pro- ducts, shell novelties and pearl essence. Se species are used primarily for industrial purposes. Fbr example, menhaden and anchovy are utilized extensively for preparation of fish meal, and added as- a protein supplement in animal feeds; oils are used in shortening, margarine, lubricants, and cosmetics; and fish solubles are used as liquid fertilizers. SOURCES AND CHARACTERISTICS OF WASTES 8. Edible product yield is highly variable. In general, yields for shellfish are in the 15 to 20 percent range while that for fish such as tuna or salnon yield reach the range of 60 or more percent. Extensive beneficial uses made of non-edible fish portions greatly reduces waste dis- charge. 9. Wastewater parameters of major inportance in the canned and preserved seafood processing industry are the 5-day, 200 C, biochemical oxygen demand (BOD5), total suspended solids (TSS), combined oils and greases, and pH. Normally, these wastewaters contain no hazardous or toxic materials (heavy metals, pesticides, etc.). Occasionally highly concentrated sodium chloride (NaCl) solutions may be discharged. These can interfere with biological treatment system unless pretreatment, such as dilution or flow equalization, is provided prior to disposal. SaLmon 10. Wastewater flow rates in a salmon processing plant will depend on whether the butchering operation is carried out by machine or by hand. Machine operations will result in higher flow rates, (BOD5, and TSS). Many plants will enplay both machine and hand butchering, depending on the species, quanity of catch to be processed and other factors. 11. In both fresh and frozen salmon processing, the principal source of wastewater is the wash tank operation. Here eviscerated fish are cleaned to renove adhering blood, tissues lining the body cavity (mesantaries), sea lice, and visceral particles. A preliminary rinse of the fish, as caught, is sometimes used to reduce the amount of slime adhering to the carcass and to facilitate handling. Wash tank and pre-rinse contribute about 90% of all wastewater flow. The remainder comes from wash down of butchering tables and other work areas. - 88 - 12. Wastewater flows fron salmon canning cperations are nuch higher than preparing fresh or frozen salmnn products, particularly where butcher- ing is done nechanically. Hand butchering and canning operation is essent- ially the sane as the fresh/frozen operaticn except for wastes fran fish cutting and can filling, which will also increase the amount of wastes into the water. 13. Typical loadings to be anticipated fran these two types of opera- ticns are presented in Table 1. Table 1 - Typical Effluent Loadings fran Salnon Processing Canned Parameter Fresh/ Frozen a . Mech. Hand Butchered a/ Butchered a/ Flow 3,750 L/Mg 19,800 I/Mg 5400 I/Mg BOD5 2.0 kg/Mg 45.5 kg/Mg 3.4 kg/Mg TSS 0.8 kg/Mg 24.5 kg/Mg 2.0 kg/Mg Oils/Greases 0.18 kg/Mg 5.2 kg/Mg 7.8 kg/Mg PH 6.6 6.5 7.0 a/ All loadings except pH, expressed as per negagram of product. 1 Mg = 1 megagram = 1 metric ton; L = liter. Tuna 14. Processing tuna requires several unit operations including re- ceiving, thawing, butchering, precooling, cleaning, canning, retorting, labeling and casing. Process and waste sources are shown schematically in Figure 1. This cperation requires large volumes of both fresh water, (us- ually fran nunicipal sources) and salt water pumped directly fran the ocean or saline wells. Both nunicipal and saline waters normally come ito con- tact with the tuna only in those stages preceding the precooking operation. 15. Typical waste flows and loadings discharged fran a tuna process- ing plant are given in Table 2. 89 RAW FROZEN TUNA FROM BOATS E PRODUCT FLOW RECEIVIN ------ WASTEWATER FLOW FROZEN i *WASTE SQLIDSFLOW STORAGE (GLOOD. JUICES) THAWING ---*- (VISCERA) BUTCHERING (BLOOD, JUICES, SMALL PARTICLES) .... . S HWASHING - * STICKWATER (OILS. SOLUBLE ORGANICS) (OILS, MEAT, BONE, ETC.) rPRECOOK 9 o. ------- LCO- (HEAD, FINS,.SKIN, DOPIE) CEN (LIGHT MEAT) (RED MEAT)GTMET IAN (VEGETABLE 0IL. MEATIPARTICLES) I I1 CAN WASHER CAN WASHER L(OILS, MEAT PARTICLES, SOAP) I ETORT RETORT 001. COOL (CRGANICS,CETEROENT) L J .- _L. - ... - - LASEL LABEL I I a CASE (SCRUBBER WATER WITH ENTRAINED ORGANICS) REDUCTiON P.ANT __ - --- J- J L * - PRESS I L LIUOR 1... . LIUORWASTEWATER (CONDENSATE WITH ENTRAINED ORGANICS) FISH CONCENTRATEO PET FOOD HUIAN MEAL SQLUBLES CONSUMPTION DISCHARGE Figure 1. Typical Tuna Processing, Waste Flows, and By-Product Usage. -90- Table 2 - pical Effluent loadings fram Tuna Processing Parameter Loadings a/ Flow - L/Mg 22,300 BOD5 - kg/Mg 15 TSS - kg/Mg 11 Oils/Greases - kg/Mg 5.6 pH 6.8 a/ All loadings, except pH, expressed as per megagram of whole tuna processed. Cn the average, 45 percent of the raw tuna intake results in food product, 54 percent (viscera, bead skin, fins, bone, red meat) in by-products, and the remaiiing 1 percent goes to waste. 16. Conmercial shrinp collecticn is done by netting at distances of same 100 km from shore. The harvest is taken directly to a processing plant or a "mother" ship. If taken to a ship, the catch must be inediately iced and reiced every 12 hours. Following peeling and preparation, shrimp are processed and marketed as frozen, or as canned or breaded products. 17. Up to the late 1950's shrinp were hand peeled for retail market- ing or further processing. Currently, peeling machines are used, thus in- creasing plant capacities some 30 to 40 fold. Peeling machines are the largest water users and also contribute to the largest waste load. Some 45 to 55 percent of the water entering a plant is used for this purpose. 18. Typical waste flows and pollutant loadings from shrinp processing operations are given in Table 3. -91- Table 3 -Typical Effluent loadings fran Shrimp Processing Parameter a/ Frozen Canned* Breaded Flow m3/Mg 73.4 60.0 116 BOD5 kg/Mg 130. 120-. 84 TSS kg/Mg 210. 54. 93 Oils/ Greases kg/Mg 17. 42. - pH 7.7 7.4 7.8 a/ All loadings, except pH, expressed as per megagram of raw shrimp input to plant. EFFLUENT LIMITATIONS 19. Limitations for liquid effluents frcm fish processing plants are given in Table 4. Under normal cperations no gaseous effluents of any con- sequence are discharged. Solid wastes, generally removed by screening, are either processed into saleable by-products or transferred to landfills or other facilities for final disposal. 20. Applicaticn of these limitations should be based on conditions at each individual plant. ' These are average values only, based on currently available technology considered to be achievable under present day opera- ting conditions at existing plants. 21. Factors which will influence limitations applicale to any indi- vidual plant, are (a) nature of the end product; (b) mechanical versus hand butchering or peeling; (c) extent of processing performed on board ship, prior to transfer to the plant; (d) water quality requirements for receiv- ing waters; and (e) remoteness of plant location. -92- Table 4 - Liquid Effluent Limitations for Fish Processing Plants a/ Max. Daily kg/Mg Live Weight Processed category BOD5 Tuna 2.2 2.2 0.27 Salmon 11. 2.8 2.8 Other Finfish 4.7 4.0 0.85 Crab 3.6 3.3 1.1 Shrimp 52. 22. 4.6 Other Shellfish 41. 41. 0.62 a/ In all cases pH should be 6 to 9. b/ 0 + G = Oils and Greases. CONTROL AND TREATME 22. Waste components of greatest concern are solids, oils and greases. The current treatment trends are toward the use of screening and air flotation, combined with effective in-plant measures, as the principal means of reducing overall waste loadings. 23. In addition to in-plant control measures, wastes from all fish- eries production operations under proper conditions are amenable to biolog- ical treatment or discharge to municipal systems. With adequate operation- al controls, no materials harmful to municipal waste treatment processes need to be discharged. 24. Application of in-plant control techniques should be the first step in handling of wastes. Basic techniques available are minimizing water use, recovery of dissolved proteins in effluent solutions and recov- ery of solid portions for use as edible products. - 93 - 25. Water-saving can be accomplished through reducing the use of flumes for in-plant transport of products. Dry handling of product or use of pneumatic ducts requires a small fraction of the water used by flumes. Spring-loaded nozzles, which autcuatically shut off when released by the user, should be utilized on butchering lines. Steam and water valves mist be properly maintained to avoid leaks and prevent losses. 26. Fish, along with meat and fewl, are frequently cateogrized as "animal proteins" because they contain the high levels of amino acid re- quired for good nutrition. Protein content will vary from 8 to 10 percent for oysters to over 25 percent for tuna. Several techniques are available for reclaiming protein from those portions not classified as "food pro- ducts. Proteins can be recovered in wet form and made into high quality frozen products. Whole fish or waste fish parts can be converted to fish meal or flour for animal feed. Protein wastes can also be converted into a high grade flour for human consumption. Concentration and utilization of fish proteins as food additives is finding increasing use in developing countries. Salmon eggs, representing up to 5 percent of by weight of the fish and formerly discarded are nov being recovered for caviar in a number of locations. 27. Seafood plants have previously been located near or over receiv- ing waters considered to have had adequate waste assimilation capacity. Therefore, there was little or no application of waste treatment technology to this industry. Despite the fact that these wastes are generally biodegradable, they do not contain unacceptable levels of toxic substances, and are amenable to biological treatment in nunicipal systems under controlled conditions. 28. Screening is extensively employed, in various forms and degrees, for solids recovery. Solids so recovered have market value and, in addit- ion, recovery eliminates their discharge into receiving waters and nunici- pal sewers. Solids may also be renoved by sedimentation basins. 29. If by-product recovery is not practical, proper disposal of solids nust be considered. Where permitted and where land is available, private landfill may be a practical solution. Land application of unstabi- lized, putrescible solids as a rutrient source may be impractical because of nuisance conditions which could be created. 30. Another alternative is deep sea disposal. Such a method does not subject the marine environment to the potential hazards of toxic substances and pathogens normally associated with the dumping of human sewage sludges, nunicipal refuse, and industrial wastes. Tb minimize any detrimental ef- fect on the marine environment, waste solids should be ground before dispo- sal, should be discharged only to waters subject to strong tidal flushing action, and at depths of not less than 13 to 15 meters. 31. Wastewaters from which the solids have been separated may be sub- jected to either physical-chemical or biological treatment to further re- duce organic levels in the water prior to final disposal. -94- 32. The most prcmisirg physical-chemical techniques currently being investigated are chemical coagulation and air flotation. Economic corid- erations seriously limit current applicaticn of chemical oxidation, since the high cost of supplying chlorine and ozone, the two nost promising oxi- dants, -is a deterrent. 33. Air flotation, with addition of appropriate chemicals, is capable of removing high concentrations of solids, grease, oil and dissolved organ- ics. Vacuum flotation, dispersed air flotation, and dissolved air flota- ticn are systems most comlonly applied at present. In using these methods it is important to add sufficient quantities of chemical coagulants to can- pletely absorb the oils and greases present. 34. Most wastewaters have sufficient. nutrients present to make them amenable to biological treatment. Activated sludge, high-rate trickling filters, ponds, lagoons, and land disposal nay all .be applied under proper conditions. 35. Selection of a treatment system requires analysis of total plant operation and application of techniques specific for wastes to be treated. BIBLIOGRAPHY 1. U.S. Environmental Protection Agency "Development Document for Effluent Limitations Guidelines and New Source Performance Standards for the Catfish, Crab, Shrimp, and Tuna Segment of the Canned and Preserved Seafood Processing Point Source Category". Doc. EPA-440/1-74-020-a. Washington (June 1974). 2. U.S. Environmental Protection Agency "Develoment Document for Effluent Limitations Guidelines and New Source Performance Standards for the Fish Meal, Salmon, Bottom Fish, Clam, Oyster, Sardine, Scallop, Herr- ing, and Abalone Segment of the Canned and Preserved Fish and Seafood Processing Industry Point Source Category". Doc. EPA-440/1-75/041-a, Group I, Phase II. Washingtcn (September .1975). 3. "Best Conventional Pollutant Control Technology-Reasonableness of Ex- isting Effluent Limitations Guidelines". Federal Register, Vol. 43, No. 164, pp. 37570-37607, and Vol. 43, No. 170, pp. 39062-39067. Wash- ington (August 23 and August 31, 1978). - 95 - *9 5 THE WOD BANK OCTOBER 1980 OFFICE OF ENVrOPMENA AFAIRS FRUIT AND VEGETABLE PROCESSING IRDUSTRIAL WASTE DISPOSAL 1. Because of the wide variety of fruits and vegetables that are harvested and processed, in varylng degrees, discussions of industrial operations covering each of the varieties for which effluent limitations are given below is beyond the scope of this document. Therefore, the discussions are Limited to the processing of apples, citrus, potatoes and their various by-products. However, effluent limitations are inclu.ed for many other fruits and vegetables normally processed in these plants. InDUSTRIAL PROCESSES 2. Industrial operations covering apples, citrus fruits, and potatoes involve many of the procedures used in fruit and vegetable processing in general. The series of steps outlined below for each of these groups may not all occur at each plant. Therefore, it is necessary to have complete information on the final product to be prepared in order to assure proper application of the affluent limitations. 3. In addition to apples marketed directly for consumption, the fruit is used mainly for preparation of sauce, juice and frozen or canned slices. Other products, but in a lesser volume, include dehydrated apple pieces, special apple rings, spiced whole apples, and baked apples. Apple processing usually involves storage, washing and sorting, peeling and coring, slicing, chopping, extracting juice, dehydration, deasrating, and cooking. 4. Control of the temperatures and relative humidity of storage areas is critical for maintaining quality. Apples received from the field or storage must be washed to remove dirt and other residues, and then sorted to remove undersized, spoiled, or otherwise inferior fruit. Mechanical peeling is most commonly used, particularly where a sliced product is to be produced.. The peal and core particles (along with inferior fruit) are used to make juice or vinegar stock. Steam and caustic pealing are also utilized.- After slicing, the slices are deaerated in a brine solution, under vacuum. The final step is freezing and packaging or cooking and canning. -96- 5. Oranges, rapefrait, lemons, tangerines (madrarins) and limes are the citrus fruits most frequently grown and barvested. The steps in the processing include: receiving, storage and washing (to remove foreign materials, pesticides, etc.); extraction of raw juice; finishing (to separate pips and mbranA segments); and juice concentration. When segments are to be produced the fruit is mechanically peeled, subjected to canstic treatment to remove adhering membrane particles, and manual- ly or mechanically segmented to produce sections. In many cases the peel- Ings are further processed for recovery of citrus oil. 6. The principal forms manufactured by the potato processing industry are frosen products; chips; dehydrated potaroes; and canned, bash, stew, and soup products. The quality of the rav potatoes and the types of manufacturing process are the two principal factors in deternin- ing the quantity and characteristics of the waste ;enerated. Ideally, the most suitable potatoes should have a high solids content, low content of reducing sugars, thin peals, and uniforn size and shape. 7. The bulk of the potato intake is placed in storage by the processor in order to provide adequate quantities of raw material for . year-rocnd. operation. Storage facilities require high hiIdity levels to prevent shrinkage. From storage, the potatoes go to rotary drums or cylindrical washers to remove soil particles and other foreign materials. Next, these vegetables are peeled (using abrasion or rubber studded rolls, or other means). As part of the peeling proccss the potatoes are electroni- cally inspected for eyes, blemishes, and remaining peel. These undesirable . elements are then removed and the potatoes sliced or diced. Considerable starch may be released in the slicing and subsequent washing operation. The crude starch is recovered and shipped alswhere for further refining. 8. After slicing or dicing, the pieces are blanched (using steam or hot water). prior to preparation of the final product. ... - =7OURCESfD CHATMSTICS 07 WASTES 9. Effluents from the fruit and vegetable processing industry can be both solid and liquid in nature, and the process waste streams are generally a mixture of the two. Gaseous effluents are minor or non-existent, and hencs, will not be covered in this discussion. Odors related to anaerobic ponds, which are sometimes used for waste treatment, may be significant in individual situations. 10. The waste water parameters of major significance are the five- day biochemical oxygen demand (BD5), total suspended solids (TSS), and hydrogen-ion concentration (pI). Fecal coliforms may be of concern, although not generally found in wastewaters from this industry. To avoid problems in this regard, all sanitary wastes should be handled separately and should in no way come in contact with process wastewaters. This separation can be particularly critical in situations where in-plant reuse of process waters is practiced. - 97 - Table 1: Characteristics of Typical Waste Effluents - Pruit and Vegetable Processing a/ Flow 1300 TSS 1,000 gaWron ib/ton lb/ton raw product b/ raw product c/ raw Oroduct c/ Min. Mean Max. Min. Mean Max. Min. Mean Max. Apples 0.2 2.4 13 3.9 I8 44 0.4 4.5 21 Apricots 2.5 5.6 14 18 40 80 5 9.9 19 Asparagus 1.9 8.5 29 0.9 4.9 22 4.3 7.5 13 Dry tmans 2.5 8.8 33 15 60 182 2.6 43 99 Uma beans 2.4 7.7 22 9.3 48 175 4.6 39 231 Snap beans 1.3 4.2 11.2 1.6 15 81 0.8 6.1 46 Beets 0.3 2.7 67 28 53 127 7.3 22 64 Broccoli 4.1 9.2 21 5.8 20 61 4.6 17 61 Brussels sprouts 5.7 8.2 12 4.2 7.5 14 2.9 15 79 52rries 1.8 3.5 9.1 11 19 40 1.4 7.1 22 Carrots 1.2 3.3 7.1 17 30 53 4.5 17 53 Cauliflower 12 17 24 5.5 16 36 2.8 7.8 22 Cherries 1.2 3.9 14 21 38 78 1.0 2.0 3.8 Citrus 0.3 3.0 9.3 0.9 9.6 26 0.7 3.7 14 Corn 0.4 1.8 7.6 12 27 64 3.6 10 27 Grapes 0.6 1.5 5.1 6.4 9.0 13 1.5 1.7 2.0 Mushroomr 1.8 7.8 28 7.7 15 28 5.1 7.3 12 Olives - 8.1 - - 27 - - 27 - Onions 2.5 5.5 10 57 57 58 5.3 17 55 Peaches . 1.4 3.0 6.3 17 35 70 3.4 8.6 21 Pears 1.6 3.6 7.7 19 50 126 3.6 12 33 Peas 1.9 5.4 14 16 38 87 3.8 11 38 Peppers 0.9 4.6 16 5 32 50 1 58 170 Pickles 1.4 3.5 11 26 42 75. 3.0 8.2 23 Pimentos 5.8 6.9 8.2 39 55 76 4.1 5.8 8.1 Pineapples 2.6 2.7 3.8 13 25 45 . 5.2 9.1 17 Plums 0.6 2.3 8.7 6.5 10 14 0.6 2.1 4.3 Potato chips 1.2 1.6 2.2 17 25 38 22 32 48 Potatoes, sweet 0.4 2.2 9.7 39 93 217 40 57 117 Potatoes, white 1.9 3.6 6.6 42 84 167 39 128 423 Pumokin 0.4 2.9 11 9.2 32 87 2 67 12 Saucrkraut 0.5 0.9 3.0 4.6 5.6 15 - 1.0 2.6 Spinach 3.2 8.8 23 5.7 14 31 7 1.8 6.1 21 Squash 1.1 6.0 22 20 - - 14 - Tomatoes, peeled 1.3 2.2 3.7 6.3 9.3 14 5.8 12 26 Tomatoes, product 1.1 1.6 2.4 2.2 4.7 9.7 5.6 10 19 Turnips 2.4 7.3 18 - - - a/ From suggested Reference No. 5 q/ Multiply by 4.17 to convert to liters/agagram 7/* Multiply by 0.500 to convert to kg/megagram 1 Mg - 1 megagram a 1 metric ton - 98 - 31. Water is extensively used in all phases of industry, principally as (b) a cleaning agent to remove dirt and other foreign material; (a) a heat transfer medium for heating and cooling; (c) a solvent for removal of undesirable ingredients from the product; (d) a carrier for the incorporation of additives into the product; and (e) a method of transporting and handling the product. 12. Wastewaters from the processin of individual products are common to the industry as a whole, and are made up mainly of biodegradable organic matter. Although the procedures used in processing the various commodities have many aspects in comon, there are variations which affect the quantity and strength of the affluents produced. 13. Wasteater characteristics will be affected by: (a) the condition of the raw fruit or vegetable (such as freshly picked versus stored); (b) the peeling method Ccaustic peeling produces higher 30D5 and TSS than does mechanical peeling, for example; () water usage, including the extent of water transport; (d) age and efficiency of equipment; Ce) the processing operations for the commodity being produced; and (f) in-plant measures and housekeeping practices. 14. Average flows and characteristics of waste effluents are presented in Table 1. The data covers both screened and unscreened effluents, which accounts. for the wide variations between mInimu and marimr values. FLUENT LIMITAIONS 15. Effluent limitations for wastes originating from the fruit and vegetable processing industry are presented in Tables 2, 3, and 4, below. Table 2. Liquid Effluent Limitations - Specialties a/. Commndiry 30D5 TSS W Mg Raw Product Baby Foods 0.84 1.15 Chips - Corn 1.14 2.12 Chips - Potato 1.68 3.03 Chips - Tortilla 1.66 3.02 Ethnic Foods 1.59 2.83 Jams/Jellies 0.19 0.34 Mayonnaise/Dress. 0.21 0.39 1 Soups 2.77-k/ 4.93 Tomato/Starch/Cheese 0.98 1.74 Vegetables - Dehy. 1.78 3.18 a/ For plants processing approximately 1000 to 5000 magagrams per Year. b/ Represents Kg per Megagrams raw ingredients. - 99 - Table 3. Liquid Effluent Limitations - Vegetable Processing at. 30D TSS Comodity --- K8/Mg Raw Product Asparagus 0.28 0.50 Beans - Dry 1.40 2.51 Beans - Lima 1.75 3.12 Beans - Snap 1.05 1.86 Beets 0.68 1.24 Troccoli 1.89 3.34 Carrots 0.97 1.76 Cauliflower 2.36 4.17 Corn - Canned 0.45 0.84 Corn - Frozen 0.99 1.83 Mushrooms 1.19 2.12 Onions - Canned 1.72 3.14 Onions/Garlic - Dehyd 1.16 2.07 Peas 1.00 1.97 Pickles-Fresh Pack 0.64 1.14 Pickles - Process Pack 0.65 1.21 Pickles - Salt Stations 0.08 0.16 Pias=tos 2.00 3.84 Potatoes Sweet/Whita 0.52 1.09 Saurkraut - Canned 0.26 0.47 Saurkraut - Cutting 0.05 0.09 Spinach 1.18 2.08 Squash 0.30 0.53 Tomatoes Q.90. 1.74 a/ For plants processing approximately 1000 to 5000 megagram per Year. - 100 - Table 4. Liquid Effluent Limitations - Fruit Products al. BOD5 TSS Commodity Kg/Mg Raw Product Mpple Juice 0.20 0.20 Apple Products 0.20 0.20 Apricots 1.26 2.28 aberzries 0.1 0.33 rries - Sweet 0.45 0.81 Eneies - Sour 1.10 2.01 raies - Brined 0.76 1.44 itrus Products 0.14 0.20 granberries 0.62 1.12 ied Fruit 0.72 1.34 ape Juice - Canned 0.76 1.39 Prape Juice - Pressed 0.11 0.20 plives 2.28 3.93 Peaches 0.75 1.40 Tears 0.86 1.58 ineapples 1.48 2.60 lums 0.28 0.50 Raisins 0.20 0.38. Strawberries 0.62 1.10 a/ For plants processing approximately 1000 to 5000 megragram per Year. 16. In addition to the limitations given above, all effluents should maintain the MPN fecal coliform count below 400 per 100 mL and the pH at 6.0 to 9.5. --COML AM TEAfls 17. The wastes resulting from this industry are principally organic in nature. They are therefore amenable to biological treatment, either at the point.of discharge or, with pretreatment, in a municipal sewage treat- ment system. In-plant procedures and housekeeping practices can be effective in reducing the waste load to be ttaated or discharged to municipal plants. 18. A fruit or vegetable processing plant is completely dependent upon a supply of good quality water. The increasing use of pesticides and other contaminants requires more effective washing following the harvesting procass. The use of mechanical harvesting techniques results in increased quantities of soil and dirt pickup and consequently requires more extensive washing. It has been demonstrated that when washing is done at a site reoved from the processing facility ruch as adjacent to the harvesting area) total plant water usage can be reduced by as much as 8 to 10 percent. - 101 - 19. Where pealing is necessary, mechanical aeans are usually employed, using aither caustic or steam. Water sprays or rubber abrading are the two principal methods of removing the peel. The use of the rubber abrading technique can reduce the total waste flow, BD5, and TSS by as much as 50 percent. 20. Water used in the sorting, triming, and grading operation can be recirculated for a given period of time. Since it comes into contact with the interior of the fruit or vegetable there is a tendency to build up the concentration of soluble and suspended solids. When these solids reach the point where the water must be replaced, the contaminated water can be further concentrated by evaporation and used as vinegar stock. 21. Wastewater volumes can be reduced by substituting other methods (screw conveyers, air propulsion,. pump transport, etc.) in place of fluming to convey the products through the operation. The system substituted for fluming must be adapted to the product and the processing on an individual basis. Other operations which should be carefully examined for economies in water use include the blanching, container cooling, and clean-up. WAtar recirculation, using cooling towers where necessary, can also be effective in reducing effluent volumes. Flow equalization through the use of storage tanks to reduce large fluctuations in volumes will reduce overall treatment needs. 22. It is currently the general practice in this industry to separate the solid waste from the liquid waste streams. This is usually done by physical means such as screening (stationary, rotary, or vibrating), plain sedimentation, hydroclones, or flotation. For operations producing signifi- cant volumes of french fried products, traps may be necessary to reduce oil and grease discharges. 23. Waste effluents are readily treatable by biological methods, after the major volume of the suspended solids have been removed by screening, sedimentation, or other primary treatment. Once this separation has been accomplished most of the biodegradable material is in the soluble form, and may be treated by such systems as activated sludge, trickling filters, lagoons (anaerobic or aerated), rotating biological contactors, and others. 24. Land application of these effluents has been successfully utilized. Its operation depends upon a number of factors, including: (1) infiltrative and percolative capacity of. the soil; (b) clogging: (c) quality changes in the soil; (d) travel of the sprayed effluent to springs and streams or, through faults, to ground water supplies; Ce) evaporation; and (f) transpiration through cover plant growth. 25. In evaluating the application of this method it is necessary to consider: Ca) available land area; (b) soil characteristics; (e) available slope, to minimize ponding of water; (d) intervals required to rest the soil between applications; (e) nature and density of the cover crop; (f) and the characteristics7 of the wastes in terms of the components which may affect the soil mantle. - 102 - BI3LIOGRAPEY 1. Jones, L. "Waste Disposal Control in the Fruit and Vegetable -ndustry". Noyes Data Corporation, Park Ridge, N.J. and London. (1973). 2. Powers, P.W. "How To Dispose of Toxic Substances and Industrial Wastis". Noyes Data Corporation, Park Ridge, N.J. and London (1976). 3. "Treatment of Industrial Effluents". Ed. by A.G. Callely, C.F. Forster, and D. A. Stafford. Halstead Press (John Wiley & Sons), New York (1976). pp.245-257. 4. U1S,-. EaVroMental Protection Agency. "Development Document for Effluent Limitations Guidelines ate New Source Performance Standards for the Apple, Citrus, and Potato Processing Segment of the Canned and Preserved Fruits and Vegetables Point Source Category". Doc. EPA-440/1-74-027-a. Washington (March 1974). 5. U.S. Environmental Protection Agency. "Pollution Abatement in the Fruit and Vegetable Industry" Doc. EPA-625/3-77-0007 (3 Volumes). Washington (July 1977). - 103 - THE WOELD ANK MA .1979 072M-E 07ENIROMMETAL AFFAInS GEOTEEMAL DEVELOPMENT GUDELIES 1. The environmental impact of geothermal development can be import- and and should be part of any World Bank study in this field. 2. The min points to consider are as. follows: - Direct physical effects on habitat - Erosion - Surface water effects - Ground water effects - Air pollutio, - Noise - uman presence 3. The project should take into consideration the survival and well being of the wildlife species including fish. This should be done from the exploration phase through the well-field development, the plant construction, the plant operation and finally, the field abandonment. 4. Erosion of the land can be caused by waer, by wind or by stream chamnels. Pronounced erosion can result from minor disturbances of the land surface and/or the vegetation. Good planning, reasonable grading, and good construction regulations will prevent significant erosion. 5. Geothermal development will reduce some stream flows (construction . period) or increase others. The quality of. the surface water will probably be changed. .Significant alterations of the hydrology or drainage routes should be avoided. 6. Changes in ground water level, quality and temperature will occur. These should be forecast to avoid any drastic impact. Reinjection should be considered especially if the effluent is highly polluted. 7. Although the air pollution should not Se a maj or problem it should be considered in each phase especially if emission of radioactive vapors or vapor borne salts is possible. 8. Noise will be generated by several activities or pieces of equipment and could interef ere with normal behavior of animals; breeding, rest, hiber- nation and migration patterns could be disrupted. 닌 105 THE WORLD BANK JANUARY 1981 oma or EnzRoNMENTAL AFFAIRS GLASS MANUFACTURING GUIDELIM 1. The glass manufacturing industry may be divided into a number of seg- ments descriptive of the products from specific processes. However, based on the types of plants most, frequently encountered in World Bank projects, this document will confine itself to those ?1ants producing flat glass, pressed and blown glass (battles). MANUFACTURING PROCESSES Fl t Glass 2. Flat glass is produced by meltiag sand together with other inorganic ingredients a-ad then forming the molten material into a flat sheet. The tech- niques most frequently used are the float, plate, sheet, and rolled processi 2. Although the raw materials and malting operations are basically the same, ei ch process uses a different method for forming flat sheets from the molten glaski. 3. In the float process the glass is drawn across a molten tin bath. In the plate process the rollers used to form the sheets will also control the initial thickness, with the final thickness being achieved by grinding and polish- ing. The glass is formed by a vertical drawing procedure in the sheet process. Text=tzlng rolls serve to impart surface te=ures in the roUed process. The priwry glass sheets may be further fabricated into related pToducts such as orsq coated products, automotive and architectural glass, windshields, and others. 4. Mm most common type of flat glass produced utilizes the soda-lime method. Generally, about one-half of each batch consists of sand (silica). Other major ingredients include soda ash Mai C03), limestone (Ca C03). dolomite (Mg C03), and cul-Ilet. L%a cu-lat consists of the broken glass generated in the manufactux-Ing or fabricAting processes. This is recycled with the raw materials to improve the melting qualities of the batch. The manufacturing steps include (a) batching - 1"Iming of raw materials; (b) malting; (a) forming - to effect d1sne" ional control and surface texture, based on, applying sheet, plate, rolled or float processes; (d) annealing - to remove iaternal stresses; (e) grinding and polishing - to achieve flat and parallel surfaces; (f) washing; and (g) cooling. Pressed and Blown Glass 6., The pressed and blown glassware category covers the manufacture of glass containers, machine pressed and blown glass, glass tubing, television picture tubes, envelopes, inenndescent lamp envelopes, and hand pressed and hlown glass products. - 106 7. The soda-lime process is most commonly used for pressed and blown glass production, but the compositioz, differs from that used in the flat glass category. Sand comprises about'70 percent of the batch. Soda or soda ash com- prise 13 to 16 percent, with the remainder made up of cullet. Soda and, some- times, small quantities of potassium oxide are added as flaing agents. Calcium oxide (lime) and small amounts of aluminum and magnesium oxides are added to improve chemical durability. Iron and other materials may be added as coloring agents. 8. The manufacturing consists of (a) raw material storage and mixing; (b) malting; (c) forming - including blowing, pressing, drawing, and casting; (d) cullet quenching; (a) annealing; and (f) finishing. The steps will vary from plant to plant, depending upon the final product. SOURCES AND CHARACTERISTICS OF WASTES 9. Process wastewaters are considered to be those which have come into direct contact with the glass, mainly including such sources as washing, quench- ing, grinding, and polishing. No process wastes are produced in the manufacture of sheet and rolled glass. Water is added to the raw materials for dust sup- pression, but the water is evaporated and discharged as a vapor. Air Emissions 10. Although there are numerous unit operations used in glass manufactur- ing, most of the key processing steps responsible for generating the bulk of atmospheric emissions are common throughout the industry. 11. Emissions from raw material handling and storage are generally due to solid particles becoming airborne when materials are moved to storage, upon receipt at the plant or when they are moved from storage to the process. In the glass malting operation pollutants arise from two sources: combustion of fuel and vaporization of raw materials. Pollutants frequently encountered include NO, SOz, CO, and hydrocarbons, depending upon the fuel utilized. It has been estimated, for example, that a fuel oil containing 1 percent sulfur by weight will yield approximately 600 mg/L of SO2 in the flue gas. 12. The second source of air pollutants from the melting process results from the vaporizat.on of raw materials in the glass melt. This consists mainly of particulates which are vaporized from the molten glass surface and condense at lower teperatures in the furnace checkerworks or in the stack. The chemical composition of the particulates will depend upon the particular formulation used. Emission levels for uncontrolled glass melting furnaces are given in Table 1. 13. Based on current information, gaseous emissions from the final steps of glassmaking, normally referred to as "forming and finishing" operations, are generally not significant enough to be of concern. - 107 - TABLE 1 - T"ical Gaseous Emission Levels from Uncontrolled Glass Malting Furnaces a/ Plant Type Flat Con- Pressed & Blown Glass tainer Soda Non- Glass Lime Soda- Emission Gas/Kg Glass pulled from furnace Nitrogen Ozides 4.0 2.3 4.2 Particulates 1.5 1.2 1.2 5 Sulfur Oxides 1.5 1.4 2.7 3.0 Carbon Monoxide 0.02 0.08 0.10 Hydrocarbons 0.04 0.07 0.15 Fluorides - - - 10 Selenium - 0.002 - a/ From Reference (6). Liquid Effluents 14. Pretreatment of water supplies is required in some cases, depending upon raw water cualitv and intended water use. However, information on effin- ent characteristics of these auxiliary wastes is not readily available. Be- cause practices vary considerably each case should receive separate study and consideration to determine the impact on overall waste discharges. 15. For the plate glass category significant pollution results from the production of plate glass, solid tempered automotive glass, and windshild fab- rication. The major parameters of pollutional significance include suspended solids, oil, hydrogen-ion concentration, pH, 5-day biochemical oxygen demand (305), total phosphorous, and temperature. Typical increases in concentrations of tese parameters over process influent water levels are presented in Table 2. -108 TABLE 2 - Increase in Concentrations Over Levels in Process Influent Waters for Flat Susp. Solida -mg/L 15,000 15 100 25 01 -mg/L Trace 5 13 1,7C0 COD -mg/L 100 15 25 1,700 BOD5 -mg/L - 2 15 33 Total Phosph -mg/L 0 0 0 5 Dis: Solida -mg/L 175 100 100 LoV pRaU) 9 8 7 7 - 8 Temperature -*C 2.8 (g) 8 19 (a) No sigificant process wastewater discharges from rolled and sheet glass operations. (b) Typical process waters fron fabrication of windshields using ol autoclaves. (c) Process water only, exclusive of cooling water. (d) Liters per Metric Ton of production. (e) Liters per square meter of area on one side. (f) Represent absolute values. (g) Moderate increase. - 109 - 16. In glass container manufacturing the process water is used for cullet quenching and non-contact cooling of batch feeders, melting furnaces, forming machines and other auiliary equipment. Wastewater characteristics which should receive attention include flow, biochemical oxygen demand (BOD), total chemical oxygen demand (COD), total suspended solids (TSS), and oil. Typical increases in these parameters over and above the levels found in the incoming process water, are given in Table 3. TABLE 3 - Increase in Concentrations Over Lavels in Process Influent Waters for Glass Container and Machine Pressed Glass Plants. Glass Machine Parameter Containers Pressed & Blown Flow-Liters/Met. Ton(a) 1540 2920 Temperature - OC. 6 8 PH(b) 7.5 7.8 BOD - mg/L (5-day, 20*C) 5 5 COD - mg/L 50 50 Susp. Solids - mg/L 24 25 Oil - mg/L 10 10 (a) Process water only, exclusive of cooling water. (b) Represent absolute values. 17. In machine pressed and blown glass manufacturing the raw materials are first melted and then formed (by use of presses, or other techniques) into tableware, lenses, reflectors, headlamp parts, and other similar items. Water is used principally for non-contact cooling and gullet quenching. Waste- water characteristics which may be of significance include flow, temperature, hydrogen-ion concentration. '(pH), 5-day biochemical oxygen demand (30D5), chem- ical oxygen demand (COD), total suspended solids (TSS), and oil. The loadings of these pollutants added to the incoming process waters during the production process are also presented in Table 3. 18. Wa.tewaters in the hand pressed and blown glass industry originate almost entirely in the finishing steps. The finishing steps which require water and hence will produce wastewater discharges include (a) crackoff and - 110 - polishing; (b) grinding and polishing; (c) machine cutting; (d) alkali washing; (e) acid polishing; and (f) acid etching. Some plants may utilize only one or two of these steps while other plants may employ several or all of the pro- casses. Some handmade glass plants also use machine forming presses. 19. Waste water parameters which should be considered include flows, total suspended solids (TSS), fluorides (7), lead (Pb), hydrogen-ion concentra- tion (pH), and temperature. The increases in these parameters in the incoming process waters are shown in Table 4. TABLE 4 - Increase in Concentrations Over Levels in Process Influent Waters for Hand Blown and Pressed Glass Plants. Parameter Flow Temp pH TSS F Pb c. (b) Mg/Liter (a) Poess Crackoff/Polish, 9,920 2.8 3.2 36 194 0.96 Grinding/Polish. 3,460 2.8 - 4350 - 0.43 Machine Cutting. 10,880 1.6 10.0 2580 100. - Alkali Washing 4,795 57 11.2 17 - - Acid Polishing 5,380 46 2.2 220 1980 31 Acid Etching 36,530 33 4.0 8 462 7.9 (a) Process water only, exclusive of cooling waters. (b) Represent absolute values. Solid Wastes 20. There are no significant solid waste disposal problems associated with the basic glass production process. The waste or broken glass, called cullet, is normally segregated and added to the raw material batches, as al- ready discussed above. Some sludges and other solids will result from systems treating glass industry wastes. . - 111 - EFFLU T LITATIONS 21. Ambient air quality at ground levels in the vicinity of glass man- ufacturing plants should be maintained at or below the concentrations given in Table 5. These concentrations should be considered as World Bank guidelines. TABLE 5 Allowable Ambient Air Quality Concentrations at Ground Level. Pollutant Averaging Allowable Time Concentra- tions Nitrogen Dioxide Ann,. Arith. 100;ug/m3 Particulates Ann. Geom. 75,ug/m3 Sulfur Oxides (a) (a) Sulfur Oxides (a) (a) Carbon Monoxide 8-Hour 10 mg/23 Carbon Monoxide 1-Hour 40 mg/=3 Hydrocarbons 3-Hour 16041ug/m3 (a) Inside plant fence Ann. Arith. mean: 100 pg/a3 Ma.24-hr. peak: 1000 pg/m3 Outside plant fence Am. Arith mean: 100 g/m3 Max. 24-hr. peak 500 zg/m3 22. Effluent limitations for glass plants, based on the application of currently available technology are shown in Tables 6 and 7. These Tables should be considered as World Bank guidelines. -112- TABLE 6 - Effluent Limitations for Wastewater Discharges from Flat Glass Plants (a) t FSolid Wind- Plate FloatT.I Sel Parameter Glass Glass Autom. Fabric. )c) dd) pH 6 -'9 6 -9 6 - 9 6 - 9 Total Susp. Solids 2.76 2.0 1.95 4.4 Oil 0.7 0.64 1.76 COD 0.90 2.0 - 4.9 BOD (5-day, 200C) - - 0.73 Total Phosph. - 0.05 - 0.98 (a) No wastewater discharges from sheet and rolled glass plants. (b) Kg/Metric Ton. (c) Sm/Metric Ton. (d) gm/Square meter of area on one side. TABLE 7 - Effluent Limitations for Wastewater Discharges from Container and Blown/Pressed GlassPlants. Parameter Oil Susp. PH Floo- Lead Process Solids ride (a) (a) ()(b) Glass Containers 30 70 6-9 - - Mach. Blown/Press - - - - - Hand Blown/Press(c) -Leaded & EF Ac Fin. - 10 6 - 9 13 0.1 -Non Lead. EF Ac Fin - 10 6 - 9 13 - -Non EF Ac. Fin - 10 6-9 - (a) Average -.^ daily values for 30 consecutive days as g/Mfetric Ton Furnace pull. (b) Average of daily values for 30 consecutive days as mg/Liter. (c) For plants which melt raw materials, discharge over 190 liters per day and produce type of glassware shown. - 113 - WASTE CONTROL AND TREATMET Gaseous Emissions 23. For control. of particulates from raw materials handling operations, it is the general practice to enclose the unloading and conveying areas and to vent through fabric filters. The chemical composition of the fugitive dusts will be the same as the raw materials, since no chemical reactions occur during storage and handling. 24. Control of gaseous emissions arising from fuel sources can be con- trolled by changing to fuels having a lower content of certain pollutants, such as sulfur. Electric "boosting" also has been effective for this purpose. In this technique electric current is dissipated through the molten glass, supplying part of the required heat and reducing the amount of fossil fuels needed to maintain proper malting temperatures. Boosting is most commonly used in container glass plants. All-electric melters, which have been de- veloped primarily to improve melting efficiency and product control, have resulted in lowering gaseous emissions from the melting operation.. Construc- tion is less expensive for all-electric melters as compared to that for fossil fuel furnaces. 25. Several process modifications can be used to lower emissions. These include (a) reducing the amounts of materials in the fuel, which vaporize at furnace temperatures; (b) increasing the fraction of recycled glass in the furnace fuels; (a) installing sensing and control equipment on the furnace; (d) modifying the burner design and firing patterns; and (e) utilizing electric boosting, as discussed above. 26. Particulates in the glass melting furnace exhaust can be collected by discharging through fabric filters. Fabric filter systems have the advant- age of high collection efficiency, low pressure drop across the system and low energy requirements. Venturi (vat) scrubbers and electrostatic precipitators are also used for removal of particulates. 27. Sulfur oxides are the gases of principal concern in melting furnace exhausts. It has been demonstrated that wet scrubbers provide good control for both sulfur oxides and particulates. Electrostatic precipitators will re- move varying amounts of these pollutants. It has been reported that treating the exhaust streams with an alkaline spray converts gaseous sulfur oxides to solids which can then be collected as particulates. Fluorides, where present, are reduced by electric boosting. Electrostatic precipitators have proven effective in capturing arsenic in the particulate form. Liquid Wastes 28. The major constituents requiring treatment in wastewaters from pri- mary flat glass and automotive glass fabrication are suspended solids and oil. In all cases, in-plant modifications should receive first consideration. No process wastewaters are produced by the sheet and rolled glass subcategories, since these are essentially dry operations and water is used only for dust -114- control in each batch. 29. For plate glass manufacturing plants, lagoon treatment with the addition of polyelectrolyte to the incoming wastewater, has resulted in very high suspended solids removals. System efficiency can be improved in various ways such as by using a two-stage lagoon arrangement, applying sand filtration to the lagoon effluent, recycling of effluents for other plant uses, and other similar techniques. 30. Phosphorous is the pollutant of principal concern in float glass manufacturing, when detergents are used. Wastewater phosphorous loadings can be eliminated by discontinuing the detergent wash. All effluent discharges can be eliminated by recycling the washwater to the batch and cooling tower. Dissolved solids removal may be required if the water is recycled for washing. 31. Suspended solids and oils are most commonly removed by coagulation- sedimentation and filtration at plants producing solid tempered automobile window glass. A solids contact coagulation-sedimentation system, with sludge dewatering by centrifuge, is employed. A further decrease in suspended solids and oil can be accomplished by filtering the settled effluent through a dia- tomaceous earth filter containing a medium especially treated for oil removal. These measures will also effect a reduction in BOD and COD levels. 32. Oil is the major contaminant which must be removed from windshield lamination wastewaters. Most of the oil can be removed by centrifuging, plain flotation using an American Petroleum Institute (API) separator, or by dis- solved air flotation. Suspended solids and residual oil can be removed by filtration through oil absorptive media. 33. The pollutants of.principals concern in the pressed and blown glass industry are oil, fluoride, ammonia, lead and suspended solids. In current practice oil is reduced by using gravity separators such as belt skimers and API separators. Treatment for removal of fluoride and lead is accomplished by the addition of lime, rapid mizing, flocculation, and sedimentation of the remelting reaction products. Treatment for amonia removal is presently not practiced.in this industry. Amnia removal by stream stripping can be used for control of high amonia discharges. It has been reported that several plants are able to recycle non-contact and cullet quench waters. Solid Wastes 34. Control systems for air pollution control will generate solids. These presently have little or no economic value and are not considered to be an attractive source of chemicals. Generally, these solids are best disposed of by recycling back into the glass melting process or through landfilling. 35. Treatment of liquid wastes results in the production of various solids, such as sludges and spent diatomaceous earth. These should be dewatered to the degree feasible and then disposed of to landfill. The lagoons used for suspended solids removal can also serve as solids disposal sites in some cases. - 115 - BIBLIOGRAPHY 1. "Information Sources on the Glass Industry". UNIDO Guides to Information Sources-No. 16. United Nations. New York (1975). 2. United Nations Industrial Development Organization. "Glass and Glass Making". United Nations, Now York (1977). 3. The World Bank "Environmental Considerations for the Industrial Development Sector". Washington (August 1978). 4. U.S. Environmental Protection Agency. "Development Document for Proposed Effluent Limitations Guidelines and New Source Performance Standards for the Flat Glass Segment of the Glass Manufacturing Point Source Category". Doc. EPA 440/1-73/001-a. Washington (October 1973). 5. U.S. Environmental Protection Agency. "Development Document for Proposed Effluent Limitations Guidelines and New Source Performance Standards for the Pressed and Blown Glass segment of the Glass Manufacturing Point Source Category". Doc. EPA 440/1-75/034-a, Group I, Phase II. Washington (January 1975). 6. U.S. Environmental Protection Agency. "Glass Manufacturing Plants. Back- ground Information: Proposed Standards of Performance". Doc. EPA 450/3-79- 005-a. Washington (June 1979). - 116 - TE WO=LD BANK : :NA= 1980 OMFCE O ENVTIMTAL AFFAZRS EFFLUENT GUIDELINES M0W AND STME IUSTRY GENERAL CONSIDEATIONS 1. Zron and steel production utilizes a highly complux system, in which raw matarials consisting of iron are, coke, and Limestone are converted through a series of processes into steel of various compositions, sizes, and shapes as required by market demands. 2. Basically the conversion process may be broken down into five major segments: (a) ore preparation, slntering, and pelletizing; (b) cake production; (c) blast furnace operations (pig iron production); (d) steel production; and (e) rolling and finishing operations. 3. For each of these segments a document has been prepared--to cover the manufacturing process, waste sources and charactewistics, eff, ,ent limitations based on the best practicable treatment technology currentQy available, and cou- trol and treatment of wastes. 4. This document presents a broad simplified summary of the processes carried out in an integrated iron and steel plant, as well as a discussion of noise considerations, sampling and analytical aspects. These are applicable to all segments of the industry, and hence are included in this general section. Figure 1 presents a process flow diagram for the iron and steel industry. THE INUSTM 5. Iron-bearing materials consisting primarily of iron ozides, to which coke and limestone have been added, are reduced to molten iron (pig iron) in a blast furnace. The iron absorbs carbon from the coke in this step and results in cast iron, containing 3 to 4 percent carbon. Since modern steel contains less than 1 percent of carbon, the excess carbon mst be removed to convert the casr iron into steel. 6. This removal is accomplished through controlled oxidation of mixtures of molten pig iron, melted iron, and steel scrap in steelmakIng furnaces to produce carbon steels. Various elements (such as chromium, manganese, and molybdena, alone or in combination) may be added to the molten steel to produce alloy steels. 7. The molten steel, after reaching the desired composition, is poured into molds where it solidifies to form ingats. After removal from the molds the ingots are reheated to a uniform temperature and rolled into shapes known as blooms, billets, and slabs. These shapes are referred to as semifinished steel. У . �, • • � ОдrоЕи ОАЕ f1иEt [1иг[и P1 Агlг ' � • СрА� • liONE f иЕ� P�i►Ni 1иi0ri • бЕ[N1V[ �OMf Г1ЧЕ1 � оvЕи� orro[и r, • 11иiЕА � � 1 • . А1 • tюиlо . iYE[L . cRA eof �Afr1N� , . � • 1 • о • • ига[ьир� ,1 � � . . ,4л` . ' � • с ЧIiAt� . � � . fTONE �LA1r ! ' � � � tUBMAC� • •� А • 1• � С�1 • А!д•! ' •iг�!°. ' tqAP иРЕи � CASi fi[El ' Н or гп� • • fwд nЕАити 1иТЕАЧ[ouiE1 v � OVEN� 1доИ • ! ' • � ��АО • ,� . • , wс�ииlи� о цАq ' . .i � , • � . � � f и1lи � . • • cA�t 51��4 ' � •i � E�EciNOпES РдиоцtТi • сцА� ,, ' ' с11Е Ч1САl !N , , дEeuVEAr кдАР Е1.[сiдlс �1QU1o . . � flur FидиесЕ Tt Е4 , ' lдои � � � . со,►� • • , . П1lT1LlAi10N • 1дoDUCt1 ••[��ц � . • • . . Fi.g, 1-- Рrлсеее F1ои Diagrap! - Iron аnЛ S�ael Indaetry (From U.5. �РА Аос. 440/1-79f024a� Vo1. I� Oct. 1979) ' ' . • • 1 а ' � '. , . ! 118 a. The semifinished steel is tien further processed in ozo or more of several ways such as hot rolling, cold rolling, forging,, extrudingg dravingg or other moms to produce tht finished products needed to fill market demand 'Barss plates,, structural shapes, rails,, wire, tubular shapes, and coated pro- ducts axe among the,forms most frequently produced. NOISE 9. In a typical integrated iron and steel works, noise results from (a) production and processing operations; (b) handling and transport of raw materials, semi-finished and finished products; and (c) aerodynamic and hyd=- dynamic -tources. Efforts to limit noise in steelworks should bo Adayed at lowering exposure to noise in the working enviroument to an acceptable level and removing'noise problems in nearby residential areas. These two are fre-- quently complementary with the solution to the in-works problem often providing a suitable answer to the comounity situation. a general rule, the problem should be resolved as close to the source'as poss I ible in order to assure best results. 10. Typical peak noise levels are as follows: Production and Processina Operations. Ore crushing, 5 meter distance 98 dBA (continuous) Loading scrip pans., 25 ineter distince 105 dBA (intermittent) Electric arc furnace (malt down period) 6 meter distance 109 dBA (semi-continuous) fandling and Transport of Raw Materials, Semi-finished and Finished Products, Conveyor discharge point,, 5 meter distance 85 dBA (continuous) Slab m:LU roller tables, 5 meter distance 95 dBA (intermittent) Aerodynamic and Hydrodynamic Sources: Valves and dampers, blast furnace cold blast, 1 meter distance 96 dBA (continuous) Bl,a,st furnace hot stove operation, 10-mater distance-- 91 dBA (continuous) 3.1 * A number of measures may be taken to reduce noise levels, in addition to maz:Lm= possible reduction at the source. Quieter machines can be substi- tutad, and where this is not possible the noise area should be isolated and acoustically sealed. To protect neighborhoods it may be necessary to acousti- cally treat entire buildings., 'Noise controls should be incorporated in the de- sign of new plants or units. -119- 12. Conveyor belts and systems, in place of road or railway haulings, will greatly reduce noise emissions. Emissions in the handling and transfer of semi-finished or finished products can be offensive. Rolling mill finish- ing departments, for example, represent a major source. For light products the handling equipment can be modified for control purposes, but this is not always possible for the larger and heavier products. The shape, weight, speed of transport, and similar aspects should receive consideration. 13. As production units increase in size, the quantities of process and by-product gases and liquid which must be transported will also increase. Aerodynamic and hydrodynamic noises originate in the integrated collection and distribution systems used to handle these materials. Noises are caused by turbulence (due to high velocities) and pressure fluctuations. Levels can be decreased by-careful piping design, covering pipes with layers of insulation, isolating and correcting vibration sources, using low noise valves and ventila- tors, and other similar measures. Noise barriers, screens, and earth mounds are also effective in reducing noise in many cases. 14. To avoid possible hearing damage weighted sound levels per 24-hour period should be kept below 70 dBA with a maximum of 90 dBA. (See "Noise" Guideline, Office of Environmental Affairs, The World Bank, January 1979). SAMPLING AND ANALYTICAL PROCEDURES, 15. A major element of any program for management of the ehuironment is the basic information on the source, nature, levels, and the concentrations resulting in the medium to which discharged, following mixing and adsorption. Air Pollution* 16. There are two general applications in monitoring air contaminants- emission source testing and atmospheric monitoring. In both cases the location of monitoring devices, the .type of equipment, the duration of sampling, and pollutant discrimination are of paramount importance in quantitatively appraising air quality. Furthermore, these considerations require an intimate knowledge of the emission source(s), background pollution, meteorology and topography of the area under study, and other pertinent factors. 17. Source testing requires a relatively elaborate set of measurements to establish a starting or final contaminant condition. Because industrial processes involve frequent cyclic changes, the timing of source testing or monitoring must be planned accordingly. Process operations shold be carefully reviewed so that individual polluting substances and classes of pollutants can be identified. Fluctuations of peak loadings must be determined and thus pre- dictions of process peculiarities, such as equipment-caused effluent and tempera- ture variations, are possible. All the variables of source testing must be accounted for so that the final pollutant analysis will be representative of the entire source process. A review of the various combinations of devices and techniques and their inherent limitations in current literature is required. This will aFsure the application of the optimum sampling method for a general range of factors, such as greatest reliability, minimum cost, minimization of - 120 required personnAl skills, ease of access and duration of sampling for each specific sampling situation. 18. Monitoring of the atmosphere requires the establishment of an air monitoring network to supply the aerometric data necessary to supprrt air pol- lution prevention, control and abatement activities. At the same time, it should conasume the minimum amount of financial and manpower resouzces. The first step in establishing an air monitoring network is to determine the use of the aerometric data, collection devices available, the limitations of the sampling procedures and equipment, what pollutants must be monitored, location of pollutant monitors, and the duration of monitoring. The very nature of the air pollution problem varies widely from area to area, depending upon the peculiarities of meteorology, topography, source characteristics, and legal and administrative situations. 19. The decision as to which pollutants must be monitored depends on the data needs as defined by the source inventory. In most cases, it is necessary to set priorities because of resource limitations. Pollutants to be monitored should be selected on the basis of their (a) representing a definite hazard; (b) possibility of becoming hazardous to the public health and welfare at some time in the near future; and*(c) being controlled by existing or proposed standards. 20. Generally, the methods of analysis for sootfall,*dustfall, suspended particulate matter, gaseous pollutants and organic pollutants fall within the chemical, physical or biological category. Among the physical mthods are spec- trophotometry, thermal conductivity, chromatographic analysis, mass spectrometry, and gravimetric methods. Biological methods are applied in the preparation of bacterial cultures of organic contaminants and monitoring of respiration rate to correlate with quantities of organic pollutants. There are many variations to these methods. The most recent literature should be carefully reviewed and evaluated for application to -the problem at hand. Water Pollution 21. The composition of industrial wastewaters varies widely, and no truly satisfactory classification system has yet been devised. Hence, the importance of industrial wastewater monitoring cannot be overstressed. Flows are measured to determine the quantity of wastewater being discharged. The combination of flow rate data with analytical data obtained from laboratory analysis permits the calculation of weight of contaminants being discharged into the receiving stream. The next logical step after the amount of contaminants is known is to determine what effect these contaminants have on the receiving body of water and then finally establish some acceptable level of contaminant discharge. Mon- itoring of wastewater also facilitates locating major sou,ces of wastes. 22. The location of a sampling station should be selected such that the flow conditions will have achieved, as closely as possible, a homogenous mixture. The velocity of flow at the sampling point should, at all times, be sufficient to prevent the deposition of solids, thus assuring the collection of a well mixed representative sample. Homogenous flow conditions normally exist after channeling all flow at a weir, Parshall flume or hydraulic pump. A free-falling discharge from a pipe is also an excellent sampling location. A sampling point - 121 - of approximately one-third the wastewater depth from the bottom and as near to the center of flow as possible is recomended for monitoring flows in severs and channels. Types of equipment for the monitoring of industrial wastewater contaminants vary from manual to automatic type devices. The selection of the appropriate sampling .equipment is dependent mainly upon the type of sample de- sired, either "grab" or "composite". 23. The quantity of sample to be collected varies with the extent of lab- oratory analysis to be performed. A sample volume between two and three liters is normally sufficient for a fairly complete analysis. The total number of samples will depend upon the objectives of the monitoring program. The use of a few strategic locations and enough samples to define the results in terms of statis- tical significance is usually much more reliable than using many stations witi only a few samples from each. 24-. Techniques and methods for the qualitative analysis of wastewater con- taminnts may be divided into four basic categories: chemical, physical, biological and biochemical. Detailed procedures are found in the literature, and should be carefully reviewed for application to the problem at hand. Solid Wastes 25. The production and composition of solid wasti hasochanged substantially in recent years because of changing patterns of living, population shifts, and other reasons. Where once solid wastes were mostly domestic, they are now pro- duced in substantial quantities by industry as well. Solid wastes from industry may pose special problems such as nondegradability (plastics) and toxicity (chem- ical residues). Because of the increased importance of solid wastes from the industrial sector, monitoring and analytical methods have been developed for con- trol purposes. 26. The environmental and other impacts on the land disposal site and its environs should be monitored and complete records maintained at all times. Data to be kept for each disposal site should include: - Quantitative measurements of the solid wastes handled; - Description of solid waste materials received, identified by source of material; - Major operational problems, complaints or difficulties; - Vector (a carrier that is capable of transmitting a pathogen from one organism to another) control efforts; - Dust and litter control efforts; and Quantitative and qualitative evaluation of the environmental impact of the land disposal site with regard to the effective- ness of gas and leachata control, including data from leachate sampling and analyses, gas sampling and analyses, ground aud surface water quality sampling and analyses upstream and down- s9ream of the site. 122 27. Upon completa Uilling of the site, a detalled description (IncludIng a plan)should be recorded with the a=ea's Land- recordIng authority. The , description should include general types and låcation of watas, depth of fiLL, and other nformation of interest to potential futura users or owners of the land. - 28. Special attantion should be given to the disposal of hazardous materials to landfill areas. Because it is somatimes difficult to classify wastas an hazardous or non-hazardous a rough classification may be made by evaluating cach one in. tecm of (a) human toxicity, (b) groundwater co=tamin2atri potential, (c) discase transmission potntial, and (d) bicdegradab1litry. BILOGRAFET 1. "Eironmentä-Z-Control in the Iron and Stael Industry," liternatcnal Iron and Steel Tnstituta, Brussels (1978). 2. "The Maklng, Shaping aäd Treating of Steel.", Ed. by .E. McCanon. NIuth Edition. Unitad States Steel Corporation. PIttsburgh (1971). 3. Ensel, C.S. and Vaughn, W.J. "Staml Production: Processes, Products and Residuals." Mfsources for' the Futur'. The Johns Hopkns University Press, BaltImorm and London (1976). 4. Vnitad Nations Developmnt OrganIzat±on, Development and Transfer of Tecnology Series No. 11 "Technologlcal Profiles of the Iron and Steel Industry." UnItad Nations, Nw York (1978). 5. U.S. Enviro=nmtal ProtectIon Agency "Draft Development Doc ants for Proposed Effluent LImItatIons Guidellnes and Standards for the Iron and Stael Tdustry." Dec. EPA 440/1-79/024a. Washtngton.. (October 1979), as follo~s: Vol. i - General Vol. II - y-product Coka M=Cng and Beehve Coka Yakn Subcategnres Val. II - Sinterng and Z1ast Furnaca Subtcatgoras• Vol. IV - Zasic Ox7en Furnacm and Open Ecalth Furnaca- Subcategories. Vol. 7 - EAcrc Arc Furnaca, Degassjng, and ConCmous Cast±ng Subcategories. V01. VI - Pipe and Tube and Cold Rollng Subcategor±es. Vol. VT- Sulfuri Ac.d P±ckl g, Hydrochloric AcId Pickling, and Combination Acid ?±-kl<"st Subearagory. 6. U.S. Environental Protecton Agncy. "Water Quali1y Critar±a." Doc. EPA-R3-73-033, Washington (March 1973). - 123 - 7. Jarrault, P. "Limitation des Emissions de Polluants et Qualite de L'Ati - Valeurs Reglementaires dans les Principaux Pays Industrialises." Institut Francais de 1'Energie. Paris (1978). 8. U. S. Federal Register. "Interim Effluent Limitations and Guidelines, and Proposed Performance and Pretreatment Standards - Electroplating Point Source Category." V.40 No. 80. Washington (April 24, 1975). 9. U. S. Environmental Protection Agency "Guidelines for Lowest Achievable Emission Rates from 18 Major Stationary Sources of Particulates, Nitrogen Oxides, Sulfur Dioxide, or Volatile Organic Compounds." Dec. EPA-450/3- 79-024, Washington (April 1979). 10. J. X. Campbell, R. R. Willis "Protection Against Noise," J. Iron and Steel Institute, Vol. 211, Pt. 5, p. 346 (May 1973). 11. J. M. Campbell, R. R. Willis "A Practical Approach to Engineering Noise," Proc. Metals. Soc. Conf. on Engineering Aspects of Pollution Control in the Metals Industries, 17-29 Nov. 1974. P. 184. 12.. APHA, AWWA, WPCF. "StAndard Methods for theZz.nxamination of Water and Wastewater." 14th Edition. American PublicHealth Association. New York (1975). 13. United Kingdom Department of the Environment, "Analysis of Raw, Potable and Wasta Waters." H. M. Stationery Office, London (1972). 14. U. S. Environmental Protection Agency. "Industrial Guide for Air Pollution Control." Doc. EPA-625/6-78/004. Washington (June 1978) 15. U. S. Environmental Protection Agency. "Hardbook for Monitoring Industrial Wastewaters." Washington (August 1973). 16. "Environmental Considerations for the Industrial Development Sector". The World Bank. Washington (August 1978). - 124 - TEE WORLD BANK MARCH 1980 OFFICE OF ENVIRONMNZAL AFFAIRS EFLUENT GUIDELINES IRON AND STEEL INDUS2-Y BLAST' FURNACE AND DIRECT REDUCTION PROCESSES 1. Iron and steel production utilizes a highly complex system, in which iron are and other raw materials are subjected to a series of processes to con- vert them into finished steel products. 2. The series of conversion processes may be divided into five major segments: (a) are preparation, sintering and pelletizing; (b) by-product coke production; (c) pig iron production; (d) steel production; and (e) rolling and finishing operations. 3. This document is one of a series which has been prepared on the in- dividual segments. Each one presents information as needed for assessing the environmental effects of the gaseous, liquid, and solid wastes produced by the operation. In each case the document discusses the manufacturing processes, waste sources and character, effluent limitations based on best practicable treatment technology currently available, and applicable waste treatment methods. A bibliography is also included. BLAST FURNACES Manufacturing Process 4. Pig iron (containing over 90 percent iron), is the product resulting from reactions of a mixture of iron-bearing materials, coke, and limestone in a blast furnace. These furnaces are large cylindrical structures, some 30 meters in height. Heated air is blown into the lower part of the unit to promote coke combustion. The iron oxide reacts with the hot carbon monoxide from the burning coke, while the limestone reacts with the impurities in the iron-bearing material and coke to forn molten iron and slag. Materials are charged into the top of the furnace, where the reactions begin. As these melt and decrease in volume the charge passes to the bottom of the furnace, where molten iron and slag exist. The molten slag floats on top of the iron and is drawn off through an opening in the upper part of the furnace. The molten iron is drawn off through an opening at the bottom of the furnace (below the slag discharge opening), formed into ingots and cooled for subsequent processing. -125- 5. The combustion process produces gases, which are a valuable heat source. They are discharged through the top of the furnace, cleaned to re- move large quantities of solids and other pollutants, and then recycled. Waste Sources and Characteristics 6. Blast furnace operations produce wastes in the gaseous, liquid, and solid states. Air pollutants are produced by three different segments of the operation: blast furnace gas, cast house emissions, and slag handling and- processing. T. Blast furnace gas is a relatively pollution-free fuel when stripped of its dust burden. Large production,units are frequently connected to combined power and furnace blowing units. For certain other uses, the calorific value of this gas is increased by mizing it with coke oven gas. The gas must be cleaned of dust to a high degree before being used as a fuel. Cleaning or scrubbing is done by a wet process, producing a liquid waste which may contain toxic substances. Under normal operations, air pollution from blast furnace gas production is not considered significant. 8. 16olten metal and slag are discharged from the furnace and cause fume emissions as the result of exposure to air and oxidation. Further emissions arise from vaporization of alkaline oxides from slag, and sometimes from com- bustion of tars and resins in impregnated refractory clays. Emission of sulfur dioxide from molten slag may also be a problem. Manganese fumes in ferromanganese operations constitute a potential health hazard. 9. Coarse aggregate is prepared by pouring the molten slag into a slag pit in layers, either adjacent to or at a distance from the furnace. Water spraying is frequently used to accelerate the cooling process, and this can result in a hydrogen sulfide odor. A condensation chimney is often used to scrub noxious vapors. Materials from slag pits are further processed to produce aggre- gate of specific size ranges. Effective dust control measures can reduce this source to insignificant levels. 10. Blast furnace wastewaters-originate primarily from top gas cleaning. Water is also used for cooling the furnace, but this is a non-contact operation and therefore of little or no significance from the pollution standpoint. The wastewaters contain large quantities of particulate matter and quantities of cyanide, phenol, and amonia. Other pollutants include heavy metals and certain organics originating in the raw materials or formed during the combustion process. 31. Wastewater flows and characteristics will vary, according to the raw materials, the iron making process used, and the gas scrubbing process applied. Ranges of flows and concentrations that are typically found are presented in Table 1. 12. Solid wastes include blast furnace slag, dry dust and moist filter cake, cast house fumes, refractory wastes, and ladle skull (the metal shell which solidi- fies on the sides and bottoms of the ladle). The slag is processed and used as a building material, raw material for blast furnace cement, and other similar purposes - 126 Cast house dusts are collected on filter extraction systems and fed to the sinter plant. Used refractory material and ladle skulls are generally dumped on site. Table 1. - Wastewater Flows and Characteristics for a Typical Blast Furnace Operation Paranter* Concentrations Flow - L/Ms (a) 4600 - 12,900 Ammonia N - zg/L (b) 10 - 17 Cyanide mg/L (b) 1 - 54 Phenols ag/L (b) 0.05 - 2.9 Fluoride mg/L (b) 1.4 - 6.5 Sulfide mg/L (b) 2.0 - 54 Suspended Solids mg/L 354 - 7040 pH - Units 6.4 - 10.2 (a) LIMg = Liters per megagran of iron produced. (b). mg/L = milligrams per liter of effluent Effluent Limitations 13. Gas cleaning and recovery will normally reduce atmospheric discharges to concentrations well below acceptable levels. In all cases, ambient air quality should be maintained below .the following levels outside the plant fence: Sulfur Dioxide Inside plant fence Annual Arith. mean: 100'Ag/m3 Max. 24-hr peak 1000 pg/=3 Outside plant fence Ann-al Arith. mean: 100 ,ug/m3 Max. 24-hr peak 5001,ug/m3 * Mg a megagram 1 metric ton L a Liter - 127 - Hydrogen Sulfide Average 24-hour 8 ug/m3 Particulate Matter Annual Gea. Mean 75,u/m3 Max. 24-hour, not over once a year 260 'ug/m3 (a) /a/3 * MicrogramoR notr zbic meter of air sampled 14. Limitations for blast furnace wastewater effluents, based on best practicable treatment technology currently available, are presented in Table 2. Table 2.- Effluent Limitations for Blast Furnace (Pig Iron) Wastewater Discharges. fLimitation Parameter (per Mg Product) (a) Flow (b) 520 Liters Susp. Solids 26 Grams Sulfide 3.1 Grams Fluoride 21 Grams Phenols 2.1 Grams Cyanide 7.8 Grams Amnia - N 65 Grams pR 6.0 - 9.0 Units (a) Per megagram of iron produced. (b) Excluding all non-contact cooling water - 128 Control and Treatment of Wastes 15. Because blast furnace gas is recycled and reused, it undergoes a very high degree of cleaning. The cleaning process frequently involves up to three stages - dry collection in a "dust catcher", high energy scrubbing and vat electrostatic precipitation. Excessive emissions from the cast house operations can be avoided by maintaining sufficient ventilation. In the slag handling procedure, the miing of molten slag with water is in itself effec- tive in controlling much of the air pollution discharged. A condensation chimney is effective for removing any residual gases and materials. 16. Treatment of blast furnace wastewaters is concerned mainly with the removal of suspended solids. Other constitutents, such as cyanides, phenols, oils and greases, metals, and others are also of concern. These wastes originate mostly from the cleaning of gases resulting from combustion of the raw materials in the furnace. They are removed through the top of the furnace (and frequently referred to as "top" gases) for subsequent cleaning and use elsewhere in the plant. 17. Treatment in most cases consists of thickener/clarifiers for removing the suspended solids. Sludge is removed continuously from the bottom of the thickener and pumped to vacuum filters, for dewatering. The filtrate is returned to the thickener influent. Various flocculating agents such as polymers, are often used to enhance solids. removal. The clarified effluent can be used for cooling purposes. Solids removal, by itself, has only a minor effect on the chemical composition of the wastewater. Chlorination can be useful as a means of destroying cyanides and phenols. Bio-oxidation systems have also been success- ful in destroying cyanides. 18. Both organic and inorganic toxic pollutants have been found in blast furnace effluents, and hence should receive attention. Depending upon the in- dividual or combination of pollutants involved, varying degrees of removal can be achieved by the application of filtration (as part of the suspended solids removal procedure), activated carbon, and carbon adsorption. 19. Disposal of solids, filter cake, sludges, and other similar materials which cannot be recycled is to controlled landfill. Slurries from the gas scrub- bers frequently contain significant amounts of lead, zinc, and alkalis and hence cannot be recycled. without receiving additional treatment. DIECT EDUCTION PROCESS 20. In recent years, particularly in countries having adequate supplies of both high grade iron ore and energy resources, a number of methods for the direct reduction of ore have been developed. This has been particularly true in countries seeking to establish a local iron and steel industry. The process permits development of smaller production units, with capacities in the order of 1,000 tons of sponge iron per day. - 129 - 21. Basically the process utilizes the reaction between either a gaseous reducing agent or a solid fuel and the ore. The lump ore and/or pellets are charged to a vertical shaft or fluidized bed to produce matallized products containing a minimm of 90 percent iron. This sponge iron can be readily maltad in an electric arc furnace. The main advantages of the process relate solely to the size and flexibility of the operation. The direct reduction/electric furnace steelmakIng procedure is much more energy-intensive than the more con- ventional blast furnace/basic oxygen furnace procedure. 22. Dusts contained in the off-gases from these plants are usually re- moved by vet scrubbing. Cleaned gases are either used to provide heat for gas reforming or, in some instances, to preheat the feed material. The resulting slurry is filtered, pressed, and recycled. The clarified effluent can be used for cooling. Wmere pelletizing is used, the fines resulting from the screening of the pellets are fed back to the process. 23. Effluent limitations for gaseous and liquid effluents are the same as those given in paragraph 13 and 14, above. BIBLIOGRAPHY 1. "Environmental Control in the Iron and Steel Industry", International Iron and Steel Institute, Brussels (1978). 2. United Nations Development Organization, Development and Transfer of Tech- nology Series No. 11 "Technological Profiles of the Iron and Steel Industry". United Nations, New York (1978). 3. U.S. Environmental Protection Agency "Draft Development Documents for Pro- posed Effluent Limitations Guidelines and Standards for the Iron and Steel Industry." Doc. EPA 440/1-79/024a. Washington. (October 1979): Vol. Ill- Sintering and Blast Furnace Sub-categories. 4. Jarrault, P. "Limitation des Esmissions de Polluants at Qualite de L'Air - Valeurs Raglementaires dans leas Principaux Pays Industrialises." Institut Francais de l"Energie. Paris (1978). 5. U. S. Environmental Protection Agency "Guidelines for Lowest Achievable Emission Rates from 18 Major Stationary Sources of Particulate, Nitrogen Oxides, Sulfur Dioxide, or Volatile Organic Compounds." Dec. EPA-450/3-79- 024. Washington (April 1979). 6. U. S. Environmental Protection Agency. "Industrial Guide for Air Pollution Control." Doc. EPA-625/6-78/004. Washington (June 1978). 7. U.S. Environmental Protection Agency. "Water Quality Criteria." Doc. EPA- R3-73-033. Washington (March 1973) 8. APEA, AWA, WPC7. "Standard Methods for the Examination of Water and Waste- water." 14th Edition. American Public Health Association. New York (1975). 9. U.S. Environmental Protection Agency. "Handbook for Monitoring Industrial Wastewaters." Washington (August 1973). - 130 - TEE VORLD BANK MARCE 1980 OFFICE OF MNVIRNMNTAL AFFAIRS IRON AND STEEL InDUSTT iTPRODUCT CO OVENS EFFLVENT GUIDELINES 1. Iron and steel production utilizes a highly complex system, in which iron ore and other raw materials are subjected to a series of processes to convert them into finished steel products. 2. The series of conversion processes may be divided into five major segments: (a) ore preparation, sintering and pelletizing; (b) byproduct coke production; (c) pig iron production; (d) steel pro- duction; and (e) rolling and finishing operations. 3. This document is one of a series which has been prepared on the individual segments. Each one presents information needed for assessing the environmental effects of the gaseous, liquid, and solid wastes produced by the operation. In each case the document discusses the manufacturing processes, waste sources and character, effluent limitations based on best practicable treament technology currently available, and applicable waste treatment methods. A bibliography is also included. MANUFACTURING PROCESS 4. Two types of ovens have been traditionally used to produce metallurgical coke: beehive and byproduct recovery. The byproduct recovery types, discussed in this document, are the most extensively used at this time. In the United States, for example, less than 1% of the metallurgical coke produced in 1977 came from beehive ovens. 5. The byproduct recovery process not only results in a suitable high-quality coke, but also makes possible the recovery of valuable byproducts from the distillation reaction. Crude coal tars, crude light oils, ammonium sulfate, and naphthalines are the principal by- products recovered. Other products, such as creosote oils, phosphates, crasols and elemental sulfur, are also recovered in some cases. -131- 6. A byproduct recovery coke plant consists of batteries of ovens in which blends of high, medium, and low volatile bituminous grades of selected coals are heated. The heating occurs out of contact with air in order to drive off volatile components without burning them. The volatiles.are drawn off and recovered, while the residue remaining after 12 to 24 hours of heating constitutes the coke product. 7. When ready, the coke is pushed from the oven and quenched (or cooled) before going to storage or use. Two methods are in use - dry quenching and wet quenching. Dry quenching is used in some plants in Russia, England, Prance, and Switzerland. Wet quenching, the most widely used method, is accomplished by discharging the hot coke from the ovens to the quenching car. The car is then moved to the quenching station by locomotive, and water sprayed on the mass while still in the car, to cool it. The coke is then transferred elsewhere for storage or use. WASTE SOURCES AND CHARACTERISTICS 8. As previously stated, the byproduct process yields a variety of useful materials, which are either reused in the mill operation or profitably marketed elsewhere. Utilization of these byproducts keeps then out of the waste streams and hence signiflcantly reduces the waste load which might otherwise be discharged from a coke plant. There are, however, several other potential sources of gaseous, particulate, and aquaeous emissions which are not removed as part of the recovery process and can have an adverse effect on the environment. 9. Waste gas can originate in the coal preheater units utilized at many plants. Gravity charging of ovens can result in emissions of toxic and flammable gases, as well as fumes and dusts. 10. Major liquid wastes usually include excess amonia liquor, final cooler wastewater, light oil recovery wastes from the benzol plant, barometric condenser wastes from the ammonia sulfate crystal- lizer, desulfurizer wastes, and contaminated waters from air emission scrubbers at charging, gushing, quenching, preheating, or screening stations. The largest volumes of water are from indirect (noncontact) cooling operations. These are nomlally not contaminated, except from leaks in coils, tubes, or other equipment. 11. Typical wastewater flows from byproduct coke oven operations are presented in Table 1. -132- TABLE 1 - Typical Wastewater Flows from Byproduct Coke Oven Overations Flow Source L/Mg Coke.!/ Waste Amonia Liquor 162 Final Cooler Blowdown 133 Benzol Plant Wastes,. 226 Misc. Westes 259 Steam Condensates 40 (Subtotal - Basic Flow) (820) Baro. Condenser Blowdown 122 Desulfurizer, wet 1c Air Pollution Control Blowdowns Preheaters and Dryers 37 Charging 111 Quenching 1/ 2100 a/ L/Mg * Liters per magagram = liters per metric ton. i Mzy include varying amounts of non-process cooling water. / Amount applied. Generally one-third evaporates and remaining two-thirds is recirculated. -133- 12. Parameters considered of major significance in coke plant wastewaters include: total suspended solids, oils and greases, ammonia -N, total cyanides, phenolic compoTnds, sulfides, thiocyanates, and pH. In addition, coking will also produce a large number of both organic and inorganic pollutants, which may need to be eliminated from waste streams if concentrations are too high. Over 50 such pollutants have been identified at existing plaqts. 13. Available data on raw waste quality in coke plants show wide variations, and hence are not presented here. Each plant will need to be evaluated according to its own individual circumstances and merits. 14. Byproduct coke making also produces a number of toxic pollutants, both organic and inorganic. Some 30 organic substances are considered of major significance, including acrylonitrile, ethyl- benzene, naphthalene, phenol, fluorine, pyrene, toluene, and ylane. Of the inorganics, antimony, arsenic, cyanides, selenia, silver, and zinc are considered to be the most significant. 15. The use of lime to raise pd levels prior to ammonia stripping produces a sludge in the form of unreacted calcium hydroxide, along with precipitated calcium carbonates and sulfates. Other sludges include coal or coke fines. Another source of solid wastes may occur where recovered byproducts are not sufficiently pure for further use or for resale or reuse. EFFLUENT LIMTATIONS 16. Coke making may result in discharge of gaseous ammonia, hydrogen sulfide, and hydrogen cyanide to the atmosphere if collectors, ductwork, and piping are not carefully monitored and controlled. Particulates may also escape to the atmosphere. With effective controls, little or none of these substances should be discharged. Odors can be 4 a problen if not carefully controlled. 170 On the basis of best practicable control technology now avail- able, wastewaters from byproduct coke plants should be maintained at or below the levels given in Table 2. 18. The use of lime to raise pH levels prior to ammonia stripping produces significant quantities of sludge. Disposal of these sludges to landfill sites should be such as to prevent escape to the environment. - 134 - TABLE 2 - Effluent Limitations for Byproduct Coke Plant Operations Limitation Parameter (Per Mg Coke) Total. Cyanide 22 gram Phenolic Compounds 1.5 Ammonia - NH3 91 Oil and Grease 11 Suspended Solids 37-94 PH 6.0-9.0 (units) Flow a/ 730-940 liters a/ Excludes non-contact cooling water. CONTROL AND TREATMENT OF WASTES 19. Because the byproducts from coke making can be profitably recovered and marketed or reused, pollution control is largely achieved through the recovery processes. Gases and dusts which are not other- wise recovered as useful byproducts are effectively removed by dust collecting devices,, sprays, or a combination of the two. Disposal is either to recycling or to landfills. 20. Odors can be minimized or eliminated by restricting vapor losses to the atmosphere through leaking vent pipes, storage vessels, and liquor seals. Burning of coke oven gas can produce significant emissions of sulfur gas, unless the sulfur component is removed before burning. Desulfurization is most often accomplished either through absorption/desorption or absorption/oxidation. Removal efficiencies will range from 80 to 99 percent. 21. Following application of various byproduct recovery measures, there still remains a residual discharge of contaminated wastewater - 135 - which must be treated before release. The three most frequently applied methods are physical/chemical, biological, and incineration/ evaporation technologies. Flow minamization should be a first step in all cases. 22. A physical/chemical system would include a fixed leg on the ammonia still to strip additional amonia from the wastewater, through addition of lime slurry and additional steam. This step is Aollowed by carbon adsorption to remove the organic components. Prior to carbon adsorption the wastes can be oxidized with such chemicals as chlorine, chlorine dioxide, sodian hypochlorite, ozone, or peroxides to destroy the organics. Where these chemicals are used, the carbon colum acts mainly as a final polish. 23. In a biological or bio-axidation system, the wastewaters from the fixed leg to the ammonia still, which have a high pE, are first neutralized with acid and then flow into a single-stage activated sludge bio-oxidation system or pond. Aeration is provided by mechanical agitation or by use of large blowers. Depending upon the pollutants to be removed one or two additional stages may be required to remove phenols, cyanide and ammonia (oxidized to nitrates) -and provide denitrification in a final stage. Effluents from these stages are subjected to sedimentation, step aeration, and pf adjust- ment before discharge. 24. Incineration/evaporation is not widely used, and is best applied in situations where the impact on air pollution would not be significant. In this method, the total raw waste load is distilled and evaporated in a controlled combustion system. Coke oven gas -and crude coal tar are the only byproducts recovered. 25. The use of lime to raise pH levels prior to ammonia stripping produces large quantities of sludge in the form of unreacted hydroxide, along with precipitated calcian carbonates and sulfates. Disposal can be to landfill but care must be taken to prevent the sludges from redis- solving and reaching streams as runoff. Lesser amounts of sludge form when caustic soda is used as the alkali, but this will cause an increase in the. dissolved solids levels. Other sludges will contain coal or coke fines, and these can be readily recycled back to the process. 26. All sludges should be recycled to the process insofar as possible. Controlled landfill is the disposal method of choice for all solid wastes that cannot be recycled to the system, including those byproducts which are not of suitable quality for marketing purposes. - 136 - BIBLIOGRAPEY 1. Russel, C.S. and Vaughn,W.J. "Steel Production: Processes, Products and Residuals." Resources for the Future. The Johns Hopkins University Press, Baltimore and London (1976). 2. United Nations Development Organization. Development and Transfer of Technology Series No. 11 "Technological Profiles of the Iron and Steel Industry." United Nations, New York (1978). 3. U.S. Environmental Protection Agency. "Draft Development Documents for Proposed Effluent Lim1taL.is Guidelines and Standards for the Iron and Steel Industry." Doc. EPA 440/1-79/024a. Washington. (October 1979: Vol. II - Byproduct Coke Making and Beehive Coke Making Sub- categories. 4. Jarrault, P. "Limitation des Emissions de Polluants at Qualite de L'Air - Valeurs Reglementaires dans les Principaux Pays Industrialises." Institut Francais de 1'Energie. Paris (1978). 5. U.S. Environmental Protection Agency."Guidelines for Lowest Achievable Emission Rates from 18 Major Stationary Sources of Particulate, Nitro- gen Oxides, Sulfur Dioxide, or Volatile Organic Compounds." Dec. EPA-450/3-79-024 Washington (April 1979). 6. U.S. Environmental Protection Agency."Industrial Guide for Air Pollution Control." Doc. EPA-625/6-78/004. Washington (June 1978). 7. U.S. Environmental Protection Agency. "Water Quality Criteria." Doc. EPA-R3-73-033, Washington (March 1973). 8. APRA, AWA, WPCF. "Standard Methods for the Exanination of Water and Wastewater." 14th Edition. American Public Health Association. New York (1975). 9. U.S. Environmental Protection Agency. "Handbook for Monitoring Industrial Wastewaters." Washington (August 1973). - 137 THE WORLD BANK APRI 1980 OFFICE OF ENVIRONMENTAL AFFAIRS 120N AND STEEL INDUSTRY ORE PREPARATION, SINTERING, AND PELETIZING . ETSLDET GUDELINES- 1. Iron and steel production utilizes a highly complex system, in which iron are and other raw materials are subjected to a series of processes to convert them into finished steel products. 2. The series of conversion processes may be divided into five major segments: (a) ore preparation, sintering and pelletizing; (b) by-product coke production; (c) pig iron production; (d) steel production; and (e) roll- ing and finishing operations. 3. This document is one of a series which has been prepared on the in- dividual segments. Each one presents information as needed for assessing the environmental rfects of the gaseous, liquid, and solid wastes produced by the operation. Ineach case the. document discusses the manufacturing processes, waste sources and character, effluent limitations based on best practicable treatment technology currently available, and applicable waste treatment methods. A bibliography is also included. ORE PREPARATION- Manufacturing Process 4. Higher grades of ore are becoming rapidly depleted throughout the world, due to selective mining of one type or another. During the mining of high-grade ores the low-grade ores which may be present as overburden and capping will ai with the material of good grade, particularly when large-scale mechani- cal mining methods are used. To assure an acceptable and consistent ore having the desired composition for iron smelting, the run-of-the-mine ore is given special preparation, often referred to as "beneficiation." 5. Various beneficiation techniques are applied to suit the specific ore, depending upon the mineralogical and petralogical characteristics of the material. Techniques used include wet screening, gravity treatment, magnetic separation, froth flotation, reduction roasting, thickening, and drying. The combination of techniques used depends upon the cost economics, the required quality of the end product, and the possibilities of recycling waste products. Waste Sources and Characteristics 6. Raw materials are delivered by water, rail, or highway, and normally require handling within the mill, as 'well as stockpiling and blending. Within 138 - the works area, raw materials such as oies are usually transported by convey- or belts. Spray installations are used for reducing dust losses, since a high surface moisture content is necessary to avoid wind-borne losses of fine mate- rials. Where no spray facilities axe used, studies have shown losses from wind-borne drift to be in the order of 0.35 grams per ton of material stored. With adequate controls, waste production from this segment of the operation should be relatively minor. SINTEPING AND PELLETIZING Manufacturing Process 7. The benefication process produces large proportions of fines, some- times up to 50 percent by weight of the ore mined. In the case of magnetite ores, the entire quantity of concentrate is in the form of fines. Whatever the source, the fines require sintering or pelletizing before utilization for making iron. 8. Sintering produces a useful agglomerate from the mined ore and a wide variety of wastes, such as coke breeze, mill scale, flue dust,blue dust, limestone, and dolomite fines. The process has great flexibility in the agglo- meration of raw materials having different physical properties and mineralogical composition. 9. Pelletizing, another of the agglomeration processes, is most fre- quently utilized where the ore particles are in a very fine form either as a beneficiated product or as a naturally-occurring mineral like blue dust. The process is carried out in two steps - balling and induration. 10. The purpose of "balling" is to increase the particle size of the dust. After wet or dry grinding of the ore, dewatering, and partial drying, "green" pellets are formed by the addition of a suitable binder. Bentonite, .limestone, or hydrated lime are commonly used for this purpose. In order to produce pel- lets of suitable quality it is necessary to carefully control the type of grind, the size to which the are is ground, the schedule of drying and preheating, and preheating, and the cooling cycles. 11. The induration process involves the drying of the green pellets,pre- heating to proper temperatures, firing at the required temperatures, and soak- ing for a definite period to create iron oxide or a slag bond formation between grains. This is followed by regulated cooling of the final product. 12. A recent development has been the use of cold induration processes, in which special types of cements (containing no sulfur) are used with the pell- etizing feed before balling. The green balls, sometimes coated with iron con- centrate fines to prevent cluster formation, are allowed to cure and harden for periods of up to 5 weeks. - 139 - Waste Sources and Characteristics 13. Although sintering plants are generally fitted with high chimneys to assure adequate dispersion of waste gases, use of high-sulfur raw mate- rials can cause problems from sulfur dioxide combining with other contribu- tions from nearby sources. Dusts or particulate matter can also be major problems. Other gaseous pollutants, such as hydrogen fluoride and nitrogen oxide do not cause problems in most countries, although. Japan is experiencing some problems as a direct result of the potential for photochemical pollution. A typical sinter vlant wasta gas will contain 0.2 to 1.0 g/m3 (normal)*of SO2 less than 0.4. gjm3 (normal) of NO., and less than 0.01 g/z3 (normal) of F 14. The firing process employed in pellet plants may produce gaseous emissions of sulfur dioxide and nitrogen oxides. When using ores with high fluorine content, gaseous fluorine compounds may be emitted. Both sulfur dioxide and nitrogen emissions depend upon the types of burner and fuel used, and will normally not constitute a serious problem. 15. Wastewater generated during the sintering and pelletizing operation result mainly from the scrubbing of gases and dusts producted during the process. Wastewaters are also generated from7the cooling, crushing, and screening of the final product. Newer plants generally use "dry" dust collec- .tion equipment and hence have no flows from this source. The pollutants in the effluent reflect the variety of process fuel materials, such as iron and steelmaking flue dusts, ores, mill scale, coke, limestone, slag fines, and others. Oils and gases are also present, prieuz.,-zlly carried by the scrap and mill scale used in the operation. 16. The average concentrations found in typical untreated effluents from sintering plants are shown in Table 1. Effluent Limitations 17. Where effective Sas scrubbing is ued to remove gases and dusts only minor amounts of air pollutants are discharged. In all situations ambient levels of gaseous effluents, outside the plant fence, should be maintained within the following limits: Sulfur Dioxide Inside plant fence Annual Arith. mean: 100 ug/m3 Max. 24-hr peak 1000 Pg/m3 Outside plant fnca Annual Arith. mean: 100 pg/m3 Max. 24-hr peak 500 ug/m3 Nitrogen Dioxide Annual Arithmetic Mean 100 )u/'m3 (normal) Particulate Matter Annual Geometric Mean 75 ug/m,3 (normal) Max. 24-hour, not more than once a year 260 Pg/ * Normal Conditions: 0C, 101.3 kPa (760 mn Rg) -l140 TABLE 1. Sintering Plant Wastewater Flows and Characteristics Parameter Average Flow - L/MS (a) 6100 Oil and Grease - mg/L (b) 245 Suspended Solids - mg/L 6100 PH 6-12 Fluatide - mg/t 17 Sulfide - mg/L 56 (a) L/1% - Liters per magagram sinter produced (b) mg/L 1l.grams per liter of effluent. 18. Effluent limitations, based on best practicable technology currently available, should be maintained as shown in Table 2. TABLE 2. Effluent Limitations for Wastewaters from Sintering Plants Parameter Mtation (a) (Per MN( Product) Oils and Greases 4.2 grams Suspended Solid 21 grams pH 6.0 - 9.0 (units) Flow (b) 416 liters (a) Per Metric Ton of sinter produced (b) Excluding non-contact cooling water (*) 1 Mg * 1 megagram = 1 metric ton - 141 - 19. Various toxie pollutants, depending upon the raw materials used, are also generally present. These include cyanides, zinc, copper, nickel, lead, silver and others. Limitations for these substances should be as follows: Cyanides: 0.01 ag/L(a) Nickel: 1 mg/L Zinc: 1 ag/L Lead: 0.1 mg/L Copper: 3. mg/L Silver: 0.1 mg/L (a) mg/L * Milligrams per liter.of effluent 20. Solid wastes are produced from the gas and dust scrubbers and other sources. These solids are primarily metallic oxides, mostly iron, and are .recycled to the sIntering process. Control and Treatment of Wastes 21. uGas and dusts are effectively removed from exhaust streams by means of wet scrubbers or by dry methods, such as electrostatic precipitation. The removed solids are either recycled to the sintering or pelletizing processes or transferred to a waste recovery operation elsewhere. 22. Wastewaters result mainly from the vet scrubbing and cooling of gases, dusts, and other materials involved in the sintering processes. While treatment facilities are concerned mainly with solids removal, a side effect is to remove other pollutants as well. Thickeners and clarifiers or settling lagoons are used for suspended solids removal. Skimmers are effective for oil and grease removal. 23. While suspended solids removal will remove some of the toxic pollu- tants, higher degrees of treatment are usually required for this purpose. Advanced treatment technologies known to be effective for both organic and in- organic toxic pollutants include alkaline chlorination, sulfide precipitation, filtration, and activated carbon treatment. 24 Solid wastes generated from the treatment of gaseous and liquid effluents are generally recycled into the systems. BIBLIOGRAPHY 1. United Nations Development Organization, Development and Transfer of Technology Series No. 11 "Technological Profiles of the Iron and Steel Industry." United Nations, New York (1978). - 142 2. U.S. Environmental Protection Agency "Draft Development Documents for Proposed Effluent Limitations Guidelines and Standards for the Iron and Steel Industry." Doc. EPA 440/1-79/024a. Washington. (October 1979): Vol. III - Sintering and Blast Furnace Subcategories. - 3. Jarrault, P. "Limitation des Emissions de Polluants at Qualite de L'Air = Valeura Realamentaires dans les Principaux Pays Industrialises." Institut Francais de 1"Energia. Paris (1978). 4. U.S. Environmental Protection Agency "Guidelines for Lowest Achievable Emission Rates from 18 Major Stationary Sources of Particulate, Nitrogen Oxides, Sulfur Dioxide, or Volatile Organic Compounds." Doc. EPA-450/3- 79-024 Washington (April 1979). 5. U.S. Environmental Protection Agency. "Industrial Guide for Air Pollution Control." Doc. EPA-425/6-78/004. Washington (June 1978). 6. U.S. Environmental Protection Agency. "Water Quality Criteria." Doc. EPA-R3-73-033, Washington (March 1973). 7. U.S. Environmental Protection Agency. "Handbook for Monitoring Industrial Wastewa trs." Washington (August 1973). 8. APEA, AWWA, WPCF. "Standard Methods for the Examination of Water and Wastewater." 14th Edition. American Public Health Association. New York (1975). - 143 TIE WORLD AK OCTOBER 1980 OFFICE OF ENVONIENTAL AFFAIRS IRON AND STEEL IDUSTRY ROLLING AND FINISHING OPERATIONS EFFLUENT GU IDIES 1. Iron and steel production utilizes a highly complex system, in which iron ore and other raw materials are subjected to a series of processes to convert them into finished.steel products. 2. The series of conversion processes may be divided into five major segments: (a) ore preparation, sintering and pelletizing; (b) by-product coke production; (c) pig iron production; (d) steel production; and (e) rolling and finishing operations. 3. This document is one of a series which has been prepared on the in- dividual segments. Each one presents information as needed for assessing the environmental effects of the gaseous, liquid, and solid wastes produced by the operation. In each case the document discusses the manufacturing processes, wasta sources and charactir, UA.Zluant limitations based on best practicable treatment technology currently available, and applicable waste treatment methods. A bibliography is also included. MAUFACTURING PROCESS 3. Steel finishing consists of the processing of the steel from the furnaces into the range of shapes and sizes required to supply specific market needs. Because of the wide variety of possible products, the array of technology and. equipment required for any particular product, the different operating practices utilized by individual plants, and other similar factors,this is prob- ably the most complez operation in steel making. Some of the typical operations are discussed below. 4. Conventional casting involves the pouring of ingots, subsequent reheat- ing in soaking pits, followed by rolling of semifinished shapes from the ingots. A considerable amount of the original malt, averaging some 14 percent, is lost during all this handling. Losses result from pouring, unmolding, rolling, trim- Lng, and surface preparation (scarfing). This scrap is generally recycled to the steel furnaces. 5. In continuous casting the molten metal is poured into a trough, and then flows to water-cooled molds to form the desired shape. From the mold, the continuous pieces having the required cross-sections are drawn by rollers, cooled by direct water sprays, and cut into pieces of the desired lengths. Scrap pro- duction is far less (under 4 percent) in this process than in conventional casting. 144 6. Not-rolling strip mills convert heated slabs into thin steel strips, which are either cut into lengths (sheet) or rolled onto cares (coil). A plate mill converts heated slabs into thicker plates (over 6 m), and functions essentially the se as a strip mill. 7. While some products are sold as they come from the hot-rolling mill, a large portion of the hot-mill production is subject to further processing in the cold mill. In this process, sheet and strip steel products are reduced in thickness by being passed through various cold rolling configurations. As pre- paration for cold rolling,the surface of the strip is cleaned of scale formed in the hot mill and during storage. This is usually done by passing the strips through baths of dilute hydrochloric or sulfuric acid to discolve the scale, a process designated as "pickling". Since cold steel has lower plasticity, as compared with hot steel, rolling speeds are slower to achieve the same thickness. Cold rolling can produce thinner strips and a finer surface quality. 8. During cold rolling the steel becomes quite hard and unsuitable for most uses. Therefore, the strip is subjected to an annealing process to restore its ductility -and to effect other changes in the mechanical properties to render the material suitable for specific uses. 9. For certain uses it is necessary to apply coatings to the steel in order to provide corrosion protection, wear resistance, antifriction properties, lubricity, heat and light reflectivity, and other effects. The process involves the application of a thin layer of a metallic or non-metallic element to the surface. Metallic elements most frequently used include tin, zinc, chromium, and aluminum. Non-metallic coatings include oxides, sulfides, phosphates, sili- cateas, simple complex organic compounds (alkyd resins and varnishes), and mis- cellaneous inorganic coatings (vitrous enamel, etc.). The most important step in the process is the careful preparation of the surface of the steel prior to application of the coating. 10. A naber of methods are in cmmon use for applying coatings. These include the hot-dip process, metal spraying, metal cementation, fusion welding, and metal cladding. Most metal coatings are applied by the hot-dip method, ex- cept for tin which is now generally applied by an electrolytic process. 1. The electroplating process is one in which a basic ferrous or non- ferrous material is coated by electrodeposition of a metal, such as tin. Three steps are involved: (a) cleaning, to remove oil, grease, and dirt from the sur- face to be coated; (b) electroplating, in which metal ions in acid, alkaline, or neutral solution are reduced on cathodic surfaces (in this case the surface being platad); and (c) post-treatment, in which additional coatings of another material may be applied for special uses. Continuous electroplating of coil steel represents the largest application of electroplating worldwide, in terms of tonnage produced. - 145 - WASTE SOURCES AND CA2ACTE!ISTICS 12. The most likely sources of air pollutants in the rolling and finish- ing operations are the reheating furnaces, soaking pits, scarfing machines, acid recovery plants, galvanizing lines, and organic coating lines. Current control practices provide sufficient reduction, so that these sources are not considered significant. - 13. Oil firing of reheating furnaces and oil pits can produce unaccept- able sulftr gases in the 4nmedate environment. Coke oven gas, natural gas, and other alternate fuels are coming into widespread use, thus eliminating this problem. Automatic scarfing produces some iron oxide fumes, but this is con- trolled by means of irrigated precipitators. Spentpickling acids are generally recovered by heating, but effective gas scrubbing prevents fuma acid emissions. Fumes from the salt fluxes used in hot-dip galvanizing lines are controlled by extraction and ventilation. Solvent fmias from organic coating lines can be controlled with properly designed ventilating systems. 14. The primary waste constitutents from the hot-rolling processes in a pipe and tube mill are scale, oils and greases. Scale is formed as the hot steel surface oxidizes, and is continuously scaled'and chipped away. Scale par- ticles are mainly metallic iron, farrous oxide, and ferric oxide. Oils and greases originate from oil spills, equipment line leaks and breaks, dripping of lubricants, and equipment washdowns. Copper, chromium, lead, zinc, and other heavy metals may be found in wastewaters when these are used in the rolling pro- cass, but levels are usually not significant. Typical wastewater characterisitcs are presented in Table 1. 15. *Wastewaters from a cold-rolling pipe and tube mill generate a fine scale (primarily ferric oxide), as well as both soluble and insoluble oils and greases. Wastewater sources include flushing of the product, welders and rolls, and the cold drawing and pickling waste waters. Levels of toxic pollutants are below those for hot-rolling mills, and hence are considered to be of little or no significance. Typical wastewater characteristics are shown in Table 1. TABLE 1. Wastewater Characteristics for Hot and Cold Pipe and Tube Mills Parameter Rot Tube Cold Tube Kill Ml Suspended solids - mg/L 500-700 1000 Oils/Greases - mg/L 50-100 100-200 pH 6.0-9.0 6.0-9.0 - 146 - 16. The roling process generates heat. Oil solutions are added directly to the product to reduce the heat buildup and to provide lubrication for the product beng rolled. Three types of oil application systems are in use today- designated as recirculated, direct application and combination. The recirculated system is moat widely used at the present time. Due maIAly to the use of the oil solutions, high concentrations of various pollutants are discharged. The most common of these are suspended solids, oils and greases. Toxic metals and organic pollutants are also present and anst be removed before discharge of the effluent. 17. The major water use in a cold rolling mil operation is for cooling the rolls and materials being rolled. A water-oil emulsion is sprayed directly on the materials and rolls as the material enters the rolls. A flooded lubri- cation system supplies both the lubrication and cooling operations. Recycle and recovery systems are commonly used, in order to control pollution and reduce the quantities of fresh oils which anst be supplied. Characteristics of typical cold-rolling mill discharges are present in Table 2. TABLE 2. Characteristics of Typical Effluents,from Cold-Rolling Mills aa Direct' FParameter Recirculated Application Combination Flow - L/Mg 165 1772 1359 Suspended Solids Mg/L 1235 160 624 Oil/Grease - mg/L 22640 1861 1009 Diss. Iron - mg/L 140 22 7.8 pH 6.9 7.2 6.4 18. Acid pickling is the'process of chemically removing oxides and scale from the surface of a metal by means of inorganic acid solutions. The process may be.carried out using one acid alone or in combination. Sulfuric acid or hydrochloric acid are now most frequently used, depending upon the type of material to be pickled. The process encompasses three operations; pickling, rinsing, and fume scrubbing. Wastewater can originate from the rinsing and fume scrubbing steps. Spent pickle liquor is a third source, but while this is lowest in volue it is highest in contaminant levels. Typical characteristics of wastewater from combination acid pickling operations are show in Table 3. * 1 L/Mg 1 liter per megagram n 1 liter per metric ton TABLE 3. Characteristics of Typical Effluents from Acid Pickling Operations Sulfuric Acid Hydrochloric Acid Parameter Parameter Pickle Rinse Spent Fume Pickle Rinse Spent Fume Liquor Scrubber Liquor Scrubber Batch Cont. Batch Cont. Flow - Liters/Mg 960 1020 83 0 a 390 465 300 6 Dies. Iron - mg/L 375 520 41,000 1190 190 1690 52,300 402 Tot. Susp. Sol. mg/L 180 44 1,890 93 0 60 740 490 Oil/Grease mg/L 24 12 14 34 3 30 52 780 pH (Units) 2 - 6 2 -5 1 2 - 3 < 2 1 - 4 <1 < Arsenic mag/L 0.39 0.01 0.18 0.10 --- 0.11 0.01 0.07 Cadmium mg/L 1.1 0.02 0.46 0.20 -- 0.003 0.12 <0.07 Total Chromium mg/L 5.1 <0.001 30 3.2 --- 0.57 13 0.19 Copper mg/L 0.45 0.14 3.0 2.3 --- 0.72 11 0.21 Cyanides mg/L 0.01 0.01 0.006 0.002 --- --- (0.01 <0.01 Lead mg/L 0.14 0.04 1.6 1.5 --- 0.28 310 < 0.26 Nickel mg/L 0.64 0.24 21 1.9 --- 0,78 10 0.23 Silver mg/L 0.01 <0.01 0,29 --- --- -- 0.20 < 0.10 Zinc mgL 16 0.10 2.8 1.2 -- 0.49 15 0.15 Antimony Mg/L --- --- - -- --- -- 0.19 0.86 0.18 Selenium mg/L --- --- --- --- -- --- 0;04 < 0.01 Thallium mgAL --- ---- --- -- -- 0.18 < 0.05 a/ All flows returned to rinse tank - 148 19. Wastewaters generated by hot coating processes, now most widely used except for tin coating, fall into three categories: (a) continuouly run rinse waters (rinses following cleaning operations, flows from fume scrubbing systems, final rinse flows, etc.); (b) intermittent discharges (spent and flux baths, chemical treatment solutions, etc.); and (c) noncontact cooling waters. 20. Wastewater from plating processes originates in the cleani=g, surface preparation, plating and related operations. Constituents include the basic material being finished and applied,-as well as the components in the process- ing solutions. The predominant wastewater constituents are the metal cations (such as copper, nickel, chromium, zinc, lead, tin, etc.) and the anions occur- ring in the cleaning, pickling, or processing baths (such as phosphates, chlor- ides, and various metal complexing agents). 21. Steel scrap, millscale, scarfing residues, refractory material,and used oils and greases are the principal solid or semi-solid waste substances from the rolling and milling operations. Most of these are recovered or re- cycled back into the steel-making process. Scrap metal is used as feedstock, while mill scale (about 90% Fe203) can be recycled to the sinter plant. Re- fractory wastes are separated, with re-usable material going back into the plant and the non-usable portions going to a dump. Used oils and greases are either incinerated or mixed with inert materials prior to disposal to special-dumps. Spent pickling acids from both sulfuric and hydrochloric processes may be re- generated. EFFLUENT LIMITATIONS 22. Effluent limitations for specific elements of rolling and finishing operations, except for electroplating, are presented in Table 4. Materials con- sumed or processed do not provide a basis for applying effluent guidelines, in the case of electroplating processes. For this purpose, limitations are based on the surface area (square meters) of materials plated, for each opera- tion (cleaning, plating, etc.) carried out as part of the plating process. Limiting values are presented in Table 5, for a number of substances found in these wastes, depending upon the process being used. CONTROL AND TREATMENT OF WASTES 23. Discharges of gases, particulates, and fumes can be reduced or elim- inated by use of scrubber and other collecting devices, and these normally*do not constitute a problem.- When dry collecting devices ard used to isolate these materials they may be either recycled into the process, if appropriate, or taken to landfill disposal. When wet methods are.used the materials are subject to whatever treatment is provided for the wastewaters. - 149 - TABLE 4. Effluent Limitations for Steel Rolling and Finishing - Mill Wastewaters Per Mg Steel Processed Waste Source Susp. Oil Diss. Flow Solids Grease Fe PH Liters Grams .ipe & Tube Mill Rot Iolling 6700 67 100 Cold Rolling (Water) .(No wastewater discharges) Cold Rolling (Oils) (No wastewater discharges) Cold Rolling Mill Racirculated 104 3 0.14 0.10 6-9 Dir. Application 1668 104 42 4 6-9 Combination 1043 26 10 1 6-9 Pickling S04 - Satch- (N wastewater discharges) S04 - Batchb .2500 125 25 3 6-9 S04 - coNInuoua/ (No wastewater discharges) S04 - Continuous 1042 52 10 1 6-9 RCI - Batch & Cont.S! (d) 200 40 4 6-9 RCI - Batch & Cont.- () 18 35 4 6-9. Eat Coatingsl/ 5000 250 75 - 6-9 a/ Concentrates + rinses, acid recovery + " , acid ne ntralization. g/ Liquor regen. + rinse neut. + fume scrubbing. / Flow = 4047 L for batch, 2774 L for continuous. ef Neut. liquor & rinses +' fume scrubbing. 2/ Flow M 3524 L for batch, 2252 L for continuous With fume scrubbing. -150'- ZALE 5. Effluent Limitations for Electroplating Plants mg/2/Operation a/ Parameter Non-Water Water Supply Supply Sources and Sources Fish Life Copper 80 75 Nickel 80 4 Total Cr 80 15 Hexavalent Cr 8 1.5 Zinc 80 - Total CN 80 1.5 Fluoride 3200 30 Cadmium 48 2.9 Lead 80 4.4 Iron 160 45 Tin 160 Phosphorous 160 - Total Suspended Solids 3200 pH (units) 6.0 - 9.5 - Flow (liters) 145 - a/ aImum of average daily values in any 30-day period. Yxaimun daily value not to exceed 2 times 30-day average. 24. Treatment technologies are currently available for meeting the wastewater guidelines given in this document. In many cases the treatment is similar, and therefore consideration should be given to combining the wastewater flows for treatment at a common site, when two or more of the operations are carried out at the same time. Treatment processes which either alone or in combination, depending upon the waste characteristics and ultimate disposal, will achieve the limitations given in Tables 4 and 5 are as follows: - 151 - Pipe and Tube Mill a) Primary sedimentation in a scale pit, equipped Eat Rolling with oil skimming devices, followed by floccu- lation with polymer and additional sedimenta- tion in a high rate thickener. b) Solids dewatering with vacuum filtration. c) Filtration of entire flow prior to discharge or recycle. d) Recycle through a cooling tower. Pipe and Tube Mill a) Primary sedimentation in a scale pit equipped Cold Rolling (Water) with oil skimming devices. b) Flocculation with polymer and additional sed- imentation in a high rate thickener. c) Solids dewatering by vacuum filtration. Com- plete recycling following filtration. Pipe and Tube Mill a) Primary sedimentation in a scale pit equipped Cold Rolling (Oil) with oil skimming devices. b) Flat bed filtration, followed by complete re- cycle of all solutions. c) Spent soluble oil solutions and oil skimmings - removed to outside reclamation or disposal. Cold Rolling DMil a) Reuse of rolling solutions. Recirculated b) Treatment of minimm blowdown via oil separa- tio;n, equalization, chemical treatment floccu- lation, air flotation, surface skimming and .etended settling. Cold Rolling Mill a) Treatment of solutions via oil separation, Direct Application equalization, chemical treatment, floccula- tion, air flotation, surface skilming,and long-term settling. Cold Rolling Mill a) Maximum degree of reuse practical. Combination b) Treatment of Blowdown from recirculation system and water from direct application stands via oil separation, equalization, chemical treatment, flocculation, air flo- tation, surface skimming, and extended settling. - 152 - Pickling - So4 a) On-site acid recovery. Batch - Acid Recovery b) Reclaim usable sulfuric acid, and solid ferrous sulfate heptahydrate for outside resale. Pickling - SO4 a) Equalize acid and alkaline wastes; blend Batch - Acid Neut. mix, and aerate. b) Lima neutralization, with polymer addition. c) Extended settling (one day retention). Pickling - SO4 a) On-site acid recovery. Cont. - Acid Recovery b) Reclaim usable sulfuric acid, and also solid ferrous sulfate haptahydrate for outside resale. Pickling - SO4 a) Equalize acid and alkallie wastes; blend, Cont. - Acid Neut. mix and aerate. b) Lime neutralization, with polymer addition. c) Extended settling (one day retention). Pickling - ECI a) Spent pickle liquor regeneration. Liquor Regen. b) Recycle of fume scrubber water with mini- mum blowdown to treatment. .) Absorber vent scrubber once-through to treatment with rinsewater via neutraliza- tion, polymer addition and settling or clarification. d) pE neutralization. Pickling - EC1 a) Equalize acid and alkaline wastes; blend, Liquor Neut. aix, and aerate. b) Treat with lime or caustic soda, add polymer. c) Sedimentation via thickener; vacuu filtra- tion of underflow. d) pH neutralization. - 153 - Hot Coatings a) Separate collection, equalization, blend- ing, and settling. b) Lime and polymer addition. c) One day settling and continuous oil skimdng. Electroplating a) Chemical treatment providing for cyanide destruction. b) Reduction of hezavalent chaots to trivalent form. c) Neutralization and coprecipitation of heavy metals as hydroxides or hydrated oxides. d) Settling and clarification to remove suspended solids. BIBLIOGRAPHY 1. "Environmental Control in the Iron and Steel Industry," International Iron and Steel Institute, Brussels (1978). 2. "The Making, Shaping and Treatingof Steel." Ed. by H. E. McGannon. Ninth Edition. United States Steel Corporation. Pittsburgh (1971). 3. Jarrault, P. "Limitation des Emissions de Polluants at Qualite de L'Air - Valeurs Reglementaires dans les Principaux Pays Industrialises." Institut Francais de 1'Energie. Paris (1978). 4. U. S. Environmental Protection Agency "Guidelines for Lowest Achievable Emission Rates from 18 Major Stationary Sources of Particulate, Nitrogen Oxides, Sulfur Dioxide, or Volatile Organic Compounds." Dec. EPA-450/3-79- 024 Washington (April 1979). 5. T. S. Environmental Protection Agency "Draft Development Document for Proposed Effluent Limitations Guidelines and Standards for the Iron and Steel Industry." Doc. EPA-440/1-79/024a. Washington, (October 1979): Vol. VIII - Sulfuric Acid Pickling, Hydrochloric Acid Pickling, and Combination Acid Pickling Subcategory. 6. U. S. Federal Register. "Interim Effluent Limitations and Guidelines, and Proposed Performance and Pratreatment Standards - Electroplating Point Source Category." V.40 No. 80. Washington (April 24, 1975). - 154 7. U. S. Environmental Protection Agency. "Development Document for Interim Final Effluent LimItations Guidelines and Standards for the Metal Finishing Segment of the Electroplating Point Source Category." Doc. EPA.-440/1-75/040-a. Washington. (April 1975). 8. U. S. Environmental Protection Agency. "Water Quality Criteria." Doc. EPA-R3-73-033, Washington (March 1973). 9. APEA, AWA, WPCF. "Standard Methods for the famination of Water and Wastewater." 14th Edition. American Public Health Association. New York (1975). 10. United Kingdom Department of the Environment, "Analysis of Ra,Potable, and Waste Waters." H. M. Stationary Office, London (1972). 11. U. S. Environmental Protection Agency. "Handbook for Monitoring Indus- trial Wastewaters." Washington (August 1973). *15* THE WORLD ANK OCTOBER 1980 OFFICE OF ENVI30NMrAL AFFAIES IRON AND STEEL IDUSTRY STEIMAIG PROCESSES EFLUENT GUELINES 1. Iron and steel production utilizes a highly complex system, in which iron ora and other raw materials are subjected to a series of pro- cesses to convert them into finished steel products. 2. The series of conversion processes may be divided into five major segments: (a) ore preparation, stntering and pelletizing; (b) by-product coke production; (c) pig iron production; (d) steel pro- duction; and (e) rolling and finishing operations. 3. This. document is one of a series which has been prepared on the individual segments. Each one presents information needed for assessing the enviromental effects of the gaseous, liquid, and solid wastes produced by the operation. In each case the document discusses the manufacturing processes, waste sources and character, effluent limitations based on "best practicable treatment technology currently available and applicable waste treatment methods. A bibliography is also included. 4. The basic difference between iron and steel is in the relative amounts of impurities -n the two metals. The molten iron is saturated with carbon, and also contains undesirable amounts of silicon, manganese, phosphorous, and sulfur. These are removed in the steel-making process. However, in order to impart certain desirable properties to the steel, other elements are added in controlled proportions as part of the steel- making cycle. These are categorized as "residual alloy elements," and are confined mainly to tin, copper, nickel, chromium, and molybdenum. 5. At the present time steel is produced mainly in three principal furnace types or processes - the open hearth furnace, basic oxygen furnace, and electric arc furnace. 156 - OPEN EATE FUENACE Manufacturins Process 6. The open hearth furnace consists of a shallow rectangular basin or hearth, enclosed by refractory lined walls and roof, into which the charge is placed. The charge may consist of all liquid iron, liquid iron and. liquid steel, solid steel (scrap) and liquid iron, or some other similar combination of iron and scrap steel. The charge is heated by a gas flame located at the ends of each furnace. Fuels coummnly used include natural gas, coke oven gas, fuel oil, coal tar, or some combination of these. The choice of fuel will influence the sulfur dioxide generation per ton of steel. 7. There are two principal types of open hearth furnaces - the acid and the basic. The furnace is termed an "acid" furnace where the basiu refractory material consists of silicon sand. Where the basin is Lined with dolomite or magnesite the furnace is a "basic" unit. The basic furnace has the ability to remove phosphorous and sulfur from iron and its ores. The acid furnace, on the other hand, requires a minimn amount of these substanes to operate and can use only selected raw materials. At the and of the heating period the furnace is tapped, at a temperature of approximately 1650C, and the molten steel poured into moldings to form ingots, castings, or other shapes for subsequent processing. Waste Sources and Characteristics 8. Waste products from the open hearth process include slag; oxides of iron emitted as. micron dust; waste gases composed of air, carbon dioxide and water vapor; oxide of sulfur and nitrogen, and oxides of zinc (if galvanized steel scrap is used). Fluorides may be emitted, both in the gaseous and particulate states. Most of the particulate emissions consist of iron oxides (predominantly (Fe.03) generated at an average rate of 12.5 kg per NT of steel produced. 9. In addition to these primary.sources, the secondary sources should also receive attention. These include the hot metal transfer station, the hot metal mizer, the fumes caused by charging of scrap and hot metal, and the fumes emitted during tapping of the vessel. The dusts emitted at these points are largely fine grain iron oxides, and can be recycled to the sinter plant either directly or after some form of treatment. 10. The quantity of particulates will vary according to the gas cleaning systems used. A semi-wet system cools he hot gases before entry - 157 - into the dry precipitators, which remove the particulates from the gas stream. However, a small portion of the particulate matter does escape into the wastewater systems. On the other hand, the wet scrubber system is specifically designed to remove the particulates from the gas stream, and thus results .in larger concentrations of suspended matter. The gas scrubber systems essentially prevent the discharge of gaseous and particulate materials to the atmosphere. L1. Characteristics of a typical raw wastewater from an open hearth furnace are presented in Table 1. This table also includes certain components considered, to be toxic and therefore of significance. 12. Solid wastes originating from the open hearth operation include slag, scrap, slurries, dusts, and refractory materials. The largest quantity of these wastes is slag, the amount of which will depend upon the quality of steel being produced and the ratio of scrap to pig iron in the charged materials. Typically, slag quantities can vary from 70 to 170 kg perHg of liquid'steel.* Slags can be used in blast furnace sinter, in construction, and for fertilizers, and hence do not normally constitute a waste problem. Effluent Limitations 13. Open hearth furnaces are generally equipped with a cleaning system, which can efficiently cool and scrub the hot gases that are produced. The entrained gases will contain one or more of the following: sulfur dioxide, nitrogen oxides, zinc oxide, ferric oxide, fluorides, and particulates. Where the cleaning system is effective, discharges to the atmosphere would be very minor. Where gaseous effluents are discharged to the environment, ambient air quality at ground level should be maintained at or below the following concentrations: S02: Inside Plant fence Annual Arith. mean 100 ug/m3 Max. 24-br peak 1000 /3 Outside plant fence Annual Arith. mean 100 g/m3 Max. 24-hr peak 500 JUg/m3 3 N0 Ann. Arith Mean 100 g/m Fluorides (as El) Ann. Arith Mean 10 3 8-hr Peak 100'Ug/M 3 Particulates: Ann. Geom. Mean 75 jug'aq Max. 24-hr 260 )g/m 14. Effluent Limitations for open-hearth furnace wastewaters, based on application of best practicable control technology presently available, are given in Table 2. These include only suspended solids and pR. Although other pollutants are of concern, effluent limitations are still under de- velopment. Treatment methods discussed below will normally reduce these other substances to acceptable levels. * 1 kg/Mg = 1 Kilogram per megagram - 1 Xg/metric ton. - 158 - ZABLE 1.- Typical Raw Wastewater Characteristics Open Hearth Furnace Semi-vat Wet Parameter System System Flow - L/f(a) Applied 4670 8100 Discharge 288 807 Susp. Solids - Mg/L(b) 500 1100 Fluoride 260 110 Nitrate - 10 320 Zinc - 0.60 200 Chromii * 0.08 - Copper - 0.08 2.0 Cyandes - 0.04 - Nickel - 0.05 Lead- - 0.60 pE - Units 2.0 -3.0 3.0 - 7.0 (a) L/Mg = Liters per megagram of steel produced (b) agI* Milligrams per liter of discharge TABLE 2 - Effluent Limitations for 0aen Hearth Furnace Wastewaters Per Mg Steel Prod. Semi-wet Wet Parameter System System Suspended Solids - & 15 23 Flow - liters A 293 460 pH - units 6.0 - 9.0 6.0 - 9.0 a/ Excluding all non-contact cooling water - 159 - Control and Treatment of Wastes 15. Thres types of gas cleaning systems are in general use for cleaning and scrubbing the hot gases from open hearth furnaces - the dry system,.the.sai-wet system, and the vet system. 16.. By maintaining an exact balance between the water supplied for cooling the gases and the water evaporated no wastewater is produced. This is called the dry system. Cooling of .the hot gases takes place ' in an. evaporation chamber, located at the top of the open hearth building. 17. In the semi-wat system, an excess of water is supplied to the cooling chamber (spark box), thus producing an effluent discharge. The particulata matter collected in both the dry and semi-dry systems il collected as a dry dust, but some plants slurry this dust and convey it to thickeners. 18. In the wet gas scrubber system, the hot gases containing the particulates are conveyed to Venturi scrubbers for cooling and cleaning. Particulate matter is removed as a result of the pressure drop across the throat of the scrubber. Water is supplied to the scrubber to entrap particulates and cool the gases. The wastewater resulting from this system is generally discharged to a treatment facility. 19. The basic type of equipment applied to wastewaters from the gas cleaning and fume collection systems are clarifiers or thickeners for primary sedimentation. These systems are the major source of wastewaters. Clarifiers may be used ahead of the thickeners to remove the heavier solids. Because open-hearth effluents are acidic, provisions should be made to neutralize them. Either lime or caustic are effective for the purpose. Lime, polymer, or other chemicals are added to the clarifiers to aid in settlement of solids and removal of toxic metals. Clarifier sludges are dwatered in vacuum filters; the overflow is normally recycled. Where the overflow is discharged to a stream, it should receive further treatment, such as lagoon settling, prior to release. 20.* The presence of fluorides, heavy metals, and nitrates .will require advance levels of treatment. Line precipitation has been effective in removing heavy metals and fluorides. Both carbonate and hydroxide are suitable. However, the carbonate is preferable since it results in a more dense precipitate, improves solids separation, and yields lower sludge volumes. Nitrates may be removed by anaerobic biological processes, as employed in conventional sewage treatment plants. Nitrate concentrations can be reduced to 10 mg/ . - 160 - 21. Slags, which constitute the largest byproduct from steel making, have several possible uses. They can be recycled into the sinter mix and fed into the blast furnaces. Large lump size slags havn found use in reinforcement of river and canal banks, road building, or as railway track ballast. Slags containing high levels of P205 (usually over 15 percent) can be ground and used as fertilizer. Process scrap resulting from steel pouring can be readily recycled. 22. Fue cleaning dusts and slurries, depending upon their composition, are devatered and fed back to the sinter plant. Metallic components from refractory wastes are separated and reused. The residue is innocuous and convey4d to landfill. Kill scale, if virtually oil-free, can be recycled to the sinter plant. Where the oil content is high, the scale should be dumped and precautions taken to prevent oil pollution due -to runoff. BASIC OXYGEN FURNACE Manufacturing Process 23. The basic oxygen furnace for steelmaking is a relatively recent development, having been first introduced in the 1950's. The process is - now most universally used, both for new installations and for replacements of older facilities. 24. The Basic Oxygen Furnace (BOF) process produces steel in a pear-shaped, refractory-lined open-mouth furnace using a mixture of hot iron (at 13700C), cold steel scrap, and fluxes. Fluxes such as burnt lime (CaO) are used to produce a slag which floats on the molten steel surface and collects impurities during steel production. Pure oxygen is injected to the surface at supersonic velocities (Mach 2), through a water- cooled copper-tipped lance for approximately 25 minutes. The lance is lowered through the open furnace mouth and positioned about 1.5 meters above the surface of the bath. The high velocity of the oxygen results in violent. agitation and intimate mixing with the molten iron. 25. PaPid oxidation of the dissolved carbon, silicon, manganese, phosphorous, and iron occurs. The carbon in the steel bath combines with the oxygen to produce C02 and CO gases which are released from the furnace. The silicon, manganese, phosphorous, etc. oxidize into the slag. Fluaropar (Ca2) is added to the bath mixture to maintain a fluid slag. Burnt lime is added to aid in the production of a floating slag. 26. A BOF installation is generally equipped with two units, although three or more may be found in a few instances. In a dual furnace facility - 161 one furnace is operating while the other is in either the furnace reheat or brick relining mode. Some plants practice "swing" blowing, where one furnace is being blown withoxygen while the other furnace is being charged with raw materials. Wasta Sourcas and Characteristics 27. The vaste products:from the basic oxygen steelmaking process include, heat, airborne fluxes, slag, carbon monoxide and dioxide gases, and,oxides of iron emitted as micron dusts. Also,when the hot iron is poured into ladles or the furnace, submicron iron oxide fumes are released and some of the carbon is precipitated out as graphite. Fumes and smoke are also released when steel is poured into holding ladles from the furnace. Basic oxygen furnaces are equipped with some type cf air pollution gas cleaning systems for containing, cooling and cleaning the. large volumes of hot gases and submicron fumes that are released. 28. During the oxygen blowing cycle, the primary gas constituent emitted is carbon monoxide(CO). The CO will burn outside the furnace if allowed to come in contact with air, but combustion can be retarded by preventing contact of the CO with the outside air. This is referred to as "suppressed combustion." 29. Because the CO gas will burn when in contact with air, electro- static precipitators cannot be used due to arcing in the electric plates and the potential of an explosion. Suppressed combustion systems always utilize wet-type scrubber systems, since there is always some air leakage into the cleaning systems. An open hood mounted above the furnace mouth conveys gases and fumes to the air pollution cleaning systems. 30. Four principal types of gas cleaning systems are currently in use: dry, semi-wet, wet open combustion, and wet suppressed combustion. The wet suppressed combustion systems are the most widely used today. 31. In a dry precipitator system, an exact balance is maintained between water applied to cool the gases and that evaporated in the cooling process. No effluent is discharged in this case. Particulate matter is collected as dry dust. In the semi-wet method an excess of water is supplied to a chamber (spark box) to cool the furnace gases, thus producing a liquid discharge. The particulate matter is also collected as a dry dust. 32. The wet gas cleaning systems involve the use of quenchers and high-energy Venturi scrubbers. The hot gases, containing large amounts of 162 - particulates generated in the steel production process pass through a primary quencher. The function of the quencher is to cool the gases with water and remove the heavier particles contained in the gas stream. After the quenchers, the gases pass to the Venturi scrubbers for final cleaning. Particulate matter is removed. as the result of a pressure drop across the .throat of the scrubber. Water is applied to the scrubber to entrap the particulates, and the resulting effluent is pumped to the primary quencher. The quencher effluent is discharged to a treament facility. 33. Wet scrubber systems are used in both the open and suppressed combustion type furnaces.. Open combustion units require a greater pressure drop across the scrubber throat than is the case in.'suppressed combustion units. The particulate matter generated by a suppressed system is larger and easier to remove from the gas stream. On the other hand, open systems allow for more complete combustion due to the presence of excess air and thus result in smaller particles in the gas streams. 34. The fume collection scrubber and gas cleaning systems are the only contact cooling discharge from steelmaking. Othew water uses are for non-contact cooling, and these are not contaminated as they flow through the process. Suspended solids, tuorides, and pH are.the quality parameters of greatest significance. Raw effluent characteristics of typical waste- water from scrubber and gas cleaning systems are given in Table 3. TABLE 3 - Characteristics of Typical Raw Waste Waters from Basic Oygen Furnaces Flow Fluorides Susp. Sol. Source L/Mg mg/L mg/L pH Semi-Wet 1790 2.4 300 11.6 Wet-Open Comb. 3000 8.6 4000 9.9 Wet-Suppr. Comb. 3380 810 9.8 Effluent Limitations 35. Gas and fume emissions can be adequately removed from the system, and hence there should be no discharge of air pollutants from a basic oxygen furnace operation. Stack discharges of particulates should be maintained at 50 mg/n3 or less. 163 36. Effluent limitations for wastewaters are presented in Table 4. These limitations are based on application of best practicable treatment currently available. TABLE 4 - Effluent Limitations - Basic Oxygen Furnace Wastewaters Flow Fluoride Susp. 1. 1 Sol. g Per Magagram Produced Pg II Semi-Wet (No wastewater Discharges) Wet-Open Comb. 630 - 31 6-9 Wet-Suppr. Comb. 210 - 5 6-9 Control and Treatment of Wastes 37. Fuae and gas cleaning systems discussed above, normally used with basic oxygen furnaces, are effective in controlling and essentially eliminating air emissions from the operation. 38. Liquid wastes from a semi-wet system undergo primary dedientation in a thickener, to which coagulant aids are usually added. The thickener sludge is dewatered by a vacuum filter, and the filter cake disposed of to landfill or other appropriate means. The filtrate from the vacuu units is returned to the thickener. The thickener overflow is completely recycled to the process, thus resulting in.zero discharge of effluent. 39. Liquid wastes.from a wet-open combustion system undergo solids separation in a clarifier, as a first step. Wastewater is then pumped to a thikener for sedimentation, where coagulant acids may be added. The under- flow (or sludge) from the thickener is dawatered in vacuum filters, and the filter cake conveyed to landfill disposal. The filtrate is returned to the thickener. About 85 percent of the thickener overflow is recycled to the process. The remainder is acid neutralized and discharged. Makeup water is added to the recycle systems to compensate for blowdown and evaporation losses. 40. Wastewaters from a wet-suppressed combustion system are first subjected to primary treatment in a clarifier to separate the solids. It then flows to a thickener, to-which a coagulant has been added. Thickener sludge goes to the vacuum filters, from which the cake goes to landfill 164- disposal and the filtrate is returned to the thickener. Some 95 percent of the thickener overflow is recycled to the process. The remaining 5 percent undergoes further clarification. The sludge from this unit goes to the vacuum filters, while the affluent is acid neutralized and discharged. 41. Fluoride levels are not significantly affected by the treatment methods discussed above. The levels generally found are higher than would be acceptable for a receiving water used for public water supplies. Therefore, existing fluoride levels should be considered in terms of the use to be made of the receiving waters. Fluoride reduction can be achieved through applica- tion of lima reduction methods. 42. Disposal of sludges, filter cakes, and other solids may be to landfill or to process recycling via the sintering plants. For landfill dis- posal the sludge is often dried to a higher solids content to reduce the volume. In some cases the presence of zinc in the sludges may make them un- suitable for the sinters, since they could cause damage in the blast furnace operations. ELECTRIC ARC FURNACES Manufacturing Process 43. The electric arc furnace receives iron from the blast furnace, along with scrap metals and fluming materials to produce steel. Until recently, this process was used primarily for production of alloy steels, but it is now used to produce a wide range of carbon and specialty steel compositions. 44. High quality and alloy steels are produced in refractory-lined cylin- drical furnaces, utilizing a cold steel scrap charge and flazes. Sometimes a lower grade of steel will be produced in the open hearth or basic oxygen fur- nace and charged to the electric unit. This is known as duplexing. 45. The heAt for the furnace is provided by passing an electric current through the scrap or steel bath, by means of three triangularly spaced cylin- drical carbon electrodes inserted through the furnace roof. The electrodes are consumable and oxidize during the process. Furnaces range in charge capa- city from about 20 to nearly 400 metric tons. Diameters range from 2 to 9 meters; heat cycle time is 4 to 5 hours. 46. Production of some high-quality steels requires the use of two different slags for the same heat, referred to as oxidizing and reducing slags. The first slag is removed from the furnace and new fluxes added for the second slag. The heat cycle generally consists of charging, meltdown, moltan metal period, oxidizing, refining, and topping (or pouring). Pure oxygen is some- times lanced across the batch to speed up the oxidation cycle which, in turn, will reduce the consumption of electrical power. - 165 47. Within the past decade a new process, called the Argon Oxygen De- carbonization (AOD) process has been used in conjunction with electric are furnaces. When the electric furnace is used in conjunction with the AOD, the electric are unit functions as a carbon steel scrap smelter. The bat metal charge is then transferred to the AOD unit for final refining. This elimi- nates the double slag process required when electric are furnaces are produc- ing stainless and alloy steels. The AOD process allows for better control of the alloy steel composition. Waste Sources and Characteristics 48. Waste products discharged from the electric are furnace process include smoke, slag, carbon dioxide and monozide gases, and oxides of iron emitted as submicron fumes. Other contaminants, such as zinc oxides from galvanized scrap, will also be discharged depending upon the type and quality of scrap used. Scrap containing large quantities of oil will yield heavy reddish-black smoke as the oils are burned off at the start of the meltdown cycle. Nitrogen.oxide and ozone are discharged from the arcing of the elec- trades. 49. Gases and particulate matter can be effectively removed by various types of gas cleaning systems, which will limit or aliminate the discharge of these contanants. Three types of gas cleaning systems are most widely used: dry, semi-wet, and wet. Some. of the gas cleaning and resulting opera- tions, however, will result in a contaminated wastewater discharge. 50. Dry gas cleaning systems.are generally of two types: baghouses and electrostatic precipitators. A baghouse consists of a series of cloth or fiberglass bags which filter the water-cooled furnace gases. The furnace gases are first quenched by water sprays in a spray chamber and are then in- troduced to the baghouse. The bags are periodically shaken free of the dust which is then collected in hoppers located at the bottom of the baghouse structure. The dry dust thus collected is removed and landfilled. Another dry method of gas cleaning is the electrostatic precipitator, which involves the use of electrically.charged metal plates to capture the charged particu- late matter entrained in the gas stream. As for the baghouse method, the gases mst be water cooled prior to precipitator cleaning. Cooling of the furnace gases is accomplished in an evaporation chamber to which water is applied. The dust captured by the electrostatic precipitator is collected in a hopper and conveyed to landfill. Neither of these two gas cleaning systems result in an aqueous discharge and therefore do not require any water pollution control equipment. 51. The semi-vet system also involves the use of electrostatic precip- itators but results in an aqueous discharge. This system water-cools the furnace gases in a spark box chamber which is about one-third the size of the evaporation chamber used for a dry system. Water is oversupplied to the spark box to ensure adequate cooling and thus results in an effluent from the system. 166 - 52. Wet gas cleaning systems generally involve the use of high energy Venturi scrubbers. The hot particulate-laden gases emanating from the furnace are conveyed to Venturi scrubbers for cooling and cleaning. Particulate matter is removed as a result of a pressure drop across the throat of the scrubber. Water is supplied to the scrubber to entrap the particulates and to cool the gases. The resulting water effluent is discharged. 53. Wastewatar characteristics are affected mostly by the type of gas cleaning system used, the principal difference being in the quantity of fume particulates. The electric are furnace has two main water systems: (a) electric are furnace door, electrode ring, roof ring and cable and transformer cooling; and (b) fume collection scrubber and gas cooling. Only the scrubber and cooling system is important from the pollution standpoint, since all other water uses are for noncontact cooling purposes. 54. The parameters of major interest are the suspended solids and pH levels in the effluent. Characteristics of a typical wastciater effluent are shown in Table 5. TABLE 5. Characteristics of Typical Electric Arc Furnace Wastewaters Susp. Type of Flow Solids System L /M& mg/L PH Dry (No liquid discharges) Semi-Wet 630 2200 6-9 Vet 8800 3400 6-9 55. Wastewaters may also contain fluorides, zinc, copper, lead and other pollutants depending upon raw materials used, extent of recycling, and other factors. 56. Dusts, particulates, sludges, and other solid materials will be pro- duced as part of the operation and waste control processes. These will vary in quantity and must be considered on a plant-by-plant basis. Effluent Limitations 57. As previously stated, an effective fume and gas cleaning system will eliminate the discharge of any emissions to the atmosphere. Gaseous emissions are to be maintained at or below the limitations shown in paragraph 13, above. The limitations on wastewates from semi-wet and wet gas systems, - 167 - based on using best practicable treatment currently available, are shown in Table 6. TABLE 6. Effluent Limitations - Electric Are Furnace Operations Suspended Solids Source AMs at PI Semi-wet System (No wastewater discharges) Wet System 26 50 6-9 Control and Treatment of Wastes 58. Gas cleaning systems, as described above, will adequately control or prevent the discharge of gaseous and particulate emissions to the atmos- phere. Where semi-wet or wet systems are used the materials are transferred to the liquid mediun and therefore require treatment of the resulting waste- waters. 59. The treatment components required for discharges from the two gas cleaning systems are essentially the same. The basic treatment uses a clari- fier or thickener for primary sedimentation, following a classifier or other primary solids separation device to remove the heavier solids. The thickener underflow (or.sludge) is dewatered in vacuum filters. Filtrate from the vacutm unit is returned to the thickener. Chemical flucculation can be used to aid in the settlement of solids and the removal of toxic metals and fluoride. Tn the semi-wet system the thickener overflow is completely recycled. In the wet gas system a part of the thickener overflow is discharged to receiving waters. 60. Additional levels of treatment may be required, where significant quantities of inorganic toxic pollutants and fluorides are present. Several methods have been successful in controlling these substances. These methods include lime and polymer flocculation, Lime precipitation, and precipitation with sulfide compounds. The use of sulfide compounds has been more useful in reducing effluent metal concentrations than in the case of lime flocculation. 61. Significant quantities of sludge are generated from sedimentation of gas cleaning system wastes. These may be disposed of to landfill or to the sintering plant, following drying to a fairly high solids content. The presence of zinc in the sludge may make it unsuitable for recycling to the sinter plant without dezincing. The dusts collected in the dry system baghouse may be transferred to a landfill site for disposal. - 168 - BIBLIOGRAPHY 1. "Environmental Control in the Iron and Steel Industry," International Iron and Steel Institute, Brussels (1978). 2. "The Making, Shaping and Treating of Steel". Ed. by H.E. MaGannon. Ninth Edition. United States Steel Corporation. Pittsburgh (1971). 3. Eussel, C.S. and Vaughn, W.J. "Steel Production: Processes, Products and Residuals". Resources for the Future. The Johns Hopkins University Press, Baltimore and London (1976). 4. United Nations Development Organization, Development and Transfer of Technology Series No. 11 "Technological Profiles of the Iron and Steel Industry". United Nations, New York (1978). 5. U.S. Environmental Protection Agency "Draft Development Documents for Proposed Effluent Limitations Guidelines and Standards for the Iron and Steel Industry". Doc. EPA 440/1-79/024a. Washington. (October 1979): Vol. IV - Basic Oxygen Furnace and Open aarth Furnace Subcategories. Vol. V - Electric Are Furnace, Degassing, and Continuous Casting Subscategories. 6. U.S. Environmatnal Protection Agency "Guidelines for Lowest Achievable Emission Rates from 18 Major Stationary Sources of Paxticulate, Nitrogen Oxides, Sulfur Dioxide, or Volatile Organic Compounds". Dec. EPA-450/3- 79-024 Washington (April 1979). 7. U.S. Environmental Protection Agency. "Industrial Guide for Air Pollution Control". Doc. EPA-625/6-78/004. Washington (June 1978). 8. Jarrault, P. "Limitation des Emissions de Polluants et Qualite de L'Air - Valeurs Reglementaires dans les Principaux Pays Industrialises". Institut Francais de 1'Energie. Paris (1978). 9. APHA, ANWA, WPCF. "Standard Methods for the Examination of Water and Wastewater". 14th Edition. American Public Health Association. New York (1975). 10. United Kingdom Department of the Environment, "Analysis of Raw, Potable, and Wasta Waters". H.M. Stationery Office, London (1972). 11. U.S. Environmental Protection Agency. "Handbook for Monitoring Industrial Wastewaters". Washington (August 1973). 12. U.S. Environmental Protection Agency. "Water Quality Criteria". Doc. EPA- R3-73-033, Washington (March 19/3). -169- THE WORLD BANK SEPTEMBER 1982 OFFICE OF ENVIRNMTAL AFFIPS LEAD SAMPLING AND ANALYSES 1. This document covers the sanpling and analyses for determining inorganic lead concentrations in the gaseous and liquid wastes from indus- trial operations as well as other sources discharging to the environment. For gaseous and particulate discharges, both stationary and ambient sources will be discussed. 2. Stationary sources consist mainly of primary and secondary lead smelters. Primary plants are those producing lead from lead sulfide ore concentrates by pyrametallurgical processes. Secondary plants are those producing lead from scrap materials, such as nanufacturers of storage bat- tery conponents. Ambient source monitoring measures the discharges reach- ing the environment from these installations, as well as discharges from automobile exiausts and other similar sources. - STATIONARY SOURCE AIR MONITORIG .Sampln 3. Stack sanpling ports are used for this purpose. These are to be located at least eight stack diameters "downstream" of any bends, constric- tions, - abatement equipment, or other flow disturbances. If this is not possible, then the sampling location should be at least two stack diameters "upstream" of any flow disturbances. Where these criteria cannot be met a stack extension beyond the discharge and nay be required. Ports should be installed flush with the stack wall, and extend outward frcm the exterior wall for between 5 and 20 centimeters, unless additional extension is required for installation of gate valves or other appurtenances. 4. If the sun of the stack inside diameter plus one port length is less than 3 meters, two ports should be installed on diameters 90 degrees apart. If the sum is greater than 3 meters, then four ports should be in- stalled on diameters 90 degrees apart. 5. Because particulates exhibit inertial effects and are not uni- formly distributed within a stack, the sarpling procedure is more complex than for gaseous pollutants. Samples are taken at several traverse points along the stack diameters (or cross-secticn). For a rectangular cross sec- tion the equivalent diameter is to be determined from the equation De 2 where De = the equivalent diameter, L = the length, and W = the width of the cross-section. 6. When the eight and two-diameter criteria can T:e met, the minimum number of traverse points should be (a) twelve, for circular or rectangular stacks with diameters (or equivalent diameters) greater than 0.61 meter; (b) eight, for circular stacks having diameters between 0.30 and 0.61 meter; and (c) nine, for rectangular stacks having equivalent diameters be- tween 0.30 and 0.61 meter. 7. The stack sampling train for determining inorganic lead when using the atomic absorption spectropbotometer procedure is shown schemati- cally in Figure 1. It is important in the sampling of particulates that samples, be withdrawn isokinetically, i.e. the linear velocity of the gas entering the nozzle should be equal to the velocity of the undisturbed gas stream at the .sample point. 8. The filter holder uses a glass fiber filter. A temperature of 120 + 14* C is to is to be maintained by a suitable heating system sur- rounding the filter holder. The very fine particles and the vapor fraction which pass through the filter are trapped by the impingers. 9. The sanpling period is to be at least one hour's duration, and longer if required to extend over a conplete project cycle. The miniwm volume should be in the range of 0.85 to 0.9 dry standard .,cubic meter (dscm) per hour. 10. When using the dithizone analytical procedure, a different sanp- ling train is used. This is shown schematically in Figure 2. The train consists of a 0.45 micron membrane filter, or equivalent, (to capture larger particles) followed by a sanpling tube containing activated carbon (to capture particles smaller than 0.45 microns). Generally, a total sam- ple of not over 150 to 200 cubic meters is collected Analyses 11. The preferred methods of analysis for stack samples is "Method 12", as designated by the U.S. Ehvironmental Protection Agency. In this method the particulate and gaseous lead emissions (consisting mainly of lead oxides) are withdrawn fra the source and collected on a filter and in dilute nitric acid. The collected samples are digested in acid solution and analyzed by atomic absorption spectrophotenetry, using an air acetelyne flame. Ch the basis of tests on samples with concentrations ranging ftcrn 0.61 to 123.3 mg Pb/m3, the within-laboratory precision of the method var- ies frmi 0.2 to 9.5 percent. 12. High concentrations of copper may interfere with the Pb analysis at the 217.0 rinm line of the instrument. This interference can be avoided by analyzing the sample at the 283.3 rm line. (nm = nanameter = 10-9 meter) 13. Where atamic absorption spectrophotanetry cannot be used, due to unavailability of equipnent or for other reasons, the colorimetric dithi- zone method, as published by ASTM, may be used. The method measures par- ticulate lead concentrations ranging from 0.01 to 10.0 micrograms per cubic meter. It will also measure the vaporous lead, captured on the activated carbcn column, at concentrations below 0.5 microgram per cubic meter. IEMPE RATURE SENSOR ROBE M - HEAlf0 AREA TiE RMOMETER 4 ) EMPERATUIE . THERMOMETER FROB ,/~ ALLVALVE TO1uB STOR . \ -FILTER HOLDER TIEMMTR CHK PROBE STAC*K VACUUM *0* LINE REVERSE-TYPE1e_* 1 PITOT TUBE I .PITOTMANOMETR IMPINGERS ICE BATH r BY-PASS VALVE ORI1FICE.. VACUUM GAUGE MAIN VALVE THERMOMETERS ORY GAS METER AIR-TIGHT PUMP Figure 1 Inorganic Lead Sampling Train (From U. S. Federal Register, p. 16576, April 16, 1982). - 172 - INLET Y 7-mm TUBING E 0 24/40 i GLASS JOINT .- USE NO STOP COCK GREASE 24-mm ID. GLASS TUBE ACTIVATED CARBON (10.0 GRAMS ..... OF NO. 20-50 MESH SIZE) MICRON-SIZE GLASS WOOL (901R0- SILICATE GLASS) LIGHTLY PACKED TO A DEPTH OF 6mm-8mm GLASS WOOL SUPPORTS 5 o - 7-mm TUBING ACTIVATED CARBON VACUUM GAS SCRUBE-q PUMPF""METER FIGURE 3 47mm FILTER HOLDER AND GLASS FIBER FILTER Figure 2 - Activated Carbon Scrubber and Sampling Train (From ASTM Test Method D3112-77) - 173- 14. For the dithizcne nethod, the filter sample is digested with ni- tric and perchloric acid, and the dissolved lead then determined colorim- itrically. For the carbon column portion of the samples, the lead is sep- arated from the activated carbn with hychuxochloric and nitric acids, filt- ered, and the lead in the filtrate determined colorimetrically. 15. In the presence of weak amnoniacal-cyanide solution (pH 8.5 to 9.5) dithizone gives colored complexes with bismuth, stannous tin, nono- valent thallium, and indium. In strong arnoiacal-citrate-cyanide solu- tions (at pH of about 11.0), the dithizonates of these ions are unstable and are only partly extracted with chloroform-dithizone solution. The method has been found to be without interference from 20 micrograms of bisnuth, 20 of novalent thallium, 100 of stannous tin, and 200 micrograms of trivalent indium. The ASIM procedure includes various steps to reduce the effects of these and other interfering ions. AMBIENT AIR MONITORING Sanpling 16. When the atanic absorption spectrophotaneter is to be used for the analyses, ambient air sanples are best collected with a high-volume air sampler. This. type of sampler utilizes a vacuum-like device to draw large volumes of air through a fiber glass filter on which particulates are col- lected for measurement and analysis. The sampler nust be capable of pass- ing envircomental air through a 406.5 cm2 portion of a clean glass fiber filter at a rate of at least 1.70 m/;nin. The notor must be capable of 24-hour continuous ' operation, which is usually the nornal sampling period. 17. The glass-fiber filters should have a collection efficiency of at least 99 percent for particles 0.1 to 100 microns in size. If other filter naterials are used, care must be taken to use filters that contain very low background concentrations of the pollutant being investigated, which in this case would be lead. 18. The total air flow through the sanpler is based on rotameter readings taken ,at the beginning and end of the sanpling period. , The pro- cedure assumes that the decrease in flow is linear with time and that the 24-hour rate as recorded is a representative average of' the entire sampling period. 19. While the high-volume sampler does not entrap all of the vapor fraction it is considered that the portion not entrapped is widely dis-. persed and highly diluted by the time the plume reaches the ground. Ambi- ent sanpling, for the nost part, is done outside the plant fence. There- fore, it is generally assumed that the particulates collected by the samp- ler contain essentially all of the lead present in the ambient air. 20. When the dithizone analytical method is to be used, the sampling train shown in Figure 2, and briefly described above, is to be used. - 174 - Analyses 21. The U.S. Ehvironmental Protection Agency procedure designated as "Reference Method for the Determination of Lead in Suspended Particulate Matter Collected from Ambient Air" is * the method of choice for determining the lead-content of sanples collected a the high-volume glass-fiber filter. 22. Lead in the particulate uatter collected by the fiber-glass fil- ter is solubilized by extraction with nitric acid (HNO3) facilitated by heat, or by a mixture of HNO3 and hydrochloric acid (HCl) facilitated by ultrasonication, which will extract metals other than lead fron* the partic- ulate natter. 23. The lead content is determined by atomic absorption spectrophoto- metry, using an acetylene flame, the 283.3 or 217.0 rm lead absorption line, and the optinm instrumental operating conditions recomnended by the nanufacturer. 24. The typical range of the method is 0.07 to 7.5 micrograms Pb/m3, assuming an upper linear range of analysis of 15 micrograms/ml and an air volune of 2400 m3. . 25. Both chemical and light scattering interferences are possible with this method. Most analysts report an absence of chemical interfer- ences. Where interferences do occur, the published method includes the steps necessary to reduce or eliminate both types of interferences. 26. When the USEPA method cannot be used due to lack of proper in- strumentatian or for other reasons, then the ASIM dithizone method may be used. The procedure is briefly described above. WASTEWATER MONITORING Sampling 27. Wastewater sample collections should be Iased on the actual pro- cess operations. Conposition of the effluents will vary either with time or flow. Ccrposite samples, consisting of portions collected at intervals over a 12 to 24-hour period, are considered to be most representative, al- though grab or spot samples nay be collected for special purposes. 28. Where the conposition varies according to time, the sanples should be of equal volume. Where the samples vary according to the flow, the sample size should be in proportion to the flow. For situations when samples must be collected at frequent intervals over long periods, the use of autenatic samplers is recomended. I 29. Preliminary sampling throughout the plant, to include all import- .ant sources of the pollutant, will indicate the location and mininun number of sanpling stations. It is important to know the lead content of individ- ual waste streams within the plant, as well as in the final effluent. Since flows nust also be determined, it is considered best to combine the flow measurement station with the sampling station whenever possible. 175 - - 30. Sampling stations should be located so that (a) the flow of the waste streans is known or can be determined; (b) the staticn is easily ac- cessible, with no safety hazards for personnel; and (c) the wastewater is thoroughly mixed. When flumes are used for measuring flows, the sample is usually well-mixed. If weirs are used to measure flows, the, waste stream ray not necessarily be well-mixed, since solids tend to settle behind the barrier while floating naterial passes over the weir. 31. The total volume of sanple to be collected will depend upon the analytical procedure to be used. The volume should be sufficient to allow for repeating the analysis, supplying samples to other laboratories for check purposes where indicated, and similar. factors. Care should be taken to properly preserve the sanples during the -sampling period and in trans- porting to the laboratory, so that the composition does not change between collecticn and analysis. Analyses 32. Atcmic absorption spectrcphotanetry is the method of choice for routinely determining lead in waste waters, as is the case with air-borne efflueits. The method is rapid, sensitive, and specific for the particular metal involved. The procedure is described in detail in the- -Fifteenth Edition of "Standards Methods for the Examination of Water and Wastewater" . 33. Where the atcmic absorption spectrophotometer is not available, lead concentrations may be determined by the dithizone method, also des- cribed in "Standard Methods". In this procedure, an acidified sample of lead is mixed with. anmniacal citrate-cyanide reducing solution and extrac- ted with dithizcne in chloroform, to form a cherry-red lead dithizanate. The color of the mixed solution is then measured colorimetrically. The procedure may be subjected to interference from bisnuth, stannous tin, and monovalent thallium. Modifications are provided to avoid interference from these elements, particularly excessive quantities of bisnuth or tin. BIBLIOGRAPHY 1. U.S. Code of Federal Regulations, Title 40, Sub-Chapter C, Part 60, Sutpart L, "Standards of Performance for Secondary Lead Smelters" and Subpart R, "Standards of Performance for Primary Lead Smelters". Office of the Federal Register, GSA, Washington, (July 1, 1981) 2. U.S. Federal Register. "Standards of Performance for New Stationery Sources; lead-Acid Battery Manufacture" . Vol. 47,. No. 74, pp 16564- 16579. Washington. (April 16, 1982). 3. American Society for Testing and Materials (AS7M). "Standard Test Method for Lead in the Atmosphere by Colorimetric Dithizone Pro- cedure". ANSI/ASTM D-3112-77. Philadelphia (1977). 4. U.S. Code of Federal Regulations, Title 40, Subchapter C, Part 50. "National Primary and Secondary Ambient Air Quality Standards". Office of the Federal Register,. GSA, Washington (July 1, 1981). 176 - 5. American Public Health Association. "Standard Methods for the Exami- naticn of Water and Waste water ". 15th Edition. New York (1980). 6. "Treatment of Industrial Effluents". Edited by A.G. Callely, C.F. Forster, and D.A. Stafford. Halsted Press Division of John Wiley & Sons, Inc. New York (1976). - 177 - THE WORD BAK OCTOBER 1980 OFFICE OF ENVRO TAL AND EEALTH AFFAIRS HEA PROCESSING AND RENDERING TDUSTRIAL WASTE DISPOSAL 1. Meat processing plants are those whose operations are confined to dressing and curing of carcasses, to preparing specialty and other- products, and to cannig, following slaughter of the animals . The raw input generally consists of carcasses of cows and bogs. Processing operations may be carried out in conjunction with a slaughterhouse or at a separate location. Slaughter- houses will not be covered in these guidelines since they are the subject of a separate document. 2. A rendering plant is one which converts the inedible and discarded remains of the anima (such as fats, bones, heads, blood, and offal) into use- ful by-products such as lard, tallow, oils and proteinaceous solids. Rendering may be done on-site as an adjunct to processing operations or off-site as an independent operation. IDUSTRIAL PROCESSES 3. Meat processing produces a number of products which may be generally groaped as follows: - Meat cuts and related products (such as steaks, chops, roast and hamburgers) for hotels, restaurants and private consumers; - am-s and bacon, requiring curing in pickling solutions followed by cooking and smoking, cooling, and slicing or other preparation prior to packaging and marketing; - Comminuted meat products, requiring substantial size re- dntion and izing. The final product will be in a casing or container, such as sausages or sausage meat; and - Canned products such as hams, sandwich spread and pet foods. 4. Most plants will produce a mix of these, although some do confine themselves to one specialty only. 5. Plant waste waters usually discharge through catch basins, grease traps, or flotation units. While there is a waste reduction benefit, the basic purpose of this procedure is to separate the greases for later by-product recovery, rather than to provide waste treatant per se. - 178 - 6. In the rendering operation, the bulk material, (offal, bones, trim- mings, etc.) are dumped into a pit and then conveyed to a grinder, when grind- ing is necessary. The raw mixture is next heated or cooked to melt the tallow or grease and permit separation from the proteinaccous materials. The protein- aceous material, also known as "cracklings", is normally screened and ground to produce a meat and bone product. Both edible and inedible by-2rodnet result foa the r aendring operation, depending upon the composition and freshness of the raw materials and on the procedures used. SOURCES AND CEARACTE OF WASTES 7. Liquid wastes, carrying various amounts of solids are the major concern in this industry. Solid wastes, resulting mainly from screening and housekeeping, may also be of concern but this will depend upon the degree of separation and by-product recovery practiced at the individual plant. Other than odor problems, gaseous wastes are not significant. The purely hazardous types of components, such as heavy metals and pesticides, are not normally found in meat processing effluents. 8.* The most important parameters applicable to liquid effluents are 5-day biochemical oyxgen demand (30D5), total suspended solids (TSS), oils and greases (0 + G), hydrogen-ion concentration (pR), and facal coliform organisms. In addition, phosphorous may be of concern in meat processing while ammnia may be of signifiaance in rendering operations. 9. Odors can originate from both point and non-point sources. They generally result from bacterial activity on organic matter, the heating of animal materials, and the handling of warm animal residues. 10. The processing of carcasses and remains adds to the waste loadings as follows: - Preparation of meat materials. Large volumes of highly contaminated waste are generated in thawing raw materials by water immersion. The breaking, cutting, trizming, and boning of meats for further processing generates very little flow and waste load. Waste loads originate primarily from cleaning the equipment used for grinding, mixing, blending, and emulsifying the processed materials into other products. Additional wastes are generated from extrusion, stuffing, or molding operations related to forming or containeriza- tion of the product zixture prior to cooking. - Pickling or curing operation. This involves use of a solu- tion for pickling hams, bacon and other products. Wastes result from the nature of the process and the washing down of floor areas. - Product cooking. Products are generally cooked in ovens (smakahouses) or in wet cookers using live steam or hot water. Wastes are generated principally from the spray- ing applied to drench the products after cooking and from equipment cleaning. - 179 - -- ag nii. Large volumes of water are generated in the canning operation. Plants using automated canning lines will discharge less water and wastes from this source. 11. In the rendering industry the major waste sources are from raw materials receiving, condensing cooker vapors, plant cleanup, and truck and barrel washing. These mainly contain organic matter and suspended solids, along with various inorganic substances. The waste materials found in the efflunnts include blood, meat and fatty tissue, body fluids, hair, dirt, manure, bide curing solutions, tallow and grease, meal products, and caustic or alkaline detergents. 12. Typical raw waste characteristics for various types of operations are shown in Table 1. Table 1. Typical Raw Waste Characteristics - Meat Processing and Rendering. Flow BoD3 TSS 0 + G a/ Type of Plant (Liters) Per Megagraz of Final Product (TP) Small Processor b/ 3,330 1.1 0.80 0.49 Meat Cutting 600 0.52 0.64 0.12 Sausage and Lunch Meats 9,600 2.6 3.5 1.2 lam Processing 10,600 5.5 3.3 2.4 Meat Canning 11,200 12. 4.5 2.1 Per Megagram Raw Material Input (3M) Rendering c/ 3,260 2.2 1.1 0.72 a/ 0 + G - Oils and Greases b/ Total production = less than 2,700 Xg/day c/ Following in-plant materials recovery using catch basins, skimmers, etc. * 1 magagram = 1 metric ton - 180 - Table 2. Daily Magdxman Effluent Limitations - Meat Processing and Rendering Plants Type of Plant -a/ BOD TSS Oils + Greases Per Mega5ram of Final Product (FP) Small Processor b/ (No discharge allowable) c/ Meat Cutting 0.02 0.02 0101 Sausage and Lunch Meat 0.28 0.38 0.20 Ram Processing 0.32 0.42 0.22 Meat Caming 0.34 0.44 0.26 Per Megagram law Material Input (EM) endering Plant d/ 0.14 0.20 0.10 a/ For all plants: pH = 6 to 9; Facal Coliform MN 400/100 ml. / Total Production = less than 2,700 kg/day. c/ May be discharged to munIcipal system with adequate pretreatment. j/ For plants where hide curing is carried out, the following additive adjustments are to be made: OD5 = 6.2 I (no. of bides) (Kg Of EM) TSS * 12.6 X (no. of hides) (Kg of RM) 181 - CONTROL AND TEATMENT OF WASTES 13. As has already been stated, the principal and usually only air pol- lution problem connected with the maat processing and rendering industries is that of odors, particularly in the rendering operations. Other possible sources are the smokabouse operation and the dryers. Air scrubbers are most commonly used. for odor control. To avoid increasing the liquid waste loading the scrubber water may be recycled if the air is not too heavily loaded with smoke and grease particles. 14. Liquid waste discharges to receiving waters can be reduced in volume an4 concentration through effective water management, in-plant waste controls, process modifications, and by the use of treatment systems. The wastes may also be released to micipal systems provided that certain pretreatment measures are taken prior to discharge from the industry. 15. In-plant control techniques include the use of screening, skimming, or settling (alone or in combination) to reduce the discharge of solids. Be- cause these solids, to a large degree, can be processed into saleable by-products this treatnt step is routinely employed in most plants. Excess solids can be hauled to a landfill. Where possible, steps should be taken to prevent useful materials from reaching the floor in order to reduce general cleanup operations. This conserves water and reduces effluent flows. Catch basins can be employed for separation of greases and other solids. Dissolved air flotation systems have also been effective in removing grease and finely suspended solids. 16. Biological systems can generally be effective for treating these wastes, particularly where in-plant "primary" treatment for recovery of useful solids is being utilized. Secondary treatment, such as anaerobic processes, aerobic lagoons, the activated sludge process, and high-rate trickling filtration are the techniques most frequently used. 17. If treatment beyond "secondary" is required the effluent may be sub- jected to slow sand filtration, microstraining, spray-irrigation, ion-exchange, or 'other tartiany systems. SUGGESTED REFERENCES 1. "Information Sources on the Meat Processing Industry",-N Industrial Development Organization. Doc. UNO/LI3/SER.Dl/Rev.1 New York (1976) 2. Jones, Rarold R. "Pollution Control in Meat, Poultry, and Seafood Processing". Noyes Data Corporation., Park Ridge, N.J., and London (1974). 3. Lavie, Albert, "'The Meat Fandbook", AVI Publishing Co. Westport, Conn. C1963). 4. U.S. Environmental Protection Agency-Development Documents for Effluent Limitations Guidelines and New Source Performance Standards for the. Meat Products and Rendering Processing Point Source Category, as follows: -182- (a) Doc. EPA-440/1-74/031, Processor Segment (August 197 Cb) Doc. EPA-440/1-74/031-d, Group 1. Phase I, Renderer Segment (January 1975) 5. U.S. Environmental Protection Agency I'Upgradig Meat Packing Facilities to Reduce Pollution", EPA Technology Transfer Seminar Publication. 3 Vols. Washington (October 1973). -183- THE WORLD BANK JULY 1982 OFFICE OF ENVIRCRENTAL AFFAIRS GUIDELINES STRIP (SURFACE MINING OPERATIONS) SEDINT AND EROSION CONTROL (LAND RECLAMATION) 1. Ctrol of erosion and sedimentation has assumed a new imPortance in view of world-wide industrial . expansicn and increased energy needs. Greater reliance is being placed on coal as a major energy source. . Many mineral ores and coal supplies are readily accessible through strip (or surface) mining cperations. Therefore measures are necessary to protect the environment from uncontrolled soil movement ar4 offsite damage that could result from such perations. 2. Measures are also necessary to ensure the safety of workers and others who are required to be at or near the site. On March 24, 1981, 19 persons were buried alive when their bcmes, located at the edge of an cpen cast tin mine, were destroyed by a landslide. The ground an which the homes were standing slipped 60 meters downhill into an excavation. This tragic event occurred at Puchong, Selangor State, Malaysia. 3. Each Bark appraisal report should include a complete and detailed proposal, with a timetable, for controlling erosion and sedimentation which could result from projects. The plan should provide for initiating land reclamation and other necessary measures in the early project stages, and in no case later than three (3) years following the start of mining opera- ticns. 4. These guidelines present basic concepts and sources of sediment pollutin, principles, of control, and the planning needed for effective control measures. CONCEPTS AND. COURCES OF SEDIMENT POLI=TION 5. Surface mining, like any large-scale earth-imving cperation, can generate- large volumes of sediment. If the sediment can be contained within the mining site, then no problems are created. However, if the sediments are not contained but are allowed to reach adjacent waterways, as is most frequently the case, then they become pollutants. 6. As pollutants, the sediments can have a number of detrimental ef- fects, such as: -Reducing storage capacity in reservoirs; -Filling lakes and ponds; -Clogging stream channels; -Destroying aquatic babitats; -Increasing water treatments costs; and -Acting as carriers of other pollutants (such as plant nutrients, insecticides, heavy metals and diseas organisms). - 184 - 7. The najor sources of sediment pollution are those 'land-disturbing activities associated with mining, construction, agriculture, and fores- try. It has been reported that active surface mining and construction operations cause the highest rates of erosion. 8. The major sources of sediment in surface mining operations are the areas being cleared, grubbed (removal of stumps and roots), and scalped (renoval of vegetation cover); roadways; spoil pits; and active mining areas. 9. Soil losses from clearing, grubbing and scalping operations are caused by: -Failing to install perimeter control measures prior to start up of operations; -Exposing soils or steep slopes; --Clearing too far above the unexcavated face of the over- burden; -Clearing and grubbing too far ahead of the open cut; -Improperly placing or protecting the salvaged or stock- piled materials; and -Creating a surface that impedes infiltration or concen- trates surface runoff, such as leaving bulldozer cleat marks that run up and down a slope. 10. Roadways are often the major source of. sediment, and may function as conduits for sediment washing down from other areas into the natural drainage systems. This includes the roadways within the mining area itself as well as the access roads outside the actual mine. site. 11. IMng access roads can adversely disrupt the natural drainage sys- tems by intercepting, concentrating and diverting runoff. This will result in severe soil losses from roadway surfaces, ditches, cut slopes and safety bens. 12. Accelerated onsite and offsite erosicn will occur after the mine ceases operations if steps are not taken to permanently stabilize exposed surfaces with vegetaticn and to otherwise lessen disruptian of the normal drainage patterns. 13. In area strip mining operaticns, carried cut in level or gently rolling topography, the spoil accumulating belcw the outcrop line has the greatest potential for causing offsite sediment damage. Water pumped from the pit during rainfall can also contribute significant quantities of sedi- ment and other contaminants. 14. Contour strip mining, carried cut in steep or rountainous terrain has a much greater potential for sediment damage. Since contour mines have a narrcw, linear configuration nore of the- spoil area tends to discharge directly into the natural drainage systems. Another contributing factor is that the receiving waterway is generally closer to the sediment source and separated by relatively steep terrain. Additionally, the mine site receives erosive runoff from undisturbed areas above it. - 185 15. Mountain-top renoval raining bas, in recent years, been an alter- native to strip mining. The nost critical areas at this type of operation are the spoil slopes around the perimeter, mine roadway exits, and valley fills. The fills are highly susceptible to piping (subsurface removal of soil) and to landslides. Another serious problem can be the soil losses fran the face of the slope due to rainfall and runoff. Chemical and acid pollution can also cause serious problems. 16. Certain reclamation practices contribute significantly to en- vironmental damage if not properly carried out. Configuraticn of the grad- ed areas, the pattern of reestablished drainageways, revegetation measures, tillage practices, and followup maintenance will all influence the long term soil losses and offsite damages. PRINCIPLES OF EROSION AND SEDIMT TRANSPORT 17. As applied to mining operations the nost important types of eros- ion are those caused by a stornwater runoff. Three basic types are of major significance: -Sheet erosion - resulting from rain striking a bare soil surface, and displacing soil particles; -Rill and uly erosion - removal of soil by water through small, well-defined channels; and -Stream channel erosion - scouring of the stream channel by sediment reaching the stream frcn land surfaces. 18. The erosion potential of any area is determined by climate (pre- cipitation, teuperature and wind);- vegetative cover; soil characteristics (structure, texture, organic matter, moisture, and permeability); and to- pography. %hile these factors must be considered separately, it is their cambined effects which determine the total erosicn potential. 19. Sediment transportaticn and depositicn are influenced by the flow patterns of the water and the nature of the particles being transported. As velocity and turbulence increase, more sediment is transported. Small, light particles such as fine sand, silt and clay are easily transported. Ccnversely, coarser and heavier particles are more readily deposited. CONTROL TEHNOIGY 20. Stornwater runoff, which is the basic cause of soil erosicn, can be controlled through applications of proper vegetative and structual prac- tices, and constructicn measures that control the location, volume, and ve- locity of runoff. To this should be combined a suitable program of schedc- hing mining operations to minimize problems related to seasonal climatic fluctations. 21. Control nay be accomplished through one or more of the following: -Reduction and detention of 'the runoff; -Intercepticn and diversicn of the runoff; and -Proper handling and disposal of concentrated flow. -186- 22. Soil stabilization is another means of preventing soil erosion. Stabilizatin measures may be either vegetative or non-vegetative, short. term or long term, or a combination of these. Vegetative stabilization utilizes different types of vegetatici to protect the soil frcn erosion. Non-vegetative stabilization erploys a nultitude of measures that depend on materials other than vegetaticn to prevent erosion. Frequently the two types are used together. 23. Mulching and chemical stabilization are the two major types of short term measures applied. Mulching, with organic materials such as straw, bay, wood chips, wood fiber or other products, is most often used. Chemical stabilizers serve to coat and penetrate the soil surface and bind the soil particles together. These are nost. effective for dry, highly per- meable spoil or inplace soils subject to sheet flow. 24. Mulching and channel stabilizaticn are most frequently used for long term stabilization. However, mulching in this case involves the use of fiber glass, plastics, or other non-biodegradable material to protect seed beds during the germination and early plant development periods. In general, structual channel stabilizaticn involves the use of stone riprap (broken rock) or other durable material to stabilize ditches and other waterways. Stone surfacing is sometimes used to stabilize highly toxic surfaces or excessively wet seepage areas cn slopes. 25. Sediment is the product of erosion and hence must be contained, and every effort should be made to control sediments at, or as close to, the source as possible. The procedures used successfully for trapping (such as sandbags and straw bales), settling basins and chemical coagula- ticn. 26. All erosion control and sediment containment fAcilities must re- ceive proper maintenance during their design life in order to perform ef- fectively. They should be located in a highly visible area so as not to be overlooked. They must also be readily accessible to personnel and equip- ment for regular inspections, and for the performance of routine and emer- gency repairs. 27. Once the mining operaticn is finished, all sediment control structures should be disosed of in such a way as to present both the struc- tures and the accumulated sediments fran beconing nuisances and contribu- ting to envircrental deterioration. EFUENT LIMITATIONS 28. Runoff and drainage from surface mining operations should not ex- ceed the following limitations prior to discharge into surface waters: Total Suspended Solids: 30 - 100 rg/L Total Iron 4 - 7 mg/L pH 6 - 9 Alkalinity Greater than acidity Soluble Toxicants None - 187 - CONTROL PIANNING 29. An erosion and sediment control plan serves as the basis for cp- erating the mine and at the same time minimizing or eliminating environmen- tal damage. 30. Preparation of a control plan requires five basic steps: -Identification of legal and technical requirements; --Collecticn and evaluaticn of site information; -Development of a control strategy; -Interdisciplinary review of the feasibility of the preliminary plan; and -Revision and finalizaticn of the control plan 31. Table 1 presents a list of the major components which should be considered in formulating an erosion and sediment control master plan. This should be made an integral part of the overall mining, operation. IAND RECIAMATION 32. Surface mine reclamaticn shall be performed in such a manner that the lands are returned to conditions capable of supporting prior land uses or uses that are equal to or better than prior land use. The operator must backfill and grade to cover all acid and toxic materials. Highwalls and spoil piles mst be eliminated and the approximate original contour re- stored. All surface areas nst be stablized and protected in order to con- trol slides, erosion, subsidence and accompanying water pollution. Water * inpcundnents, retention facilities, dams, or settling ponds shall be ade- quate for intended land use. These faclities cannot produce significant adverse effects to adjacent water resources. Cperators nust use best prac- ticable coumercially available technology to minimize, control, or prevent disturbances to surface or underground water quality, quantity, or flow. Mining wastes and rubbish must be properly disposed of so as to minimize, control, or prevent water pollution. 33. It is inportant .that land reclamation be started as soon as pos- sible and at the latest 3 years after the opening of the mine. The Bank Mission should receive concrete and detailed proposals on the reclamation program and On the means necessary to achieve it. BIBLIOGRAPHY 1. Grim, E.C. and R.D. Hill. "Envircnmental Protection in Surface Mining of Coal". U.S. Environmental Protection Agency - Technology Series, Doc. EPA-670/2-74-093. Washingtcn (October 1974). 2. U.S. Envircomental Protection Agency "Erosion and Sediment Control". (2 Vols.) Doc. EPA-625/3-76-006. Washington (October 1976). 3. "Guidelines for Reclamation and Revegetation, Surface-Mined Coal Areas in Southwest Virginia". Virginia Polytechnic Institute and State University, Extension Division. Blacksburg, Virginia (February 1973). -188 - Zable 1. Components to be Considered for Prepatat:a.n of Erosion and Sedlment Contro ?l ans a/ Sackground information: TSchedul of acivities-continued 1. General: Mining operations-conrin*' .ocation of project 2. Overburdan handling: EUnt of arma to be af fecd Type of mining operation Method of overburden handling Evidence of comptianc~ with State's legal Handling of fim cut rMquirments Pian view of overbuden storage 2. Sitt invemory: Stornwater handling in overburden stog armas Topography Tonporary sabiliation rmeasures• Geologic analyss - Permanent stalilization meaures Soi analysis i c analysis Hydrologic analysi Reiamato opermionr: Vegetaive analyuis Land usa analys 1. H.andling of toxic material: Method of handling toxic material Equipmem to be used Schedule of activies 2. Spoil rehandling and grading: Site preparation: Typical cross section of regrading 1. Accs mads Euipment to be used Method of spreading tosoii or upper Plan view (location) hor~an material on the regradd Typiclrssuection are, including aroximate Prof iles thicinms of the final ~rfacing Maintenance requirements Und schedule nmtrial Mehod of drainage contol for the 2. Orainage and hent ibmrol srcmre: finl regraded mec Plan view (location . .. 3. Rugetada 7 Typil crom sions Detnilm (where needed) . Method to be usd Design computatons (where needed) SUrface preparadon Maintnance requirwnu and w*hedule Type of vegestion P~dl~ appication (method and 3. CW~ring and grubbing: . rWW ' . , Seasonal ruegetation schedule and Plan views of lienks of ares to be ciaed r=m Ducripio of procedure Mulch application (method and mte) V.xhinesy to be und Maintenance reument and sched- Mehod of diposing of timber, brudand . ue idemificeaion of crt~l r ruquinng 4. Mine abandonmenu Meshod for disposul and stliation of drainge stuctures noto. Maing op.rdons: ee abov. partcicuary uediment bjaaficften . Seiping:•. Medud for smbiånsi ad/or aln donment of hiulroad ' Method of se~iping tpsoAi meriad Auignnt of mponsii-y for any Equipentu to be us~ psnnenen t u rci keft bwhind Plan viw of tassoö norage m . Maintnance progid sceduie Tmorary s Sge d ~twe sabiliaton of '6 for aW PrLbZonnt_truc 1urs 't -i USEL "EroionP and S n Control". Do. EP-2/s.600. (cte 1976) 189 THE WOILD BANK FERUARY 1981 OFFICE OF ENVIRONMENTAL AFFAIRS UNDERGROUND COAL MINING EFFLUENT GUIDELINES 1. Many of the world's mineral resources are extracted from the earth through underground mining operations. The principal ones include coal, and to a lesser degree, copper, lead, zinc, molybdenum, uranium, and others. This document will be confined to the environmental effects of underground coal production and its associated operations. NIG PROCESSES 2. Underground mining is a highly complex operation, involving basic- ally working beneath a thick overburden, connected to the outside by shafts and passageways which are sometimes hundreds of meters long. Major problems which are not found or are of lesser importance in surface mining include roof supports, ventilation, lighting, drainage, methane release, equipment access and coal conveyance. 3. Once a main access portal has been established, parallel entries are driven into the coal deposit to provide corridors for haulage, ventilation, power and other operational needs. Cross-corridors then reach to the sides of the mine, leaving pillars in a checkerboard fashion to support the roof and overburden. The deeper the mine, the larger the pillars must be relative to the mined out areas. Where large pillars are required for support during operations it may be desirable to mine the pillars as the equipment retreats back toward the main tunnel. The roof must then be supported by other means or allowed to collapse. 4. Equipment used in underground mining ranges from relatively simple to highly automated machinery. Many small mines still rely primarily on hand labor. Coal is blasted from the face of the seam and loaded into shuttle cars, using mechanical techniques in most cases. This involves undercutting, drill- ing, blasting and loading. Shuttle cars, filled by portable conveyor belts, take the coal either to an underground transfer point or directly out of the mine. 5. These operations produze.large amounts of dust and liberate methane trapped in the coal, requiring that exposed areas be kept essentially free of particulates or open flames to prevent coal dust or methane explosions. Machines are usually connected to a watar supply to provide a spray for dust control. Frequent methane testing is required at the seam face to avoid danger to the workers. - 190 - 6. Continuous machines are employed in many locations. Basically a rotating head digs into the coal and loosens it while arms scoop it onto a conveyor belt for loading into a shuttle car. 7. Longwall mining has been used in Europe for many years and is now gaining popularity in other regions. Corridors about 100 to 200 meters apart are driven into the coal and interconnected. The longwall of the in- terconnection is then mined in slices. The roof is held up by steel supports while the cutter makes a pass across the face. The roof supports are advanced with the shearing machine to make a new pass, while the roof in the mined out area collapses behind the supports. 8. For most uses, the mined coal must be processed to meet consumer needs in terms of size, moisture, mineral concentrations, heat content and other properties. This may be done by either physical or chemical procedures, and usually takes place at the mine site. 9. Physical coal cleaning involves crushing, grinding, sizing, solids separation, washing and flotation in various combinations. These techniques remove portions of the sulfur and ash contents. Although the sulfur exists in the coal in both the organic and inorganic forms, physical cleaning is effective'anly in reducing the inorganic portion. Because of partial ash removal, the procedure also 4acreases the per kilogram heat content. 10. Chemical coal cleaning or desulfurization involves treating coal with a reagent capable of converting the sulfur to a soluble or volatile form. Leaching solutions such as nitric acid, hydrofluoric acid, :hlorine, ammonia, and organic solvents have been reported to be successful. Eowever, this cleaning procedure is still in the experimental stage and is not currently being applied commercially. SOURCES AND CHARACTERISTICS OF WASTES 11. Coal mining operations and equipment choices vary widely, and are generally selected on the basis of local geology and other natural conditions. The specific environmental effects will depend upon the mining techniques utilized and the existing geological or geochemical characteristics. Air Emissions 12. Air pollutants from coal mining operations are not considered to be significant. Dusts originate from drilling and blasting procedures, but these are generally controlled by water sprays at the working face. Methane is controlled through effective ventilation with air in order to reduce the gas concentrations to levels below the flamable or toxic limits, and thus avoids the possibility of underground explosions. The methane problem increases with greater depths because the methane has less opportunity to diffuse to the surface over geologic time. It has been estimated that at mining levels methane is produced at an average rate of 5 cubic meters per ton of coal mined. - 191 Liquid Effluents 13. The principal environmental pollutant resulting from underground coal. mining operations is acid mine drainage. The acidity results when naturally occurring pyrite (FeS2)in the coal seam and wastes is ozidized in the presence of air and water to form sulfuric acid (32 SO4) and iron sul- fates (7e S04 and Fe2 (SO4) 3. This very acidic (pH 2 to 3) effluent must be treated for pH and dissolved iron before release to water courses. At the low pH values heavy metals (such as iron, manganese, cadmium, copper, zinc, and. lead) are more soluble and can create serious water pollution prob- lses. Continuous acid discharges will seriously affect aquatic ecosystems. Acid waters containing heavy concentrations of dissolved heavy metals will support only a limited water flora, such as acid-tolerant molds and algae, and will not support fish. Acid waters are not suitable for human consumption nor for most industrial uses. 14. The amount and rate of acid formation and the quality of water dis- charged will depend upon the amount and type of pyrite in the oterburden and in the coal, time of exposure, characteristics of the overbutdenl and amount of available water. It has been estimated that in the Appalachian bituminous coal mining regions of the eastern United States an average of 1200 liters of acid mine water is discharged for each metric ton of coal mined. 15. Water is supplied to coal mines primarily for suppressing dust (con- tinuouj, mining and conveyor belt operation) and for equipment cooling. Rain water can enter mine areas through infiltration. Hence, continuous water re- moval is required to assure continuity and efficiency of the mining process. 16. In coal preparation the water is deliberately introduced into the unit process operations which include vet screening, tables, cyclones, gravity separation and heavy media separation. Water is also used for dust control, equipment cooling, and transporting coal in the washing process. 17. The parameters of principal concern in underground coal mining opera- tions and for coal preparation plants include hydrogen ion concentrations (P), total suspended solids (TSS), total iron, and total manganese. Average levels of these parameters found in typical underground mining and coal preparation plants are given in Table 1. Solid Wastes 18. Solid wastes are generated both during underground mining and during the preparation process. The solid waste from underground mines (commonly re- ferred to as "gob") results from the digging required to reach the coal seams. Normally this material is transported to the surface and dumped in piles on the land. Its composition in general corresponds to the overburden found in the mining area. - 192 ' Table 1. Average Quality of Raw Effluents From Acid Mine Drainage and Coal Preparation Parameter Acid Coal Drainage Preparation Total Susp. Sol. - mg/L 158 218,000 Total Manganese - mg/L 4.9 8.4 Total Iron - mg/L 135 733 pH - Units 5.7 7.0 Ls. Pefuse from the coal extraction and preparation, consisting of solid wastes and other impurities, is also generally disposed of by dumping, on nearby land areas. 20. The waste piles are unsightly, causing degradation of local prop- erty values and destruction of esthetics. The refuse contains flanmable material readily susceptible to spontaneous combustion and difficult to quench. This burning produces particulate matter and fumes high in sulfur dioxide. Acid mine drainage and siltation can also result from runoff from the piles. Siltation is influenced by the steepness, compaction, drainage control structures, and cover material of the pile. WASTE DISCHARGE LIMTATIONS Air Emissions 21. Dust and methane-gas are the principal air pollutants of concern in underground mining. Particulates should be controlled by water sprays. Methane gases should be controlled by efficient ventilation systems bringing outside air to the working areas. 22. Coal preparation plants can be sources of discharges of particulate matter to the atmosphere. Pneumatic cleaning and thermal drying are the chief sources. Particulates should be limited to: Ann. Geom. Mean 75 ag/m3 Max. 24-hours 260 ag/m3 (outside the mine fence at ground level) 193, Liauid Effluents 23. Liquid effluents from subsurface mining add coal preparation opera- tios should conform to the limitations shown in Table 2. Table 2 - Effluent Limitations for Acid Mine Draina2e and Coal Prevaration Parameter TAimtation Total Susp. Sol. - mg/L 70 c Total Manganese - mg/L 4 Total Iron - mg/L 6 pH Units 6 to 9 CONTROL AND TREATHET OF WASTES Air Emissions 24. Dust control in the mines is effected by continuous spraying of the working face. The methane is diluted with air to less-than-flammable limits to avoid the possibility of underground explosions. In some instances the methane can be drained from the coal seam before mining. Such an operation recovers the gas for use as a fuel and at the same time reduces the danger of mine explosions. 25. Particulate matter from coal preparation originates from crushing, pneumatic cleaning and thermal drying. These emissions can be effectively con- trolled by use of baghouses or other dust collection devices. Liauid Effluents 26. The acidity in the acid mine drainage may be controlled through pH. adjustment and chemical precipitation. Hydrated lime (Ca (OH)2) is most comonly used for this purpose, and can be introduced as an aquaeous slurry or as a dry powder. In large installations calcined lime (CaO) (also termed "slaked" or "quick" lime) or limestone (Ca C03) may be more economical to use. Caustic soda (Na OH) or soda ash (Na2 CO3) can also be used, but are much more expensive. - 194 - 27. Control of the pff will also result in a reduction of the iron and manganese levels in the effluent, by causing oxidation which converts the ferrous iron to ferric iron and thus precipitates it out of solution. The upward adjustment of the pH causes a solubility decrease and precipitation of the heavy metals in the effluent. The precipitates can then be removed by settling. 28. The effectiveness of neutralization and settling in controlling the effluent is governed by the reagents used, the influent and effluent pH, temperature, volume of flow and the presence of any side reactions, including metal chelation and mixed-metal hydroxide complaxing.. (Chelation is a chemical reaction in which a central metallic ion is captured in a complex within a ring containing several atoms). 29. Oxidation of certain components common to coal mine wastewates (such as ferrous ions) to easily removed compounds can also be accomplished by aeration, either mechanical or simple cascading flow. The resulting sludge and other solids are readily settled in settling basir,. 30. Wastewater from coal preparation plants may be satisfactorily treated by settling. If the settling pond capacity is limited it may be necessary to use a coagulant. The overflow from the ponds is generally suitable for recyc- ling through the preparation systems, resulting in little or no discharge to surface waters. Where sufficient land area is available two or more ponds are used on an intermittent basis. As a pond is filled with settled solids, it is taken out of service for removal and disposal of the sludge. Solid Wastes 31. Refuse from the mining operation may be left underground but in most cases it is brought to the surface and dumped nearby. Refuse from the coal cleaning is generally collected and also dumped near the site. 32. Steps should be taken to assure that leachate and surface runoff from the piles does not cause harm to surface waters or groundwater supplies. Leaching,which should be monitored, can be minimized or prevented by careful composition and layering of the refuse material. Leaching water will be treated if need be. 33. Sludges from the settling ponds can be dredged and conveyed to a refuse pile and sludge lagoon. Where sufficient pond capacity is provided, the sludge may be allowed to dry in the lagoon. This will reduce the volume and facilitate removal and final. disposal. COAL SLRRY PIPELINES 34. Although it is not being widely applied at this time, coal slurry pipeline technology has already proven to be a commercially successful alterna- tive for transportation of coal. Because use of this technology is expanding, - 195 - it is considered advisable to outline the possible environmental effects. Guide- lines on use of pipelines for transportation of petroleum and its derivatives have been prepared by the Bank's Office of Environmental Affairs. 35. The major risks of environmental damage occur during the construction phases of slurry pipelines. The environmental effects and measures that can be taken to minimize these effects are shown in Table 3. Coal pipelines may ex- tend for distances of as much as 500 to 2000 kilometers. The facilities are usually buried underground and hence cause no permanent esthetic damage. Table 3 - Environmental Effects of Coal Pineline Construction- Activity Environmental Effects Mitigation Measures (1) Clearing and Destroys wildlife habitat Revegetate quickly grading Encourages runoff and Slow runoff erosion Leave screening Degrades esthetics vegetation (2) Ditching Potential runoff from Close ditch as soon as spoil pile possible Covering top soil may Separate top soil and produce rock rubble set aside Haul to appropriate disposal site (3) -Rauling and Increased truck Limit haul hours and Stringing Pipe traffic route (4) Welding Pipe None None (5) Coating Pipe Accidental spill of Normal care in operation coating materials . and availability of cleanup materials (6) Backfill Extra top soil or Use existing or properly ditch "padding" soil sited borrow pits may be needed (7) Clean-up Erosion of right-of- Adequate revegetation way program Restore drainage patterns Monitoring of recovery (8) Testing System Requires large volumes Careful selection of of water water source and discharge a/ From EPA Document EPA - 600/7-77-013 (See Bibliography) -196- 36. The risk of spills from such facilities is considered to be negligible. The control and prevention of corrosion are well developed technologies because of extensive use of these underground systems to transport petroleum, natural gas, and other resources. 37. Operational impacts are affected jy the coal preparation, pumping stations, and dewatering facilities. Problems are associated with preparation of the coal slurry, inter-basin transfer of large quantities of water required, and discharge or disposal of the separated water at the destination. 38. Since preparation of the slurry is generally done at the site of coal preparation, as previously discussed, the handling of wastes is genrally included in the measures otherwise taken at the site. To prevent settling and possible obstruction in the system, ponds are provided at intervals for emptying the line in case of a system breakdown or other interruption. 39. At the discharge end, the coal slurry goes into agitated tank storage, from which it is conveyed to the dewatering systems. Dewatering is done by natural settling, vacuum filtration, or by centrifuge. Additional thermal drying is required before use of the coal. The finely ground coal still remain- ing in the water is generally removed by chemical flocculation. The reclaimed water may be used for cooling or other purposes. BIBLIOGRAPH! 1. Lajzerowic, J. "Environmental Factors and t:ae Requirements for Control of Effluents", in "Economica of Mineral Engineering". Inter-regional Seminar organized by the United Nations in cooperation with the Govern- ment of Turkey, held at Ankara, April 1976. Mining Journal Books Ltd. London (1976). 2. Lajzerowicz, J. "Institutional Aspects Related to Coal Development in Canada". Presented at United Nations Symposium on World Coal Prospects, Katowice, Poland, October 15-23, 1979. 3. Alexanderson, G. and Klevebring, B.-I. "World Resources: Energy, Metals, Minerals". Walter de Gruyter. Berlin and New York (1978). 4. "The Direct Use of Coal-Prospects and Problems of Production and Combustion". Office of Technology Assessment, Congress of the United States. Washington (1979). 5. U. S. Environmental Protection Agency". Monitoring Environmental Impacts of the Coal and Oil Shale Industries: Research and Development Needs". Doc. EPA-600/7-77-015. Washington (February 1977). - 197 - 6. U. S. Environmental Protection Agency. "Development Document for Proposed Effluent Limitations Guidelines, New Source Performance Standards, and Pre- treatment Standards for the Coal Mining Point Source Category". Preliminary Contractor' sDraft. Washington (January 1980). 7. "Standards of Performance for New Sources - Coal Mining Point Source Category". U.S. Federal Register, V.44, 9'. pp 2536-2592. Washington. (January 12, 1979). 8. "World Glossary of Mining, Processing, and Geological Terms". Ed. by R.S.M. Wyllie and G. 0. Argall, Jr. Miller Freeman Publications. San Francisco (1975). 9. Powers, Philip W. "How to Dispose of Toxic Substances and Industrial Wastes". Noyes Data Corporation. Park Ridge, New Jersey and London (1976). 10. "Pollution Control Objectives for the Mining, Smelting, and Related Industries of British Columbia". British Columbia Ministry of Environment, Pollution Control Board. Victoria (1979). - 198 THE WORLD BANK NOVEMBER 1982 CEICE OF ENVIRONMENTAL AFFAIRS NITFCGEN OXIDE EMISSIONS GUIDELTIES 1. Oxides of nitrogen present in ths atmosphere originate fran both natural and nan-made sources. Natural souxces include lightning, volcanic eruptions, and bacterial acticn in the soil. . Although these natural emis- sians far exceed those generated from nan-made activities they are not c- sidered significant. They are distributed over the entire earth, and the resulting air concentrations are practically negligible. The background concentration of nitrogen dioxide in land areas generally ranges between 0.41 and 9.4 micrograms per cubic meter. 2. This document will concern itself with those axides of nitrogen discharged fran man-made sources. They include nitric oxide (NO) and ni- trogen dioxide (N02). At the point of discharge the predominant form is nitric oxide, but this is readily converted to nitrogen dioxide through chemical reactions in the atmosphere. SOURCES AND EFFECrS 3. The principal source of nan-made emissions is the acbustion of fossil fuels. In this context fossil fuels include coal, oil and its de- rivatives, and natural gas. The predoninant oxide of nitrogen emitted by cmbustion processes is nitric oxide, with small amounts of nitrogen diox- ide. Enissions originate fran both stationary and nobile sources. Specif- ically, emissions originate fran transporaticn (principally autaobile ex- bausts); fuel arnbustion for power generation and industrial production; and certain non-carbustion sources. Hane abusticn of fuels may also make significant contributions in sane locations. Other industrial sources in- clude fertilizers, glass, ircn ore preparaticn (sintering and pelletizing) plants, and petroleum refineries. 4. Stationary combustion sources will generally account for 50 per- cent or more of the total nitrogen oxide emissions. For example, the pro- portians are estimated to be 60 percent in Japan, 59 percent in the Nether- lands, 82 percent in the United Kingdom, but only 44 percent in the United States. Hane combustion of fuels is said to contribute between 5 and 6 percent of the emissions in the United Kingdan and the United States. 5. Transportaticn sources include personal autaobiles, buses, trucks, railroad vehicles, aircraft, and ships cn inland waterways. Gaso- line powered vehicles are by far the largest contributors among these. Of the total emissions, transportation facilities contribute approximately 40 percent in Japan, 41 percent in the Netherlands, 18 percent in the United Kingdom, and 51 percent in the United States. - 199 - small portion of the* total nitrogen oxide emitted, they can be significant in. certain local situations. The manufacture of nitric acid is the nost inportant of these. Other exanples include electroplating and processes using concentrated nitric acid, such as the manufacture of explosives or the producticn of sulfuric acid by means of the chamber process. 7. Oxides of nitrogen formed in conbusticn processes are usually due either to thermal fixation of abmspheric nitrogen in the cmbustion air (resulting in "thermal NOx") or to the conversion of chemically bound nitrogen in the fuel (resulting in "fuel NOx"). For natural gas and dis- tillate oil firing, nearly all NO% emissions - result fran thermal fixation. For residual oil and coal, the contribution fran fuel-bound nitrogen can be significant, and even be predominant under certain operating conditions. 8. When a mixture of oxygen and nitrogen (such as air) is heated above 1600* C, oxides of nitrogen will result. Noral combustion tempera- tures in car engines are well above this level. As a result, over 0.3 per- cent of the exhaust can consist of a mixture of NO and NO2. Enissions are lowest at lower engine speeds. The character of the emissions will depend upon the operating characteristics of the engine, such as toerature, du- ration of the cwbusticn cycle, air/fuel ratio, etc. Diesel engines also are emission sources but to a much lesser degree because of the lower com- busticn temperatures in the cylinders. Gas turbines and other similar en- gines are also less significant as sources. 9. Autcmobile exhausts will al]o release unburned hydrocarbons into the atmosphere. While hydrocarbons are not in themselves generally haium- ful, they can form photochemical oxidants ocamonly known as smog when re- leased in the presence of oxides of nitrogen and exposed to sunlight. Pho- tochemical smogs can occur anywhere, but they have been nost severe in Los Angeles, California, where they are a year-round phenanenon due to frequent temperature inversions. 10. Ozone is the rain constituent of photochemical oxidants and can have severe effects on the respiratory system. Smog can irritate the lungs and seriously aggravate asthma or other respiratory diseases. Coughing, eye irritaticn, headaches, and throat pain are conmonly experienced during exposure to smog. U. The nitrogen oxides fran man-made sources can also exist as pri- mazy pollutants in areas not subject to formaticn of smog. Such exposure is believed to increase the risks of acute respiratory disease and suscept- ibility to chronic respiratory infection. Nitrogen dioxide (NO2) contri- butes to heart, lung, liver, and kidney damage, and can be fatal at high concentrations. 12. Nitrogen oxides are also toxid to vegetation. Although many plants can metabolize low concentrations of NOx' the higher concentrations will reduce growth and the fertility of seeds. - 200 - 13. Nitrogen oxides can also affect the environment by contrituting significantly to the acid rain problem. Through cotmlex atmiospheric reac- ticns, these oxides can be converted to nitric acid, which is then depos- ited with rain or snow. In the United States acid precipitation, nuch of which is due to nitric acid, has reduced or destroyed cumiercially and re- creationally important species of fish in several areas. FMISSIC SAMPLIG AND ANALYSES 14. The unit of mearuement used to denote the ambient concentrations of nitrogen oxides in the atmosphere, after emission from either stationary or mobile sources, is expressed as weight per- unit volume of air or, spe- cifically, as micrograms of nitrogen dioxide (N02) per cubic meter (g/m3)* This unit is to be used in all World Bank project reports. 15. Plant emissions, prior to reaching the atmosphere may be express- ed in terms of plant input or output. Examples of these limitations, as applid to fossil fuel and nitric acid plants, are given below. 16. Sampling and analytical procedures for determining nitrogen ox- ides are covered in a separate guideline issued by the Office of Environ- mental Affairs. ACCEPTABLE STANDARDS 17. Two types of standards are generally used - ambient and emis- sicns. Ambient standards express the allowable concentration of a contami- nant in the air (in this case) surrounding the industrial site, following discharge and mixing.. Ambient levels are essential for detenning poss- ible environmental damage and for evaluating adverse physical, health, and other effects upon the surrounding area and its inhabitants. 18. Eission standards express the allowable concentrations of a con- taminant at the point of discharge, before any mixing with the surrounding medium (air). Emission levels are necessary for identifying specific pol- lution sources and designing remedial works. 19. For all Bank projects ambient air concentrations of nitrogen ox- ides, expressed as NO2, should not exceed the following: Annual J.ith. Mean: 100g/m3 (0. 05 ppn) 20. For guidance purposes, emission levels for stationary source dis- charges, before mixing with the atmosphere, should be maintained as fol- lows: (a) For fuel fired steam generators, as Nanograms (10-9 gram) per Joule of beat input: Gaseous fossil fuel 86 Liquid fossil fuel 130 Solid fossil fuel 300 Lignite fossil fuel 260 -201- (b) Nitric acid plants: 1.5 Kg N02/metric ion acid produced. 21. In special situations, strict adherence to these standards may be difficult for a number of reasons. Where this occurs, Bank missions should very thoroughly document such cases, with sufficient information to allow a judgement to be made. Examples of situations where these standards could not be. met, with acceptable nodifications, include: - Expansion of existing plants - The Annual Arithmietic Mean and the maximum 24-hour peak resulting from the ambination of the old units with the new ones should be no greater than the values existing prior to operation of new units. In addition, the new units by themselves should meet established standards. More simply, emission plumes fran new and existing sources should not mix to the extent that combined ambient concentrations exceed maximu ambient concen- trations obtained from the existing source aione. This may be accomplished by (a) increasing the stack height of the new source, (b) changing the stack location of the new source, or (c) reducing the new source emission levels. Furthermore, if plume mixing is not a problem the new source units should, by themselves, meet the above standards. - Revamping of existing plants - Every effort should be made to decrease existing pollution levels and provide measures which will minimize concentrations without placing unreasonable economic burdens on the * industry. - Inversions - When the NOx source location is in a valley or surrounded by nountains, inversion layers which may occur during certain seasons of the year could trap the stack emissions. These same emissions can drcp back to ground level, stagnate there, and damage crops sensitive to both SO2 and Tx. In World Bank financed pro- jects it may be impossible to change the site loca- tion (i.e. in the case of an expansion of an existing plant) . To protect hman and plant life in such cases, the peak concentration should be decreased fran 500 pg/m3 during any 24-hour period down to 350 pg/m3 d ing 4 hours, unless it can be shown that the effluent will not be trapped by the inversicn layer. -202- CONTR TECHNOIGY 22. EnissicL control measures must be designed for each ind-iviAual plant, particularly since the system nust be capable of reducing norre than one polludant in nost situations. 23. The most commcn method currently used to reduce NOX emissions from autcnobile exhausts (which are the major sources) is the catalytic ccnverter. The method utilizes a catalyst instead of high tboperatures to achieve sinultaneous oxidation of the runinaing fuel, and reduction of NOx to N2. The catalyst achieves the double goal of decreasing concentrations of both NOx and hydrocarbons cn a metal catalyst deposited on ceramic na- terial. 24. Mobile source emissions are also reduce t.hrough changes in com- bustion chamber design (such as lower compression ratios), spark retar- daticn (including both basic timing and a "slower" advance curve), and ex- haust gas recirculation. 25. The NOz emissions fram oil-fired canbustion systems can be re- duced by mixing water with the oil before it is sprayed into the burners. Water decreases the canbustion temperatures, and can reduce NOx emissions frcm light-weight oils by as much as 15 percent. Energy-wise, however, the method is considered to be costly. 26. xnissions fran stationary sources, such as utility and industrial. canbustion installations, can be reduced by a number of methods. Among these, staged coabustion, low excess air cperation, and flue gas recircula- tion are widely used.. 27. Staged canibustion is effective for control of both thermal and f-Uel nitrogen oxides. The method cansists of initially providing less .than the amount cE air (02) required for cnplete coabustion. After a time de- lay more air is added in one or nore steps or stages. The method is appli- cable to a wide range of fuels and facilities, frcm pulverized coal burners to small scale industrial boilers. Addition of this method to existing coal-buring installations has resulted in a 30 to 50 percent reduction of T0x emissions. 2S. In the low excess air method, the principal mechanism is also the lack of available oxygen for canbining with either thermal activated or cracked fuel activated nitrogen atos. This method can be conbined with the staged canbusticn process, and can reduce nitrogen oxide enissions by 40 to 70 percent, without seriously increasing carbon nonoxide enissions. 29. Flue gas recirculation has been effective in controlling thenral nitrogen oxides. 'The recirculaticn of exhaust gases to the flame regions reduces peak temperatures and oxygen availability, thus reducing nitric oxide formation. This method is more difficult to aply, since it requires increased operation controls and greater capital investment. - 203 - 30. A number of methods are under further study for stationary source emissions. These include burner design changes, water/steam injection, wet scrubbing with aqueous ammonia, and fluid bed combustion. BIBIOCGRAPHY 1. World Health Organization "Oxides of Nitrogen". Environmental Health Criteria 4. Geneva, (1977). 2. Organizaticn for Economic Cooperation and.Developnent. "Photochemical Snog-Contribution of Volatile Organic Ccmpounds". Paris (1982). 3. U.S. Environmental Protection Agency. "Technology Assessment Report for Industrial Boiler Applications - N0X Combusticn Modification". Document EPA-600/7-79-178f. Washington (December 1979). 4. Diamant, R.M.E. "The Prevention of Pollution". Pitman Publishing. Landon (1974). 5. U.S. Envircrnental Protection Agency. "Research Summary-Controlling Nitrogen Oxides". Document EPA-600/8-80-004. Washington (February 1980). 6. Jarrault, P. "Limitations des Emissions de Polluants et Qualite de L'Air. Valeurs Reglementaires dans les Principaux Pays Industri- alises". Institut Francais de L' Energie. Paris (1978). 7. World Health Organizastion. "Air Quality Criteria and Guides for Urban Air Pollutants" WHO Technical Report Series No. 506. Geneva (1972). 8. U.S. Code of Federal Regulations, Title 40, Sub-Chapter C, Part 60, Subpart D "Standards of Performance for Fossil-Fuel Fired Steam Gen- erators for Which Construction is Canenced After August 17, 1971". Office of the Federal Register, GSA. Washington (July 1, 1981). 9. U.S. Code of Federal Regulations, Title 40, Sub-chapter C, Part 50.. "National Primary and Secondary Ambient Air Quality Standards". Office of the Federal Register, GSA, Washington (July 1, 1981). 10. Organization for Eco=anic Cooperation and Development. tMhotochemical Oxidant Air Pollution". Paris (1975). - 204 - THE WDRLD BANK NOVEMBER 1982 OFFICE OF ENVIROMENTAL AFFAIRS NITROGEN CIDE SAMPLING AND ANALYSES 1. This document supplements a ctrpanion Bank document, titled "Nitrogen Oxide Emissions". It provides procedures required for sampling and analysis of stack emissions and the ambient atnosphere to determine capliance with NCx pollution limits for Bank projects. 2. Major man--made emissions of nitrogen oxides are fossil fuel com- busticn in stationary sources (heating, power generation, etc.) and ex- hausts from notor vehicles and any novable sources utilizing internal cmn- bustion engines. 3. Land areas normally have natural background concentrations of ni- trogen dioxide in the range of 0.4 to 9.0 micrograms per cubic meter. In urban areas, world-wide, average annual background concentrations may vary fron 20 to 90 micrograms per cubic meter. 4. Oxides of nitrogen, for purposes of this document, include nitric oxide (NOJ) and nitrogen dioxide (NO2). At point of discharge fran man-made sources, the principal oxide is nitric oxide. This is rapidly converted to nitrogen dioxide by atmospheric chemical reactions. Nitric oxide and ni- trogen dioxide can be measured separately or collectively by various tech- niques. STATIONARY SOURCE MONITORING 5. Stationary source samples are collected through openings provided for that purpose in stacks or other ducts- carrying emissions fran combus- tion chambers. Sampling ports should be located at least eight stack di- ameters beyond any bendS, constrictions, abatement equipment, or other causes of flow disturbance. If this is not possible then the sampling lo- cation should be at least two stack diameters ahead of the flow disturb- ance. Nhere these anditions cannot be net, it nay be necessary to extend the stack. 6. Sampling ports should be flush with the stack walls, and. extend outward fron the exterior wall for 5 to 20 centimeters. However, addition- al extension may be required for installing valves or other appurtenances. - 205 - 7. The sampling apparatus is shown schematically in Figure 1. The sampling probe may be placed at any locaticn across the stack diameter, and a grab sample collected in an evacuated flask containing a dilute sulfuric acid-hydrogen. peroxide solution. This solution reacts with the nitrogen oxides. The volumetric flow rate and moisture content of exhaust gas stream nust be determined for calculating the total mass emission rate. 8. Each grab sample is obtained rapidly (15 to 30 seconds) and four grab samples constitute a run. A minimum of three runs should be taken, or a total of 12 grab samples. An interval of 15 minutes .should elapse be- tween each grab sample. 9. Since a grab sample collects a relatively small amount of materi- al over a relatively short period of time, the result obtained will be es- sentially an instantaneous measure of the nitrogen oxides. It will be rep- resentative of the emissions only if the gas stream is well mixed and the concentration is constant with time. Multiple samples are .therefore neces- sary. Analyses 10. Nitrogen oxide levels are determined by the EPA procedure desig- nated as "Method 7". Nitrogen oxides (except for nitrous axide-N20) are measured coloranetrically using the Phenoldisulfonic Acid Procedure. The method is applicable for measurement of nitrogen oxides (as NO2) from sta- tionary sources in the range of 2 to 400 milligrams per dry standard cubic meter, without having to dilute the sample. 11. A similar method has been developed by the American Society or Testing and Materials, designated as Method ANSI/ASIM-D-1608-77. This meth- od is applicable to concentrations ranging fran 4 to several thousand mill- igrams per dry standard cubic meter. AMBIE AIR MONITORIN Sampling 12. The number of sampling points required for an ambient air moni- toring network will depend upon program objectives, effluent requirements, meteorological conditions, topography, and other related factors. For a small source, particularly if. cne wind direction . predominates, only two sites are required. One site would be for monitoring source effects while the other would provide upwind or background concentrations. Where wind directions are variable several sampling points are required. 13. It is desirable to place collecticn. devices in areas most likely to receive the highest ground-level concentrations of pollutants. Plume trajectory frcm emission source to the point of ground-level impact may be predicted roughly fra a knowledge of predominant wind directions. A con- venient tool for performing such an analysis is the "wind rose"; a chart which plots wind directions and percentage of time, annually, that wind is blowing frca that, direction. Where more precise information is required for site selection, computerized atmospheric dispersion models may be nec- essary. EVACUATE YY j....SQUEEZE BUL8 e PURGE UMP VALVE PROBEFLASK VALV SAMPLE PUMP est a .MANOMETER GROUND-GLASS SOCKET. FLASK EVACUATE NO. 12/5 , 50 mm *.VENT FLASK SHIELD , .* 110 MM . PURGE THERMOMETERo 65mm or 3*WAY STOPCOCK. RBRE. -PYREX. 2-nvn BORE. 0-mim OD 210 mm FO4AM ENCASEMENT GROUND-GLASS CONE. OMCSE STANDARD TAPER. GROUND-GLASS 7 (M SLEEVE NO. 24/40 SOCKET. NO. 125t PYREX... 180 m SOILING FLASK* .-LITER. ROUND-BOTTOM. SHORT NECK. WITH SLEEVE NO. 24/40 Figure 1.- Nitrogen*Oxide Sampling Train for Stationary Sources (From U.S. Code df Federal Regulations, Title 40, Part 60 Appendix A-July 1, 1981). - 207 14. The principal factors in selecting the sampling locations are topography and meteorology. Other considerations include: (a) Location of the sampling site, relative to pollutant source, accessibility, and operation. (b) Sanple delivery to laboratory facilities. (c) Proper handling of samples to prevent deteriora- ticn or conversion that would produce inaccurate results. (d) Availability of suitable analytical procedures and instrumentation for generating acceptable quantitative and qualitative data. (e) legal restrictions (such as effluent limitations) affecting the discharges fran existing sources. 15. Preferably, ambient levels should be monitored continuously.Con- tinuous samples nay be obtained by a variety of instrument techniques and are particularly suitable for averaging over long time periods. Non-auto- natic (or dynamic) samples may be used When continuous types of equipment are not available. 16. A typical continuous monitoring device consists of an inlet sec- ticn, gas pretreatment section, detector, photamultiplier, spectrometer, and readout device. Depending upcn conditions of the gas to be analyzed, pretreatment could include pressure adjustment, particulates removal (usu- ally by filter), moisture renoval (usually with silica gel column) and tem- perature adjustment (usually by condenser). 17. Basic COmLpcnents for a dynamic sampling unit (shown in Figures 2 and 3): include inlet, fritted bubbler, drying tube, temperature gauge, dry test meter, pump, and anameter. Analyses 18. The chemiluminescent method, adopted by the U.S. Eavironmental Protection Agency, ard cited in the Bibliography, is the preferred analyti- cal method for determining nitrogen dioxide levels in ambient air samples. This is an autcmated continuous method Widh records a measurement every few seconds, and readily permits determination of specific time average levels. The method is applicable to measurements in the range of zero to about 2,000 milligrams per cubic meter. [ 209 19. Chemiluminescence analyzers wil-I respond to otber nitrogen con- taining compounds,, such as peroxyacetyl nitrate. A±mospheric concentra- tions of these potential interferences are generally 1cW relative to NO2,, and bence valid NO measurements imy be * Where levels of inter- fering substances ?S ch as sulfur dioxide and ozone levels) are suspected of being high. then an alternate method should be used. 20. Nitrogen dioxide levels may be determined manually by the Griess- Saltzman Method,, adopted by the American Society for Testing and Materials,, and cited in the Bibliography. The sanpling train shown in Figures 2 and 3 should be used for this purpose. Sampling periods should be 'between 15 and 30 minutes, at a flow rate of about 0.4 liter/per minute. The method is applicable for levels in the range of 4 to 10,000 microgram per cubic meter. 22. In the Griess-Saltzman Methodt N02 is absorbed in an azo-dye- forming reagent. A red violet color is produced witl 15 minutes, and its intensity measured spectrometrically at 550 nanometers. 23. A ten-fold ratio of sulfur dioxide to nitrogen dioxide produces no effect. A 30-fold ratio slowly bleaches the color to a slight degree. Addition of acetone to the reagent retards fading, and permits reading the color intensity within 4 to 5 hours instead of 45 minutes required without aontone. A 5-fold ratio of ozone to nitrogen dioxide will cause a small interference, with the maxinal effect occurring within 3 hours. Other ni- trogen oxides and other gases that may be present in polluted air could al- so interfere with the accuracy of the manual method. BIBLIOGRAPHY 1. World Health Organization "Oxides of Nitrogen". Environmental Health Criteria 4. World Health Organization. Geneva (1977). 2. U.S. Code of Fedeal Regulations, Title 40,, Part 60, Appendix A,, Method 7. "Determination of Nitrogen Oxide Emissionss from Stationary sources". office of the Federal Register. Washington (July 1, 1981). 3. U.S. Environmerrtal Protection Agency. "Handbook-Industrial Guide to Air Pollution Control". Document EPA-625/6-78-004. Washington (June 1978). 4. American Society for Testing and Materials. "Standard Test Method for Oxides of Nitrogen in Gaseous Cmbustion Products (Phenol-Disulfcnic Acid Procedures)". Method ANSI/ASTM D-'1608-77. Philadelphia (1977). S. Organization for Economic Cooperation and Develolxrent. Photochemical Oxidant Air Pollution,", Paris (1975). - 210 - 6. U.S. Code of Federal Regulations, Title 40, Part 50, Appendix F. "Measurement Principle and Calibration Procedure for the Measurement of Nitrogen Dioxide in the Atmosphere (Gas Phase Chemiluminescence) ". Office of the Federal Register. Washingtcn (July 1, 1982). 7. American Society for Testing and Materials. "Standard Test Method for Nitrogen Dioxide Content of the Atmosphere (Griess-Saltzman Reacticn)". Method ANSI/ASTM D-1607-76. Philadelphia (1976). - 211 - TE WOELD BANK OCTOBER 1980 OFFICE OF ENVIRONMENAL AFFAIRS NOISE 1. Bank missions will be concerned with noise and its environasntal affects in various types of projects. Among these are highway and railway projects, airports, agricultural enterprises (from .9peration of farm machinery), and industrial installations. BASIC CONCEPTS 2. Noise may be described as sound without agreeable musical quality, or as "unwanted sound". Generally, noise is produced when an object or sur- face vibrates rapidly enough to generate a pressure wave or disturbance in the surrounding medium. From the standpoint of environmental effects the medium of greatest concern is air, although sound may also be transmitted through liquids and solids. 3. Sound is transmitted by wave motion. It propagates as the result of the elastic interactions between the molecular components of the medium through which it travels. The speed of sound, therefore, depends upon the mass of molecules (density) and their elastic reactions (pressure). The human ear responds to the pressure fluctuations set up in the surrounding medium. Air- borne sound travels at a speed of 344 meters per second at a temperature of 200C. In seawater sound travels at the rate of about 1490 meters per second. 4. The decibel (dB) is used to measure the relative pressure of differ- ent sounds. The decibel is equal to 20 times the logarLthm of the ratio of sound pressure to a reference pressure of 20 #Pa*, or., Sound pressure level (dB) a log10 Measured Pressure Reference Pressure Thus, a sound with 10 times the pressure of another is considered to be 20 dB louder, and each succeeding 10-fold increase adds another 20 dB to the sound level. Relative sound pressure levels for various degrees of "loudness" are presented in Table 1. 5. The quality of sound (or noise) is measured by flow of energy per unit area. Frequency is a measure of the number of complete vibrations occur- ing per second, and is measured in "hertz" (z). Thus, 1 Ez equals 1 cycle per second. Normally, the human ear cannot detect sounds above 15,000 Ez (ultrasound). The lower limit of human detection depends more on the quantity- of sound. At 65 Ez the human ear does not normally detect sounds below 60 dB. *.1 Pascal = 10 dyne per square centimeter. -212 Table 1. Relative Sound Pressure Levels for Various Sources of Noise a/. Relative Sound Ptessude Lavels Appar=nt EdsB .ø .o Pascals Loud~s 0 dB Deafening Jet aircraft 140 10,000900 200 Threshold of feeling 130 3,162,000 Very loud Elevated train, thunder 120 1,000,000 20 Subway train, rtveter 110 316,200 Noisy Ind. Plant 100 100,000 2 Loud street noise 90 31,620 Noisy office 80 10,000 0.2 Loud Av. St-eet noise 70 3,162 Av. office 60 1,000 0.02 Moderate Mod. restaurant clatter 50 316 Private offica 40 100 0.002 Fa-nt Rustling leaves 20 10 0.0002 Very faint. Normal breathing 10 3 Theshold audibility 0 1 0.00002 From '"So nd Control Costruction" U. S. Gypsu Ca. EASUREET OF NIZSZ 6. The basic goal in quantifying sound is to determine the time and location variations of noise in the environent throughout a com=uity and to assure that the data can be used as a measure of the effects of environ- mental noise en people. - 213 - 7. The Sound Level Meter (SLM) is the basic instrument for measuring sound or noise. While such instruments are available from a number of manu- facturers, all meters to be used for this purpose must meet the American National Standards Institute (ANSI) specification S1.4-1971, or the latest ANSI issuances. Both Type 1 (Precision) and Type 2 (General Purpose) meters are acceptable. The Type 2 meter has broader performance tolerances,and is usually less bulky, lightex, and less expensive than.the Type 1. 8. A sound. level meter electronically weighs the amplitude of the vari- ous frequencies in accordance with a person's hearing sensitivity and sums the resulting weighted spectrum into a single number. "The typical meter contains three different response weighting networks: A, to match the response of the ear to sound of low intensity; 3, to match response to sound of moderate in- tensity; and C,to match response to sound of high intensity. The A scale is most commonly used, since it most closely approximates the human perception of sound. The weighted sound level unit, at the A setting is commonly designated as dB (A). 9. The SLM A-setting measures the sound level at a frequency of 1,000 Rz. Where frequency readings differ from the standard of 1,000 Hz, then a correction muist be made to convert "flat" response readings to the A levels. The term "flat'response designates the uniform response of an instrument over a wide frequency range, up to 20 K Hz. Table 2. Corrections from "Flat" Resonse Levels to A Levels. Octave Band Center Correction Frequency (Ez) (d) 31.5 - 39.5 63 - 26 125 - 16 250 - 8.5 500 - 3.0 1000 0 2000 + 1.0 4000 + 1.0 8000 - 1.0 16000 - 6.5 - 214 - EFFECTS OF NOISE 10. A universal effect of noise is its interference with the understand- ing of speech. This is one aspect of "masking" - an interaction of two acoustic stimli whereby one of then changes the perceived quality of the other, shifts its apparent location or loudness, or makes speech completely inaudible. Various factors enter into the degree of speech interference, such as speech, age, and hearing of individuals. Children have less precise speech than do adults, while older persons are more susceptible to interference from background noise. 11. Noise can elicit a variety of physiological responses, but no clear evidence exists to indicate that continued activation of these responses leads to permanent health effects. Sounds of sufficient intensity can cause pain to the auditory nervous system. It can be presumed that noise exposure can cause general personal stress, either by itself or in combination with other stress sources. Noise exposure to moderate intensities that may be found in the environ- ment does have some effect on the cardiovascular system, but no definite permanent affects on the circulatory systems have been demonstrated. Moderate noise levels have been known to cause vasoconstriction of the periphe-al areas of the body and pupillary dilation, but there is no evidence that these effects can lead to harm- ful consequences over a period of time. 12. Continuous noise levels above 90 dB (A) have detrimental effects on human performance, especially in so-called "noise-sensitive" functions, such as vigilance tasks, information gathering, and analytical processes. Noise levels below 90 dB (A) can be disruptive, particularly if they have predominantl high frequency components, and are intermittent, unexpected and uncontrollable. 13. Frequencies below 16 Hz are referred to as infrasonic, and include such sources as earthquakes, wind, thunder, and distant jet aircraft. Man-made infra- sound occurs at higher intensity levels than those found in nature. Effects associated with infrasound resemble mild stress reactions and bizarre auditory sensations, such as pulsating and fluttering. Ultrasonic frequencies are those above 20,000 Rz, and are produced by a variety of jet engines and industrial equipment. Above 105 dB, the effects of high intensity ultrasounds resemble those observed during stress situations. 14. ' Noise has the same general effects on wildlife and other anials as it does on humans Noise of sufficient intensity can disrupt normal patterns of animal existence. Exploratory behavior can be curtailed, avoidance behavior can limit access to*food and shelter, and breeding habits can be disrupted. Hearing loss and the masking of auditory signals can complicate an animal's abilities to recognize its young, detect and locate prey and evade predators. Physiological effects of noise exposure-such as changes in blood pressure and chemistry, hormone balance, and reproductivity-have been demonstrated in labora- tory animals and, to some extent, in farm animals. 15. Secondary effects of noise on the health and welfare of man include three general types: sonic boom effects, noise induced vibration and sonic fatigue. Saund can also cause buildings to vibrate, and this can have a direct effect on humans.. Some booms of sufficient intensity not only can break windows, - 215 - but they can also damage building structures. However, sonic booms can be con- trolled to levels which are innocuous in relation to buildings and structures. Noise induced vibrations near rocket launch sites can also cause window break- age. Construction activities may have similar effects. Sonic fatigue is also a problem where material is used near intense sound sources, but such problems can be avoided by proper design and this type of fatigue does not usually cause environmental problems. NOISE CONTROL TECENIQUES 16. Noise control techniques fall into two general catetories: control at the source and control of.the path of sound. Within the urban environment noises originate principally from aircraft and airport operations, industrial operations, construction activities and highway traffic. 17. Aircraft related noises mainly,.affect the populations living near airports or in the flight paths of low flying airplanes. Although many new types of jet-powered ships introduced since 1972 emit less noise than earlier models, noise continues to be the most serious constraint currently facing air- port operations. 18. A number of techniques may be applied, alone or in combination, to the reduction of aircraft noises and their affects. The principal ones include: - Operational measures designed to limit the production of noise by aircraft. This could involve special take- off and landing procedures, restrictions on the total noisy aircraft traffic, banning of night traffic, diversion of part of the traffic to other regional airports, and appli- cation of local airport noise regulations. - Measures aimed at changing the land use in areas exposed to heavy noise. This requires close coordination of airport planning with regional and local land use policy. Such an ap- * proach is most easily implemented in the case of new airports in areas not yet intensely developed. Eowever, even around . existing airports it is possible to re-z=ne the heavily im- * pacted areas over a period of time and minimize noise exposures for private dwIellings, schools, hospitals and recreation areas. - Measures aimed at reducing the impact of noise at the point of receiption. This will require sound-proofing of private residences, hotels, offices and other structures. Such measures should be taken as a last resort, since they do nothing to eliminate the source of the noise or to improve the outdoor environment. 19. Noises resulting from industrial operations are generally confined within the plant structure. Machinery and equipment are the main sources, and the effects are felt mostly by the individual workers. Controls may be accom- plished through measures at the source (relocation, vibration, vibration control, - 216 etc.); installation of acoustical shields, enclosures, or other barriers to interrupt the path of the sound; or through limiting the duration of the ex- posure by the receiver. The first two of these measures will help reduce the noise levels in the environment outside the plant. 20. While construction operations are not permanent, large projects are carried out over relatively long time periods, and measures are frequently re- quired to reduce noise emissions. Construction noises can originate from such sources as crane and hoisting equipment, air compressors, concrete mixers, tractor and bulldozing equipment and materials delivery vehicles. 21. Noise control at construction sites will require an analysis of each individual situation to determine which measures should be applied. The gen- eral measures which can be effective include* - Assurance that the manufacturer has designed, built and equipped the unit to conform with existing noise control regulations. - Adequate operation and maintenance of equipment. - Limiting the time of day during which equipment may be operated. - Limiting the places or zones in which equipment may be used. 22. The effect of vehicle noise on populations is usually dependent upon traffic concentrations rather than on any one individual vehicle. Although trucks are normally fewer in number, they tend to contribute the largest share of the noise. Motorcycle traffic can also be a significant contributor. For highway vehicles, noises originate from the exhaust systems, engines, special features (such as loading machinery on solid waste carriers and other heavy duty trucks), and other individual characteristics. 23. Noise abatement measures are similar to those for construction equip- ment, as given in paragraph 21. Additional controls may be imposed through licending and inspection procedures, and through driver education on operational procedures. ACCEPTABLE NOISE LITATIONS 24. There are considerable variations in the recommended allowable noise levels emitted by the many individual sources existing in the environment. The limitations presented in Table 3 reprasent the net effect of cumulative contribu- tions from all sources. The levels &Lven are considered adequate for protecting the health and welfare of the general public in the specific environmental situ- ation. The term "public health and welfare" denotes personal comfort and well- being as well as the absence of hearing damage or other clinical symptom. - 217 - . Table 3. Yearly Average Equivalent Sound Levels Reguired for Protection of Public Health and Welfare 17 Indoor To Protect Qutdoor To Protect Activity Hearing Loss Aamst Activity Huarinc Loss Against Measure Inter- Considera- Both Ef- Inter- Considera- Both Ef- 2/ ference tion fcts (b) frence tion ct (b) Residential with Out- Ldn 45 45 S5 55 side Space and Farm Residerces Leq(24) 70 Residential with No Ldn 45 45 outvide Space .0 c(24) 70 Commercial Leq(24) (a) 70 70(c) (a) 70 70(c) Inside Tr4nsportation Leq(24) (a) 70 (a) Industrial Le(24)(d) (a) 70 70(c) (a) 70 70(c) Hospitals Ldn 45 45 55 55 Leq24) 70 70 Educ2ticonal Leq(24) 45 45 S $5 Leq(24)(d) 70 70 Recreational Areas Le9124) (a) 70 70(c) (a) 70 70(c) Farm Land and Leq(24) (a) 70 70(c) General Unpopulated I Land Code: a. Since different types of activities appear to be associated with different levels. identifi- cation of a maximum level for activity interference may be difficult except in those * circumst2nces where spexch cuniaiUOn is, %x.;itica! activity. bt, Basud on lowest level. c. Bused only on hicaring loss. d. An L.q(8)I of 75 dB may be identified in these situations so long as the exposurc over the remaining 16 hiours pvr day ii low enough to result in a negligibiecLzontribution to the 244hout averie, i.e.. no greater than an Lq of 60 d3. / From Ref. 4 / L = Day-night average A - weighted equivalent sound level, with a 10-decibel weighting applied to night time levels. L eq (24) - Equivalent A-weighted sound level over 24 hours. - 218 - BI3LIOGRAPET 1. Peterson, A.P.G. and E.E. Gross, Jr. "Eandbook of Noise Measurement" General RadIo Inc. Concord, Mass. (1974). 2. U.S. Department of Commerce/National Bureau of Standards. "Quieting: A Practical Guide to Noise Control", NBS Handbook 119. Washington (1976) 3. U.S. Environmental Protection Agency. "Public Health and Welfare Criteria for Noise". Doe. 550/9-73-002. Washington (July 27, 1973). 4. U.S. Enviromenta1 Protection Agency. "Information on Levels of Environ- mental Noise Requisite to Protect Public Health and Welfare with an Ade- .quate Margin of Safety". Doc. 550/9-74-004. Washington (March 1974). 5. United States Gypsum, "Sound Control Construction-Principles and Performance 2nd Ed. Chicago (1972). 6. United Anto Workers, "Noise Control-A Worker's Manual". Detroit (February .1978). 7. U.S. Federal Register, "Noise Emission Standards for Construction Equipment- New Wheel and Crawler Tractors". Vol. 42, No. 132, pp. 35804-35820. Wash- ington. (July 11, 1977). 8. "Transportation Noises", A Symposium on Acceptability Criteria. Ed. by James D. Chalupnik. University of Washington Press. Seattle and London (1970). 9. "Airports and the Environment". Organization for Economic Cooperation and Development. Paris (1975). 10. U. S. Enviromental Protection Agency. "Fundamentals of Noise: Measurement, Rating Schemes, and Standards". Doc. NTID 300.15. Washington (December 31, .1971). -219- THE WORLD BANK FEBRUARY 1983 OFFICE OF ENVIIMENTAL AFFAIRS 1CtT-FERROUS METALS INDUSTR ATI4INE4 PRODUCTION ENVIRONMENI'A GUIDEf.INS 1. The non-ferrous metals category includes a large umber of metal- lic elements, but only a few are of concern to World Bark operations at this time. Those nost freqently encountered in Bank activities are cover- ed in four separate documents in the series, as follows: (a) alumirm; (b) lead and zinc; (c) copper and nickel; and (d) silver, tungsten, columbium, and tantallum. This document will concern itself with alumirmm production. 2. Both primary and secondary aluminum will be discussed, the class- ification being based upon the raw materials used in the production. Norm- ally, the primary metal is produced fron the raw ore, while the secondary metal is produced fra manufacturing scrap, discarded consumer items, and other residues containing economiically recoverable quantities. The manu- facturing process and waste sources are shcwn in Figures 1 and 2. .. 3. Aluminum is considered to be the nost abundant metal in the earth's crust. The aluminum industzy is international in scope, and its m anufacture, fabrication, and use are currently worldwide. The wastes re- sulting fron the industry's operations are of significant proportions, and hence their effects must be considered in environmental inpact assessments. .NUFACIURIN PROCESSES 4. The basic material used in the manufacture of aluminum metal is bauxite ore. Major sources of the mineral are South America, the Caribbean and Australia. Specific sources include Jamaica, aiti, Costa Rica, Suri- nam, Guyana, French Guiana, Brazil, Ghana, Guinea, Sierra Leone, Cameroon, . Sumatra, Java and Borneo. 5. The nost CaIonly used method for the production of aluminum met- al fran bauxite ore is the Bayer Process, follcwed by the Hall-Heroult Pro- cess. Thus, aluminum production my be considered a two-step process. 6. In the Bayer Process the bauxite is digested with a bot, strong alkali solution (generally sodium hydroxide) to form a sodium aluminate solution and an undissolved residue MUmnonly called "red mad". The red mid is separated by filtration and reworked for recovery of additional alum- ina. The sodium aluminate solution is hydrolyzed to aluminum hydroxide by cooling and dilution, and the hydroxide then induced to crystallize by seeding with alumina crystals. The precipitate (which is the aluminum by- droxide) is separated fran the liquor, clarified in tray thickeners, washed with hot water, and filtered. As the final step the hyudroxide is calcined ANTHRACITE, PITCH COKE BLENDING ADE PSTE E BLENDIENDG14 CLSIYN ___ECTCL______________ POTL NING SOLIDS DISPOSAL COOLING PRESSING EMISSIONS ELECTROSTATIC PASTE PLANT LIOUOR BAKING PRECIPITATOR SCRUBDER SODERIIERG ALUMINA DIRECT CURRENT 40. * ~ POTLINE &--- ECRYOLITE. Caf. MF, . LECTROLYTIC EMISSIONS POT ROOM KE PLANT LIOUOR DISPOSAL SPENT POTLINER LIOUOR ALUiNUM CRYOLITE EA31GACITD R CEyRY DEGASSIdU. --VA D I CO :LE Y AUMINJA T- - - - ----ABSORPTION SOEIDS TO .4*I1TI W LANDFLL CIaOR MIXED GASES IFUMES ACTIVATED ALUMINUM TO ELECTROLYTIC *aO CELL COOINGCASIN LIQUOR E WAER COOLINGSCRUBBER BLOWDOWN ALUMINUM TO TREATMENT Fig. 1 - Primary Aluminum Reduction Process (From US EPA Document EPA 440/1-79/019a) -221- ALUMINUM SCRAP WASTE -- AGHOUSE SORTING SOUD3 DRYINGFUMES ADUST CRUSHING ,REMOVED IRON SEPARATION .CHARGING3 SREVERBERATORY FUMAES AFTERBURNER EXHAUST * FURNACE SLUDGE NoCS, KCI. Ca Cit. Not, Na, AP& DISCHARGE FLUX ADDITION TREATMENT OR RECYCLE AALLOYING,TS Zin. 81. Cu, Mg.*n DEMAGGING ruMAES7 FUMES ,SCRUSSER DEGAS31NG .St.AG TO DISPOSAL OR MILLING MOLTEN ALUMINUM M2O TO RECYCLE OR TREATMENT II CASTING 4CRUCIBLE Ha COOLING S SHIP (OLTE ALUMINUM SHIP ALUMINUM INGOTS Fig. 2 -Secondary Aluminum Smelting Process (From US EPA Documient EPA 440/1-79/019a) --- 222 in rotary kilns, at tenperatures up to 1800*C to produce alumina 4Al2 03), cooled, and shipped to reduction plants. 7. The alumina is then reduced electrolytically by the Hall-Heroult Process, to produce aluminum. This invlves the electrolysis of alumina dissolved in a fused salt electrolyte consisting of cryolite (Na3Al F6),* with minor additions of other fluoride salts. The process is carried out in a cell (pot) - consisting of a carbon anode, a cathode, and the elec- trolyte - contained in a carbon-lined steel box. This is followed by al- laying and casting into ingots. The ingots are then shaped for final use by casting, rolling, forging and/or extrusion. 8. For secondary alumim production, the raw materials include new clippings; forgings and other solids; borings and turnings; residues; old castings and sheets; and high iron scrap. 9. The smelting process for secondary aluminum generally consists of six steps: charging scrap into the furnace, addition of fluxing agents, addition of alloying agents, mixing, demagging (magnesium removal) or de- gassing, and skinmiig. Sae plants also process residues to recover a high aluminum fraction for smelting and a low aluminum fraction for use by steel manufacturers as ingot topping. High-iron scrap undergoes presmelting treatment for iron removal. WASTE SOURCES AND CHARACTERISTICS * 10. The irjor environmental concerns in bauxite mining operations are :Aand erosion, runoff water control, and dust control. In the processing of bauxite to produce aluminum the principal environmental concerns include: (a) disposal of bauxite residue (red mud); (b) dirt losses (c) emissions fran fuel burning; and (d) waste liquid and slurry streams. Air Enissions 11. In the primary aluminum industry, gaseous emissions originate fron the potlines, potroom, paste plant, anode bake plant, and the degassing operation. Most plants effectively collect and renove the various emissions and therefore very little escapes to the atmosphere. In the secondary aluminm category, emissions originate in the deagging (nagnesium reroval) operations and fron processing of furnace residues. These also are effectively collected and removed. 12. The emissions, in both primary and secondary plants, will contain dusts, fluorides, sulfur compounds, fuel combustion products, certain or- ganic pollutants, phenols, cyanides (in cryclite recovery) and organic car- bon in varying amounts. Liquid Wastes 13. The conventional water pollution parameters (biochemical oxygen denand, chemical oxygen demand, total organic carbon, oils and greases, etc.) have limited values in the non-ferrous metals industry. High concen- trations of metals, a characteristic of the wastes, will inhibit biological activity and render these tests ineffective and of limited value. 223 - 14. In primary aluminum production the significant parameters are to- tal fluorides, total suspended solids, and pH. For secondary production these are also significant, but to them nust be added amonia nitrogen, aluminum, and copper. 15. Process wastewater in primary aluminum production originates fran the wet scrubbers used for air pollution control in the potline, potrooan, paste plant, anode bake plant, and the degassing operation. Other waste stream originate from the cryolite recovery, ingot cooling, and cathode making. For secondary aluminum operations the wastewater results fron de- Wagging, wet milling of residues, and contact cooling. Solid Wastes 16. Solid wastes include bauxite residues (red nud), residues fran air pollution control devices (precipitators and scrubbers), and the waters used to cool the ingots and castings. The cathodes, consisting of carbon liners which hold the molten aluminum, are replaced periodically and re- quire disposal. Spent cathodes will have a significant fluoride content, and water runoff fron storage areas used for the spent units will. contain fluorides. Scrubbers, furnaces, and ingot cooling are the principal solid waste sources in secondary aluminum production. E FN LIMITATIONS -.AIR EMISSIONS - 17. Control measures should be such that there will be very minor or no emissions to the atmosphere. The dusts and gases are usually collected for recycling and byproduct recovery, or for discharge with the wastewater streams. 18. Where gaseous emissions are discharged to the atmosphere, the following limitations are to be observed: Sulfur Dioxide (SO9) Inside Plant Fence Ann. Arith Mean 100 pg/m3 Max. 24-hour Peak 1000 pg/m3 Outside Plant Fence Ann. Arith Mean 100 ig/m3 Max. 24-hour Peak 500 3g/m3 fluorides (as HF) Ann. Arith Mean 10 jg/m3 Max. 8-hour Peak 100 pg/m3 Particulates Ann. Gecn. Mean 75 pg/m3 Max. 24-hour Peak 60 pg/m3 Liquid Effluents 19. Discharge limitations, based on the best practicable control technology currently available, are as follows: 224 - Primary Aluninum - Srelting Max. 24-hour Fluorides (total) 0.05 Ng/Mg* Aluminum TSS 0.10 " " pH 6 to 9 units Secondary Aluminum - Smelting Max. 24-hour -Fluorides (total) 0.4 NG/Mg * Alumimm TSS 1.5 " " NH3 (as N) 0.01 " " - Al 1.0 " " CU 0.003 "" PH 6 to 9 units * 1 Mg = 1 Megagram = 1 Metric ton. Solid Wastes Bauxite Minin (a) There is to te no disposal of mine tailings to waterways or to the sea, except urxer very special circumstances and very carefully controlled conditions. (b) A reclamation program is to be established for handling mine tailings. The project sponsor is to submit a proposed plan of action, which will be. evaluated as part' of the project appraisal. (c) The reclamation program is to be initiated within three (3) years of the start of project perations. Bauxite Processing and Refining There is to be no disposal of red nud into either the waterways or into the sea. CONTROL AND TREA'IMEN OF WASTES Air Muissions 20. The industry makes extensive use of both wet and dry methods for control of particulates ard gases. Liquid effluents fran the wet systems are discharged with the wastewater, except, where there is byproduct recov- ery or utilization. Dry systems are preferable to wet systems, since re- movals are just as effective and liquid waste flows are reduced. -225- Liquid Effluents 21. In-plant controls should be carefully considered as the first step in reducing wastewater loadings and volumes. In-plant measures include improvemnt of bousekeeping practices, byproduct recovery, wastewater recycling (with or without treatment), and others. 22. Technology applicable to primary aluminum wastes includes treat- ment of wet scrubber water and other fluoride-containing effluents to pre- cipitate the fluorides. This is followed by settling of the precipitate and recycling of the clarified liquid to the wet scrubbers. Pecycling will control the volume of wastewater discharged. 23. Wastewaters containing fluorides will originate fran the potline, potrooms, anode bake plant, used cathode disposal, used cathode storage area, and storm water runoff. Precipitation of these. effluents may be ac- conplished by addition of cryolite or lime. Holding ponds or lagoons should be provided for settling of that portion of the flow. not recycled. 24. In secondary aluminum production, wastewaters originate fran met- al cooling, fume scrubbing, and residue milling. Metal cooling flows may be reduced or eliminated through air cooling of ingots or recycling. Fume scrubber wastewaters may be recycled after pH adjustment and settling. Ef- fluents fran residue milling should be given three or four-stage settling, pi adjustment, and total impoundment. Solid Wastes . While a nmiber of disposal methods for bauxite residues have been investigated, scme forM of dumping is currently considered to be the best method, including (a) land impoundment; (b) ocean dumping by ships, barges, or pipelines; and (c) seashore reclamation. 26. Land impoundment in a diked impevious area is most frequently used, and is the method to be generally employed for Bank-supported pro- jects. Care must Ie taken to avoid contamination of ground waters. The settling ponds can remove 30 to 60 percent of the solids. In scme cases, water from the inPoundment area can be returned to the process as make-up water. 27. Sea disposal is practiced in a number of areas. At scme sites in the Mediterranean, the residue is discharged via pipelines into underwater canycns at depths of over 2,000 meters. In Japan sea dumping is permitted, but only to areas and by methods specified by government regulations, with disposal areas being located over 300 kilometers fra shore. Use of baux- ite residue fcv seashore reclamation is permitted in Japan cn a limited basis, but ms -teen found to be very costly. For Bank-sponsored projects sea disposal may be used in special cases only, under carefully controlled conditions, and with the assurance that there will be no harmful effects on sea life. -226- 28. Sludges fra settling or other treatment of waste streams are transferred to contractors or reprocessors for recovery of metals. Drying beds, lagoons, landfills, or incineration are also used. Gravity thicken- ing, vacuum, filtration, or other conditioning may be applied ahead of ulti- mate disposal. 29. Particulate matter frn dry scrubbers is burned, dumped on land, or recycled for byproduct recovery. BIBLIOGRAPHY 1. "The Aluminium Industry and the Environment." UNEP Industry Sector Seminars, Aluminium Meeting, Paris, 6 to 8 October, 1975. Papers and Documents. (1975) 2. "Environmental Aspects of the Aluminium Industry - An Overview." UNEP Industry Progranme. Paris (May 1977) 3. "Environmental Recommendations for Siting and Operation of New Primary Aluminium Industry Facilities." International Primary Aluminium Insti- tute. London (1977) 4. "Air Pollution Control in the PriTary Aluminum Industry." Singmaster & .. Breyey. New York (1973) . 5. U.S. Environmental Protection Agency. "Environmental Considerations of Selected Energy Conserving Manufacturing Process Options." Alumina/ Aluminum Report. Doc. EPA 600/7-76-034 h. Washington (Decerber 1976) 6. U.S. Enviromental Protection Agency. "Development Document for Pro- osed Effluent Limitations Guidelines and New Source Performance Stand- ards for the Bauxite Refining Subcategory of the Aluminum Segment of the Nonferrous Metals Manufacturing Point Source Category." Doc. EPA 440/1-74-019-c. (March 1974) 7. U.S. Environmental Protection Agency. "Development Document for Pro- posed Effluent Limitations Guidelines and New -Source Performance Stand- ards for the Primary Aluminum Smelting Subcategory of the Nonferrous Metals Manufacturing Point Source Category." Doc. EPA-440/1-74-019-d. (March 1974) 8. U.S. Environmental Protection Agency. "Development Document for Ef- fluent Limitations Guidelines and New Source Performance Standards for the Secondary Aluminum Smelting Subcategory of the Aluminum Segment of the Nonferrous Metals Manufacturing Point Source Category." Doc. EPA-440/l/74-019-e. (March 1974) 9. U.S. Environmental Protection Agency. ,"Development Document for Ef- fluent Limitations Guidelines and Standards for the Nonferrous Metals Manufacturing Point Source Category." Doc. EPA-440/1-79/019-a. (September 1979) - 227- 10. "Standard Methods for the Examination of Water and Wastewater." 15th Edition. American Public Health Association. New York (1980) 11. "Code of Federal Regulations - Protection of Environment, " Title 40, Parts 400 to 424, U.S. Government Printing Office. Washington (July 1, 1981) 12. Atkins, M.H. and J.F. Lowe. "The Econanics of Pollution Control in the Non-Ferrous Metals Industry." Pergamon Press. , Oxford (1979) 13. Boodson, K. "Non-Ferrous Metals - A Biographical Guide. " Macdonald & Co. (Publishers) Ltd. London (1972) - 228 - THE WORLD BANK MARCH 1983 OFFICE OF ENVIRONMENTAL -AFFAIRS NON-FERROUS MEnUS INDUSTM COPPER AND NICKEL PRODU)CTION ENVIF4ENTAL GUID S 1. he non-ferrous metals category includes a large number of metal- lic elements, but only a few are of concern to World Bank operations at this time. Those most frequently encountered in Bank activities are cov- ered in four separate documents in this series, as follows: (a) aluminum; (b) lead and zinc; (c) copper and nickel, and (d) silver, tungsten, colum- bium, and tantalum. This document will cover the production of primary and secondary copper, and primary nickel. MANUFACTURI1G PROCESSES COPPER 2. shelting is the first step in the production of prinary copper from the are. One of two main process schemes is generally used: roast- ing, smelting, and converting; or simply smelting and converting. Roasting is used where nmerous types of ores are processed, in order to reduce the content of sulfur and other impurities in the feed stock. Ore concentrates of uniform consistency frequently do rot require the roasting step. 3.. Selting is carried out in either a reverberatory furnace or an electric furnace. 7he smelting and refining processes are illustrated in Figures 1 and 2. The end product is a nolten copper-iron-sulfide material called matte. The matte goes to a converter, while the slag containing the inpurities is skimned- off as waste material fbr .disposal. 4. In the converting step, the iron-sulfide co=ponent of the matte is oxidized to sulfur dioxide and iron oxide. The sulfur dioxide is carried off in the exhaust air streams. The iron oxide further reacts with silicate (added as a fluxing agent) to form iron-silicate slag. This slag contains significant amounts of copper and is thus recycled to the smelting step. The product from the converter units is called blister copper. 5. Blister copper, which contains various impurities, -is cast into anodes and sent to electrolytic refining for purification. A small percen- tage of plants use fire refining to produce refined copper. Insoluble slimes are generated during the electrolytic process. These may contain economically significant amounts of copper, selenium, tellurium, lead, sil- ver, and other precious metals. - The slimes are usually treated off site, but nay be treated on site, for byproduct recovery. . -229- COPPER CONCENTRATES GREEN FEED STEAM TO ROASTING SOLIDS TO DISPOSAL POWER PLANT EMIS ON CALINEGANGUE SOLIDS TO WAS LEAT EMISSIONS SMELTING AG GRANULATION I -- WATER SMELTING EMISSIONS MATTEy Ir7 WASTEWATER ELECTROSTATIC' COVERTING SLAG PRECIPITATOR AIR SO. SULFUrIC OLISTER BLOWDOWN ACID PLANT SLAG COPPER G FIRE NING AIR inr oCARBON WATER WASTEWATER - R CASTING WS COOUiNG ANODE OR FIRE REFINED COPPER TO ELECTRO&YSIS OR MARK T Figure 1. Primary Copper Smelting and Fire Refining Processes. (From U.S. EPA Document EPA 440/1-79/019a) - 230 - BLISTER COPPER POLE INTERMACIATE OnADE COPPERAT00 UFURNACE ELECOLYELEATHOLYT ECLEREUS CO ORLDCSROL SLMEROB-PODCTSEOVR H1 AODES . ELECROVNNIG LECTROLYTEEATE COD USECPZDomn ELECTROLYTE AsH, FUMES VENTTO ATMOSPHERE SVAPORATOR MELTING SCRUBBER LIOUOR 'FURNACE CENTRIFUGE BLACK ACID HCRU IH2 , CAKE ..( . DRYERCASTING WASTEWATER DRYERCOOLING NISO4* ALTERNATE USE COPPER- OR DISPOSAL PRODUCTS. Figure 2. Primary-Copper Electrolytic Refining Process. - (Pronm-U. S*. .EPA.Do.cwment 440 /1-79 /019a) - 231 - 6. Industrial copper-bearing scrap, discarded consumer items, and residues fran melting and refining are the basic raw materials used in sec- ondary copper production. The manufacturing process consists of pretreat- ment of scrap, smeltingi and refining. The processing depends upon the raw materials used and the desired end product. The process is illustrated in Figure 3. NICKEL 7. The nickel extraction industry may be divided into two major seg- ments, based on the composition of the raw ore. Those ores which are mined underground are mainly sulfide ores. The nickel minerals are concentrated by physical methods, and the concentrates then smelted by pyrometallurgical methods. 8. Nickel oxide ores (also known as laterite -ores) cam fron open pit mines, at or near the surface at naxium depths of sone .30 meters. The nickel deposits fron open mines cannot be concentrated by physical means. The metal is extracted either in a chemical form by leaching or as ferro- nickel by smelting. 9. Nickel sulfide concentrates Ure smelted with a flux to produce a copper-nickel-iron matte. The resulting furnace matte is treated to renove iron slag and part of the sulfur as sulfur dioxide gas, and to produce a sulfur-deficient copper-nickel matte. 10. The copper-nickel matte is slowly cooled to form copper and nick- el sulfide crystals, plus a nickel-copper alloy containing significant quantities of precious- metals4 The crystal nass is pulverized to separate the conponents fran each other. The nickel-copper alloy in the pulverized mixture is extracted magnetically and then refined electrolytically. The nickel-copper sulfide minerals are separated by flotation. 11. In one type of process the nickel sulfide concentrate is treated by selective leaching with amonia, under pressure, and the solution then heated to precipitate the copper. Nickel and cobalt are recovered separ- ately, as metal powders, by hydrogen reductioh of the purified solution. 12. The carbonyl process can be also used to recover nickel fran the nickel-sulfide concentrate. The sulfide is roasted to produce nickel ox- ide, and this is reduced with water gas to form crude sponge nickel. The sponge is then treated with carbon monoxide to form nickel carbonyl. Heat is applied to the carbonyl to decampose the Ni (CO)4 mixture and produce nickel pellets or nickel powder. Iron sulfide concentrate, the residue fron the carbonyl process, is further treated to recover nickel oxide as a marketable product. 13. Nickel oxide laterite ore, after drying and screening, is pro- cessed by smelting with coke, limestone, and gypsum to form an iron-nickel matte. The matte is then treated in the same way that mattes with similar conposition are smelted and refined in the processing of sulfide ores. . 〕 233 14. Another metbod of processing laterite ores is to smelt them with coke and limestone,, or other carbon reductant,, to produce ferronickel. The ferronickel 'is refined by depbosphorization, and removal of the silicon and cbromium as a slag. M6 refined product is marketed. is. Cxide ores may also be processed by leaching with ammonia or with asulfu.:-ic acid. Ammonia will produce nickel oxide,, which can be marketed or further refined by the methods used for sulfide ores. In sul- furic acid leaching the nickel and cobalt are precipitated as sulfides by hydrogei, lvilfide. Mie crude sulfide is leached in a weak acid solution to redissolve the nickel and cobalt,, then . ralized with ammonia and pro- cessed for recovery & nickel arxi cobalt powders. MASTE SOURCES AND CHAPJC=ST'-rC-S COPPER Air Emissions 16. Emissions fran the copper smelting and refining cperations i i nate in the roasting, smelting, and converting processes. Sulfur dioxide and partaculates are the principal pollutants. In some.plants these gases pass through a boiler for beat recovery and then through a low-velocity flue device to settle cut the heavier particulates. The smaller particles are usually removed by electrostatic precipitators or by baghou-ses. 17. Mere gases are not burned in a boiler, the sulfur dioxide is re- covered as liquid S02 or as sulfuric acid. Gases are preconditioned by electrostatic precipitators or scrubbing towers to remove the particulates and prevent the buildup of soluble salts such as metallic sulfates and hiorides. In secondary copper production, sone emissions result from burning,, drying,, and shredding of the raw stock,, but these are n::)t consid- ered to be significant. Uquid Effluents 18. Wastewater from smelting in primary copper production originates frcrn the acid plant blowdown, contact cooling, and slag granulation. In the refining facilities the effluents consist of waste electrolyte and cat- bode wash,, anode wash,, and contact cooling waters. Sources within a secon- dary copper plant include slag millirig and classification, smelter air pol- lution control,, contact cooling, electrolyte, and slag granulation. Solid Wastes 19. Solids are produced mainly frau air scrubbers and precipitators, furnaces (as slag), and scrap pretreatment in the case of secondary copper. - 234 - NICKL Air EInissions 20. Enissions fran the processing of nickel sulfide ore concentrates contain significant amounts of both particulates and gases. These origi- nate nainly fran the roasters, smelters, and converters as well as from power generation facilities which nay be part of the production facility. The character of the particulates depends upon the source. Gases will in- clude one or nore of the following: Sulfur oxides, nitrogen oxides, carbon nonoxide, and water vapor. Sam nicKeA oxide is carried to the atnesphere fran roasting of precipitated nickel carbonate to remove carbon dioxide. Nornally there will be no visible emissions from a well-operated nickel electrolytic refining operation. 21. Emissions from processing of nickel oxide ores will also contain significant amounts of particulates and gases. Sources and con1position are similar to the emissions from nickel sulfide ore processing, but levels will differ. In furnaces which produce ferronickel, for example# sulfur oxides are a nuch lesser problem . Annmnia and sulfuric acid leaching operations are generally carried out in closed systems and hence contribute no emissions to the atmosphere. Liquid Effluents 22. The najor sources of liquid effluents will be the waters used for cooling at various points in the process. This woud include the converter natte, furnace natte, converter slag, driers, reduction kilns, pelletizers, and wet scrubbers, where used for emissions control. Power generation facilities, if operated as part of the installation, may also be a source of cooling water. 23. Significant paraneters governing discharges to adjacent waters will be terperature and total suspended solids. Oils and greases sbould also be considered in case of equipnent leakages, spills from oil storage facilities, or other possible sources. Solid Wastes 24. Solid wastes will originate periodically fran emission control devices, settlings in cooling pits, and sludges from waste treatment facil- ities. EFFIDENT LIMITATIONS Air Emissions 25. Wet or dry systems for renoval of particulates, combined with collection of the gases for recycling or product recovery, will nrnally provide sufficient control to drastically reduce or eliminate discharges to the atmosphere. Where discharges are nade to the environment then emission levels, for both copper and nickel production, are to be maintained at or below the following levels: - 235 - Sulfur Dioxide (SO9 Inside P:ant Fence Ann. Arith. Mean 100 ug/m3 Max. 24-hour Peak 1000 ug/m3 Outside Plant Fence Ann. Arith Mean 100 ug/m3 Max. 24-hour Peak 500 ug/m Particulates Ann. Geom. Mean 75 ug/m3 Max. 24-hour Peak 260 ug/m3 Nitrogen Oxides (as N07) Ann. Arith. Mean 100 ug/m3 Carbon monoxide (CO) Max. 8-hour Aver. 10 ug/m3 Max. 1-hour Aver. .40 ug/m3 Nickel Ccmpounds (as Ni) All processes Maxim= 20 mg/m3 Liquid Effluents - Copper 26. Plants which engage in the smelting of primary copper froa ore or ore concentrates are those whose operations include, but are not limited to, roasting, converting, leaching (if preceded by a pycometallurgical step), slag granulation ar dumping, fire refining, and the casting of pro- ducts frcn these operations. 27. Based on the application of the best practicable control technol- ogy currently available, there should be no discharge of process waste- waters to surface or ground waters. Effluents may be impounded, with or without pretreatment, and recycled in n'st cases. 28. Where inpoundment is not practicable or there rmst be periodic releases, then the following effluent limitations apply: Max. 24-hour Consecutive 30-day Aver. Mg/Liter of Effluent TSS 50 25 - As 20 10 CU 0.5 0.25 Pb 1.0 0.5 Cd 1.0 0.5 Se 10 - 5. Zn . 10 5, pH 6 to 9 Units 6 to 9 Units - 236 - 29. Plants engaged in the elecrolytic refining of copper are those whose cperations include, but are rxt limited to, anode casting (performed at refineries which are - not located onsite with a smelter), product cast- ing, and by-product recovery. 30. On the basis of best practicable control technology currently available, wastewater effluents frca such plants should not exceed the following limitations: Max. 24-hour Consecutive __37 - 30-da y Aver. 7EMetric Ton of Product TSS 0.10 0.05 Cu 1.7x10-3 0.8x10-3 Cd 6x10-5 3x10-5 Pb 6x10-4 2.6x10-4 Zn 1.2x10-3 0.3x10-3 31. Plants engaged in secondary copper production are those which re- cover, reprocess, and remelt new and used copper scrap and residues to pro- duce copper metal and copper alloys. There should be no discharge of liquid effluent fram this source. Wastewaters may be impiounded and in many cases. recycled, either with or without pretreatment. 32. Where inpoundment is not practicable, or periodic releases are necessary, then discharges should meet the following limitations: Max 24-hour Consecutive 30-day Aver. Mg/Liter of Effluent TSs 50 25 Cu 0.5 0.5 Zn 10 5 Oil & Grease 20 10 pH 6 to 9 Units 6to 9 Units Liquid Effluents - Nickel 33. Based on best practicable control technology currently available, wastewater discharges from primary nickel production may be impounded and recyled in many cases, with or without pretreatment. Where irpoundment is not possible then discharges are to meet the following limiations, based on results achieved at Canadian plants: -237- Consecutive 30-day Aver. Mg/Liter TSS 15 Co 0.2 Ni 0.5 Fe 0.5 pH 6 to 9 Units CONTROL AND TREATMENT OF WASTES 34. As a first step in developing measures for control of emissions, wastewaters, and other sources of wastes, a critical analysis should be made of plant operations to determine what internal measures can be taken to reduce discharges to the environment. This includes, utilization or recycling of waste products, process changes, isolation of highly concentrated waste streams for separate treatment, inproved housekeeping procedures, control of water use, and other similar measures. Air missions 35. Gaseous and particulate emissions can be controlled by wet or dry scrubbers, cyclone filters,, electrostatic precipitators, or other devices. Discharges from wet systexs are added to other liquid process wastes and receive the same treatment. Dry systems 'e preferable where possible,. since they are generally as effective and b not add to the volume of wastewaters. The collected dusts and particulates are nore readily' disposable or reusable in the dry state. Tall chimneys (with heights in the 75 to 125 meter range) may be needed in addition to the scrubbers or other emission systems. Liquid Effluents 36. Scrubber waters fran prinary copper smelters can be treated by settling, coibining the supernatant with the cooling water, applying chemical precipitation, and recycling. Contact cooling waters fram. primary copper refineries way be recycled. Acid plant blowdown waters should receive chemical precipitation and filtration, and the filtrate recycled. 37. Slag mill wastewaters in a secondary copper plant can be settled, and the supernatant cobined with the contact cooling water for treatment by chemical precipitation. The supernatant may receive further filtration, stored and recycled, thus resulting in zero discharge. 38. Oil leakages, in both copper and nickel production facilities, from nachinery, fuel storage, or other sources can be controlled by * installing oil trapping and recovery systems. A dike system nay be advisable for the oil unloading and storage areas. - 238 - 39. Most of the liquid discharges in nickel production will come from cooling the mattes and slag casts. These streams will be high in suspended solids and contain varying degrees of nickel, cobalt, iron, and other inpurities. The wastewaters should be settled in ponds or tanks, and the supernatant cooled and reused within the plant. Depending upon the suspended solids contents, the supernatant waters may require filtration or other additional treatment before reuse or discharge to surface waters. 40. Where waters are discharged to nearby surface waters temperatures nust be reduced in order to avoid interference with other uses of the receiving waters. Discharge temperatures should be about 300C or lower. Solid Wastes 41. Solid wastes nay contain reusable naterials, and this should be the first consideration in developing disposal measures. Sludges, if not sold for reprocessing, may be discharged on-site to drying beds, lagoons, landfills, or similar facilities. Dried sludges, dry particulates, and other siMilar residues can be piled on land or used for landfill. Care should be taken at dunp sites to avoid contaminating ground waters and to prevent the pollution of surface waters by runoff. BIBLIOGRAPHY 1. National Academy of Sciences. "Medical and Biologic Effects of pollu- tants - Nickel." Washington (1975) 2. Canada Department of Mines and Resources, Mineral Resources Division. "Nickel-Canada and the World. " Mineral Report 16. Ottawa (1968) 3. United Nations Industrial Development Organization. "Non-Ferrous Metals - A Survey of Their Production and Potential in the Developing Countries." Vienna (1972) 4. Jarrault, P. "Limitation des Emissions de Polluants et Qualite de L'Air." Institut Francais de L'Energie. Paris (1978) 5. U.S. Environmental Protection Agency. "Guidance for Lowest Achievable Enission Rates from 18 Major Stationary Sources of Particulate, Nitrogen Oxides, Sulfur Dioxide, or Volatile Oreganic Ccmpounds." Document EPA 450/3/79-024. Washington (April 1979) 6. U.S. Environmental Protection Agency. "Development Document for Effluent Limitations Guidelines and Standards for the Nonferrous Metals Manufacturing Point Source Category." Doc. EPA-440/1-79/019-a. Washington (Septenber 1979). - 239 - 7. Atkins, M.H. and J.F. Lowe, "The Economics of Pollution Control in the Non-Ferrous Metals Industry." Pergarnon Press. Oxford (1979). 8. Powers, P.W. "How to Dispose of Toxic Substances and Industrial Wastes." Noyes Data Corporation. Park Ridge, NJ. and London (1976) 9. "Standard Methods for the Examination of Water and Wastewater. " 15th Edition. American Public Health Association. New York (1980). 10. Nevala, E.C., H.R. Butler, and H.J. Koehler. "Aquaeous Effluent Treat- ment at the Sudbury Processing Ccaplex of INO Limited." Presented at 24th Industrial Waste Conference, Toronto, Ontario, May 29 to June 1,. 1977. 11. U. S. Code of Federal Regulations. Title 40, "Protection of Environ- ment". Chapter 1, Part 42, "Nonferrous Metals Manufacturing Point Source Category". Washington. Washington (July 1, 1981). - 240 - THE WORLD BANK FEBRUAY 1983 OFFICE OF ENVIFNMENTAL -AFFAIBS NON-FERIUS MEIS INDUSTRY LEAD AND ZINC PROCTION ENVII01MENTAL GUIDELINES 1. 'fe non-ferrous metals category includes a large number of metals, but only a few are of concern to World Bank cperations at this time. Those most frequently encountered in Bank operations are covered in four separate documents in this series, as follows: (a) aluminum,; (b) lead and zinc; (c) copper and nickel; and (d) silver, tungsten, columbium, and tantalum. This document will be confined to the production of primary and secondary lead, and primary zinc. MANFACTURING PROCESSES IiAD 2. Galena, cerusite, and anglesite are the pri %ipal mineral ores used in the primary lead industry. The manufacturing process includes both refining and smelting. Usually both operations are czrried out at the same locations, but are independent of each other. The manufacturing process is shcn in Figure 1. 3. The smelting process consists of blending the ore concentrates with. recycled products and fluxes. The blend is pelletized and fed to a sintering machine. From the machine, the sinter passes through a breaker for breaking and sizing. Oversized particles are charged to the blast fur- nace and the small particles returned to the sinter feed operations. 4. The blast furnace is the primary reduction unit of the smelter process. Three molten layers are usually formed in this unit. The top layer consists of a slag containing silicate of iron, calcium, magnesium, trace impurities, and sanetimes significant quantities of lead and zinc. The middle layer (which does not always form) is carposed of copper and iron sulfide, along with some precious metals. The botton layer aprises the lead bullion which goes to the refining process. 5. Hard lead (sometimes referred to as antimonial lead) is the principal product of the primary lead industry. The initial step in the refining process is usually called "dross decopperizing" and serves to re- nove the copper. The dross (or skimned slag) is treated in a reverberatory furnace to separate the lead. The copper matte from the decopperizing goes to a copper smelter. The separated lead is further processed to remoave the antimony, gold, silver, bismuth, zinc, and any other inpurities which may be present. 州 242 6. The principal raw materials used in the secondary lead industry are storage battery plates and lead residues. Scme use is also made of solder, babbit (an allcy used to line machine bearings), cable coverings, and others. The lead is produced by dbarging the scrap materials to a re- yerberatory furnace (to produce soft lead) or to a blast furnmace (to pro- duce bard lead). The soft lead my be further refined to produce lead Ox- ide. The. bard lead may'either be shipped without additional processing or further processO the site to fill specific needs. A flow diagram for the secondary V ,,-,) , --int mewny smelting process is presented in Figure 2. ZIW 7. The two major sources of raw material cr prod ction of primary zinc are the zinc concentrate recovered as a co I product fka, lead and cop- per ores and the zinc ores frcm mining cperations. The,prolytic and elec- trolytic processes are the two methods in general use for primary zinc pro- duction. 8. In the pyrolytic process, sbown =1 Figure I the concentrates are roasted after drying and blending to remove sulfur as sulfur dioxide, as well as to remow varying amoun:tz of other volatile impurities such as mer- ct=y, lead,, and calcium. The roasted concentrate (calcine) is blended with coke, moisture, and sometimes silica sand, and thenpelletized. The pellets are sintered and crushed, and then fed to a reduction furnace. Most of the cadmium and lead is removed during sintering. 9. The zinc contained in the sinter is reduced to zinc oxide or metallic zinc in a vertical retort furnace or- an electrothermic furnace. In either case, the resulting zinc vapor is condensed and cast into in- gots. The uncondensed zinc axid carbon monoxide are passed through a wet scrubber. The exhausted carbon monoxide is used as a fuel, and the zinc is removed f=aL the scnibber water for reprocessing. 10. In the electrolytic process,, presented in Figure 4,, the roasting is fol1cwed by leaching of the calcine with spent electrolyte (H2SO4) to dissolve the'*zinc and cadmium. The solids (-gangue) are sepaiated by sedi- mentation and filtration,, and sold to other processors for recovery of the le&d and copper. 11. The zinc solution is further purified by adding zinc dust (and scmeti:mes scrap iron) in stages. These steps first precipitate copper and other bpurities and then cadmium. The pure solution is filtered, cooled and then passed to electrolytic cells,, where the zinc is deposited on alum- 2i= cathodes. The ptnIfied zinc is stripped fran the cathode, melted, and cast into various shapes for marketing. 12. The solids fran the filtration step are usually processed on site to recover the cadmium, if they are rich in cadmium, and the residues sent elsewhore to other processors for recovery of other metals. Cadmium-rich solids are leached with sulfuric acid to dissolve the cadmium, and then treated with zinc dust and other reagents to precipitate a cadmium sponge. The sponge is then further processed to produce cadmium met al, which is cast into shapes (usually small spheres) suitable for electrciplating. WASTE BATTERIES LEAD RESIDUES HSO, RATTERY wH0 + ELECTROLYTE CRACKING TO TREATMENT. 5 CASINGS TO DISPOSAL SCRAPIRON EMISSIONS SLAG LEMISSIONS WSEREVERBERATORV LA BLAST hWASTE BAGHOUSE ER ORY A SBAUS - S SOFT LEAD LIOUOR TO RECYCLE UBBER ANTIMONIAL SCRUBBER -10.FSCRLEAD LIOUOR TO RECYCLE .EMISSIONS - A*.Cw L -REMELT BARTON ,I REMELT KETTLK OXIDATION KETTLE REFINED LEAD LEAD OXIDE ANTIMONIAL LEAD LEAD ALLOY Figure 2- Secondary Lead/Antimony Smelting Process. (From USEPA Document EPA 440/1-79/019a) - 244 - ZINC CONCENTRATES WATER SLUDGE DUST CONCENTRA1TE COLLECTION DRYING WATER GaS" WASTEWATERt STO TREATMENT ON40ASS RCOLLECTION PA . CALCINE CADMIUM + PLANT LAD SINTERING COLDEC0N AS 21NC*RICH RESIDUE CADMIUM PLANT (RomESIDU DcmetEA-4/-7/1 COKE . mBLUE POWDER REDUCTION ZINC OXIDE RESIDUE . FURNACE CO. PLANT USE TREATMENT FERROSILICON 25CPOOR WATER CAS OLGW ER WN RESIDUE TO LEAD REFINERY $ LAD . BLOCKS OTHSER. . . . SHAPES. Figure 3- Pyrolitic Zinc Production Process (From US-4-7A Document EPA-440/1-79/019a) -245 - ZINC CONCENTRATES STORAGEWAEGS PRELEACH PLANT ROASTER DI H.SO. . CALCINE CLASSIFIER DUST BALL MILL UNDERFLOW ZINC SOLUTION FROM CADMIUM PLANT , LEACHING SOLIDS TO COPPER OR T . LEAD THICKENERS REFINERY FILTERS SOLIDSTOZ CADMM SOLUCON ZINC DUST PLANT IPURIFICATION ELECTRLYSISSPENT CELL ACID ELCOLYSIS .. . .CATHODE MELTING ZINC OXIDE FURNACE COOLING TOWER WATER CASTING BLOWOOWN . .SLAB BLOCKS OTHER SHAPES Figure 4- Electrolytic Zinc Reduction Process (From USEPA Docurent EPA-440/1-7S/019a) - 246 - WASTE SOURCES AND CHARACTERISTICS LEAD Air Missions 13. The smelting process in primary lead production generates gaseous emissions of sulfur oxides, arsenic, antimony, and cadmium in the sintering of the ore blends. A highly concentrated SOx stream produced during the initial phase of the operation may or may not go to a sulfuric acid plant. Particulates are removed by flue, baghouse, or wet scrubbers for recycling to sintering machines. 14. In the refining process, sare fumes are produced, mainly by the softening furnace. Established air pollution control devices are used to renove these emissions, and no significant quantities are normally dis- charged to the atmosphere. 15. Secondary lead, produced nostly from discarded storage battery plates, generates gaseous emissions fran both reverberatory and blast furnaces, and the remelt kettles. These are renoved by baghouses or scrub- bers. Water fran the scrubbers is generally recycled. Liquid Effluents 16. Liquid wastes in primary read smelting originate fran sintering air pollution control units, acid- plant blowdowns, blast furnace emission control devices, zinc fuming control units, slag granulation, and dross re- verberatory furnace emission control devices. Wastewater. in the refining process can originate from wet scrubbers, but this water is usually re- cycled and no discharge results. Cooling of the castings is usually a non- contact operation and the water is normally recycled. 17. For secondary lead plants the waste streams include battery acid, raw cooling,' and washdown fran the battery - cracking. Furnace and kettle air pollution control devices and contact cooling contribute wastewater in the smelting process. Battery acid streams are strongly acidic and contain significant levels of suspended solids, as well as several metals such as antimony, arsenic, cadmium, lead, and zinc. Metal cooling is usually ac- complished by non-contact methods. Solid Wastes 18. Solid wastes originate fram air pollution control devices, prepa- xation of feeds, furnace operations, and other sources. A significant por- tion of these residues are reused in the process. - 247 - ZINM Air missions - 19. missions originate fron the drying process in pyrolite zinc pro- duction, fran which they are renoved by wet scrubbers and discharged with the wastewater. The roaster. units renove sulfur as sulfur dioxide, as well as other volatile inpurities such as arsenic, lead, and cadmium. The exhaust gases pass through a dust collection system before transfer to an acid plant for conversion to sulfuric acid. The waste solids are later treated to recover cadmium. 20. The blending and pelletizing of the ore concentrate also produces a dust, which is collected and treated to recover cadmium and lead. The reduction of the zinc contained in the sinter to zinc oxide or metallic zinc produces uncondensed zinc and carbon monoxide. These -are passed through a wet scrubber, with the carbon monoxide being used as a fuel and the zinc recovered for reprocessing. 21. The roasting furnaces in electrolytic refineries renove sulfur as sulfur dioxide fron the ore concentrates, and this goes to a sulfuric acid plant. These emissions ay also contain other inpurities. such as mercury, lead, and cadmium. Calcine dust fron the roasters is *separated fron the sulfur dioxide in the dust collectors and returned to the process. Liquid Effluents 22. IsWstewater flows in prinary zinc production originate fra the wet scrubbers which collect emissions fron the concentrate, roasting, sint- ering, and leaching units. Other effluents are discharged from the acid plant blowdown, reduction furnace, preleaching, anode/cathode washing, and contact cooling. Depending upon the source, the waste streams will contain varying concentrations of lead, arsenic, cadmium, zinc, and other pollut- ants. Toxic heavy metals should be renoved by neutralization before dis- charge. Solid Wastes 23.. In general, the dusts and other solids resulting from zinc pro- duction contain significant quantities of other netals, such as lead and copper. These residues are sold to other processors for recovery of valuable corponents. 24. Cadmium byproduct recovery, nearly always practiced at primary zinc plants, does not generate any significant quantities of solid wastes. - 248 - - EFFLUET -IMtTATIONS Air Emissions 25. For both lead and zinc plants, equipmnt is readily available (sudh as wet or dzy scrubbers) to avoid the discharge of particulates and gases to the atmosphere. However, where these substances cannot be or are not removed, then the following limitations will apply: Sulfur Dioxide (SO,) Inside Plant Fence Ann. Arith Mean 100 ,ug/m3 Max. 24-hour Peak 1000 ug/m3 Outside Plant Fence Ann. Arith Mean 100 ,ug/m3 Max. 24-hour Peak 500 ug/m3 Particulates Ann. Geon. Mean 75 ag/m3 Max. 24-hour Peak 260 ug/m3 Arsenic (as As) Inside Plant Fence 24-hr. Av. 0.006 mg/m3 Outside Plant Fence 24-hr. Av. 0.003 mg/m3 Camium (as Cd) Inside Plant Fence 24-hr. Av. 0.006 mg/3 Outside Plant Fence 24-hr. Ave. 0.003 mg/n3 Lead (as Pb) Inside Plant Fence 24-hr. Av. 0.008 mg/m3 Outside Plant Fence 24-hr. Av-. 0..004 mg/m3 Liquid Effluents 26. On the basis of best practicable control technology presently available, liquid discharges should not exceed the following limits: Primary Lead Consecutive Max-24 hour 30-day Aver. K44g/MT Product TSS 4.2x10-2 2.1x102 Cd Sx0-4 4x10-4 Pb 8xl0-4 4x10-4 Zn 8x10-3 4x10-3 pH 6 to 9 units 6 to 9'units -249- Secondary Lead (Battery Cracking) TSS - 5x10-2 2.5x1 -2 Cd 4x10-5 2x10~ Pb 1x103 0.5x10-3 As 1X104 0.5x10-4 pH 6 to 9 units 6 to 9 units Consecutive Max-24 hour 30-day Aver. Eq/Mr Metal Product Primary Zinc TSS 0.42 0.21 As 1.6xlQ-3 8x04 Cd .S860-1 4x10-4 Se 0.08 0.04 Zn 0.08 0.04 pH 6 to 9 units 6 to 9 units CONTROL AND TREMT OF WASTES Air Eissions 27. Both the lead and zinc industries nake extensive use of wet and dry methods for renoval of particulates and gases. Liquid effluents fran the wet systems are bandled with the wastewaters and receive the same treatment. Dry systens are preferable, since removal efficiencies are high and wastewater volumes are reduced. Current trends are toward dry system for new plants and replacements. Liquid Effluents 28. The initial step in disposing of wastewaters is to critically ex- amine housekeeping practices. Inrplant measures such as process changes, nonitoring of water use, byproduct recovery, and recycling can make signif- icant reductions in the anunt of liquid effluents that nust be treated and discharged. 29. Except for acid plant blowdown water, zero discharge by recycling is achievable in a primary lead plant. Acid plant blowdown waters ay be treated by chemical precipitation and filtration. 30. Wastes from secondary lead production fran battery. cracking can be treated by using lime for pH adjustment, followed by flocculation, pre- cipitation, and settling. 31. Waste streams from primary zinc production can be treated by chemical precipitation, using alumina, and filtration. Cooling waters nay be cmbined with other streams and receive the same treatment. Generally, all effluents can be collected, after- treatment, and recycled. 250 - Solid Wastes 32. Sludge disposal is a problem in these industries, since the waste streams my carry large concentrations of metals. Sludges are frequently -removed by contractors for off-site disposal or sold to reprocessors for recovery of metals. Drying beds, lagoons, landfills, incineration, or a cmbination of these can be effectively used for on-site disposal. 33. Particulate matter frcm dry scrubbers may be burned, placed in a landfill or reprocessed for byproduct recovery. BIBLIOGRAPHY 1. United Nations Industrial Development Organization. "Non-ferrous Metals - A Survey of Their Production and Potential in the Developing Countries." Vienna (1972) 2. Atkins, M.H. and J.P. Lowe, "The Economics of Pollution Control in the Non-Ferrous Metals Industry." Perganon Press. Oxford (1979) 3. Boodson, K. "Non-Ferrous Metals - A Biographical Guide." Macdonald & Co. (Publishers) Ltd. London (1972) 4. Powers, P.W. "How to Dispose of Toxic Substances and Industrial Wasted". Noyes Data Corporation. Park Ridge, NJ. and London (1976) 5. "Standard Methods for the Examination of Water and Wastewater." 15th Edition. American Public Health Association. New York (1980) 6. "Chemical Engineers Handbook." Ed. by Robert H. Perry and Cecil H. Chilton. Fifth Edition. McGraw-Hill Book Co. New York (1973) 7. U.S. Environmental Protection Agency. "Develoment Document for Ef- fluent Limitations Guidelines and Standards for the Nonferrous Metals Manufacturing Point Source Category." Dc. EPA-440/1-79/019-a. (Sep- tember 1979) - 251 - THE WOLD BANK MARCH 1983 OFFICE OF ENVIIUNENTAL -AFFAIRS NCN-FERROUS METALS INDUSTRY SILVER, TUNGSTEN, CO4MIMM AND TANTALIM PROUCTION hENVIOMETAL GUIDELINES 1. The non-ferrous metals category includes a large' number of metal- lic elements, but only a few are of concern to World Bank operations at this time. Those nost frequently encountered in Bank projects are covered in four separate documents in this series, as follows: (a) aluminum; (b) lead and zinc; (c) copper and nickel; and (d) silver tungsten, columbium, and tantalum. This document will cover the production of (a) secondary sil- ver from photographic and non-photographic wastes; (b) primary tungsten salts (anmonium paratungstate-APT) and metal; and (c) primary columbium and tantalum salts and metals. MANUFACTURING POCESSES SECONDARY SILVER 2. The principal sources of raw materials are photographic wastes, plating and sterling ware wastes, electrical components, and miscellaneous sources. Photographic wastes are the largest single source. Typical pro- duction processes are shown in Figures 1 and 2. - 3. r In the recovery of silver frn photographic natprials, the film is chopped into small pieces, followed by separation of the silver from the films by nitric acid stripping. Then follows sedimentation, decantation and filtration. The plastic residue is disposed of as solid waste, while the liquid portion is mixed with chemicals to precipitate the silver. Spent photographic solutions may also be added at this point for recovery . of the silver. The supernatant is decanted and sent to treatment. The sludge is thickened, filtered or centrifuged, .dried, roasted, and cast into ingots (also known as Dore plates). The ingots nay be further refined on site or shipped elsewhere. The roasting furnace slag is crushed and class- ified, the silver concentrate is returned as furnace feed, and the tailings go to landfill. 4. Cyanide solutions fran the plating and sterlingware industries are treated with sodium hypochlorite to precipitate the silver and oxidize the cyanide. Following initial settling more sodium hypochlorite and lime are added, and the solution resettled. The resulting silver-chloride pre- cipitate is washed and dried for further processing or sold as a final pro- duct. -252- PHOTOGRAPHIC FILM SCRAP DUST GRANULATION BAGHOUSE STRIPPING NITRIC ACID WASTE FILM SEDIMETATION TO LANDFILL & FILTRATION PRECIPITATION REAGENTS RECOVER ED DUST * SILVER-FREE PRECIPITATION W EPOTAPHIC WATER WASTE PHOTOGRAPHIC SOLUTIONS SILVER-FREE SILVER SLUDGE. WATER FILTRATION SILVER-BEARING PHOTOGRAPHIC FILM ASH CASTING O ELECTROLYSIS SLIMES E ROLYSIS TO Au & Pt RECOVERY MELTING &CASTING. SILVER INGOTS Figure 1. Silver Refining From Photographic Wastes * (from US EPA Document EPA 440/l-79/019a) ―쩐 254 5. 'When electrical caLpcnents scrap is not suitable for electrolytic refining, it must be further processed to recover the silver. The scrap is firsit melted in a reverbatory furnace to produce lead bullicn, copper matte,, and slag. The lead bullicn is melted to produce litharge and preci- ous metals layers. The litharge goes to a lead refinery and the precious metals layer is cast into anodes for electrolytic- refining. The ccpper matte is processed to separate the silver, which is cast as ingots. The slag is smelted in a blast furnace to separate the lead and ccpper por- ticns. Blast furnace slag is discarded as waste. This procedure is shown in Figure 2. PRmARY TUNGSTEN.. 6. A number of processes are available for producing' tungsten salts and metal- Ferberite (FeM4) and scheelite (CaM4) are the two cres most widely used to produce ammonium paratungstate (APT) and tungsten metal pow- der. Typically,, tungstate (W04) is purified from concentrates and convert- ed to tungstic acid (H2WO4) through a series of filtraticn'and precipita- tim reacticns. Further processing produces the intermediate product des- ignated'as APT. The APT is dried,, sifted, and converted to oxides which, in* turn,, are finally reduced to tungsten metal powder - The powder is eventually used to produce the metal,. or comb3ned with carbcn or other metals to make carbides cr metal alloys. The production process is shown in Figure 3. PRnvMEY COLUMBIUM AM TANVUM 7. Columblum. is th-we more pcpular name for nibbium. uhich is element 41 in the periodic system. Tantalum, (nunber 73 in the periodic system) and columbium generally occur together in nature as the minerals tantalite and columbite, respectively. 8. Raw materials . for the production of primary columbiLun and tanta- lum salts are ore concentrates and slags. The slags used are generally those resulting from. tin production. Mwee types of plants are encount- ered: producers of metals and salts -fran concentrate and slags; producers of purified salts aily fraL concentrates and slags; and producers of metals fran purified salts. The salts of these two elements are produced first in the process. r1he salts are then subjected to aluminothermic,, sodium, or other reducticn 3n order to produce the two individual metals. Production processes are illustrated in Figure 4. %A= SOURCES AND CHARAC=STICS SEXX)NDARY SILVER Air Emissions 9. In the producticn of silver from film, dusts and particulates originate in the film chcpping cperat!.-.,-t. Particles are also released when the film is incinerated. The dusts are collected and return- ed to the process for recovery of the silver. Roasting furnaces also cause emissions butthese are readily controlled by the use of wet scrubbers. 255-.. GROUND CONCENTRATE. DIGESTION 4NaOH SETTLE WASTE SOLIDS E FLILTER NaaWO& PRECIPITATION NaCI & caCI, DECANTATION CaWO SLURRY . . HCI WASTE SCRUBBER WATER - CaCI2 SOLUTION -o TO WASTE HaWO4 SLURRY . NH40H DISSOLVINGNH0 WASTE SCRUBBER WATER 0 - WASTE SOLIDS NH4WO4 ~~DRYIGJ WASTE SCRUBBER WATER APT REDUCTION 1 TO WASTE SCRUBBER WATER METALS TUNGSTEN POWDER Figure 3. Primary Tungsten Production Process (From US EPA Document 440/1-79/019al -256- DIGESTION AIR SCRUBBER WASTES OF B GANGUE CONCENTRATE Cb/Ta BEARING . SOLUTION AIR SCRUBBER WASTES EXTRACTION FLOOR WASHING WITH RAFFINATE I-WASTES MIBK . Cb/To IN WATER NH3 KCI NH To Cb V TO WASTE PRECIPITATION PRECIPITATION TO NH3 TREATMENT Ik &T STRIPPRNG FILTRATION FILTRATION I AIR To CbAI *RWAER SALT SALT SCRUBBER TI WAT RINRaN TO NH TREATMENT SDRYING DTRIRNNG SCRUBBER a RINSE 4-F REDUCTION REDUCTION WATER L To METAL Cb METAL Figure 4. Primary Columlium and Tantalum Production Process (From US EPA Document EPA 440/1-79/019a) - 257 10. Secondary silver production from non-photographic materials re- sults in emissions fron the leaching and stripping of the scrap materials. These will contain significant levels of acids, cyanides (if used in the process), and metals. Smelting furnaces will also produce emissions of particulates and fumes. Wet or dry dust-fume collectors isolate the materials for return to the process or to waste. Liquid Effluents 11. Liquid waste sources in the processing fran photographic films and other photographic wastes include leaching and stripping, precipitation and filtration, roasting furnaces, electrolysis units (for recovery of other metals) and contact cooling. Wastewater fran the. leaching process will be strongly acidic or caustic, depending upon the leachate used. This effluent nay also contain significant quantities of chromium, copper, lead, and zinc as well as scue organic pollutants which are used in the manufac- ture of the film. 12. Waste effluents also result fran the precipitation of silver fron the leaching and stripping solution. These are similar to the leaching wastewaters, but will also reflect the omposition of the chemical addition used. Iron, zinc, and soda ash are among the chemicals used for precipita- ting the silver. The precipitate is dried, roasted, cast, and cooled. Direct contact cooling water is discharged. .. 13. In silver production fron non-photographic materials, a highly acidic wastewater results fran the control of emissions in the stripping units. This effluent may also contain significant quantities of cyanides (if used in the stripping process) and other metals. The filtrate fran the precipitation of the silver in the stripping solution is also discharged as wastewater. Wet scrubbers used to collect furnace emissions are another liquid effluent source. In those plants using electrolytic refining, the spent electrolyte, wastewater, and wet scrubber systems contribute to the final effluent. Contact cooling is a final scurce of waste flows in the plants. Solid Wastes .. 14. Solid wastes generated in these processes include the plastic portion of the film remaining after stripping, solids fron wet and dry scrubbers (when not recycled to the system) and sludge residues fron which silver has been renoved. PRIMARY TUNGSEN Air Emissions 15. Principal emission sources in tungsten production are the leach- ing, dissolving, drying, and reduction units. Wet scrubbers are usually installed for this purpose, and discharges to the atnsphere are insignifi- cant. -258- Liquid Effluents 16. Wstewaters originate fron precipitation and filtration, leach- ing, and the wet scrubbers, in the conversion of ore concentrates to amnan- ium paratungstate (APT). The wastewater streams reflect the conposition of the ore concentrate and the processing steps used prior to leaching. They are typically strongly acidic, very high in chlorides, and ay contain sig- nificant levels of such metals as arsenic, lead, and zinc. Scrubber efflu- ents from the drying nay contain high concentrations of amnonia, and may be subjected to amnania recovery before discharge. 17. 7he reducticn units, which convert the salt into the metal, will produce wastewaters from the wet scrubbers. Wtile this effluent ay be high in anmenia, it usually is not treated for annonia recovery. Solid Wastes 18. A gangue, or residue, results fran the fusion reaction in the fornation of soluble sodium tungstate from the cre concentrates. These waste solids are usually transferred to landfills, but in sane cases the residue is sold for nolybdenum recovery. PRIMARY COUMBIUM AND TANIALUM Air Enissions 19. Air emissians from the production of columbium and tantalum salts and metals originate frcn the treatment with methyl isobutyl ketone (MIBK) or other organic solvent, the salt drying units,,. and the reduction of salts to the pure metal. Liquid Effluents 20. The most significant wastewater sources are the digestion, sol- vent extraction, and precipitation processes required for extraction of the salts fram the concentrates and slags. The processing involves the use of acids, amnania, and organic solvents. All of these are present in the final effluent. Production of the metals fron the salts results in waste- water fra the leaching operation (following reduction) and from wet air pollution control devices. Solid Wastes 21. Treatment of the wastewaters and quench waters results in produc- tin of sludges, for which disposal must be provided. EFFUT LIMITATIONS Air Emissions 22. In general, particulates and gases emitted fran the production of the metals covered IW this document are readily controlled and eliminated - 259 - by the use of wet or dry scrubbers. Where any of the emissions are dis- charged to the atmosphere, then the following limitations are to be observ- ed in all cases: Sulfur Dioxide (s0') Inside Plant Fence Ann. Arith. Mean 100 pg/m3 Max. 24-hour Peak 1000 pg/m3 Outside Plant Fence Ann. Arith. Mean 100 UG/r3 Max. 24-hour Peak 500 pg/rn3 Fluorides (as HF) Ann. Arith Mean 10 ug/m3 Max. 8-bour Peak 100 pg/m3 Particulates Ann. Geom. Mean 75 pg/m3 Max. 24-hour Peak 260 pg/m3 Liquid Effluents 23. On the basis of best practicable technology currently available, liquid discharges are to be maintained within the following limitations: Secondary Silver - Photographic Max 24-hour ig/MT Metal Prod. TSS 0.60 Cr lx10-3 CU . 6x10-4 Pb 2x10-4 Zn 1x10-2 - 4x10-4 pH 6 to 9 units Secondary Silver - Non-photographic TSS 0.30 Cu 3x10-2 Zn 0.10- Ag 3x10-3 pH 6 to 9 units - 260 - Max. 24-hour Ng/MT APT Prod. Primary Tungsten - Ore to Salt - TSS 1 NH3-N 1 Cr 2x10- 3 cu 6x103 Pb 4x10-3 Ag 4x10-3 pH 6 to 9 units Primry Tungsten - Salt to Metal Max. 24-hour Kg/Mr Metal Prod. TSS 9x10-2 NH3-N 4x10-2 Cr .4x10-4 Cu 6x10-5 Pb 2x10-2 Ag 6xl0-5 pH 6 to 9 units Primary Columbium and Tantalum - Ore to Salt Consecutive Max. 24-hour 30-Day Aver. K/MT of Purified Salt Fluoride (total) 11.8 5.9 TSS 8.4 4.2 NH3-N 10 20 pH 6 to 9 units 6 to 9 units Primary Columbium and Tantalum - Salt to Metal Consecutive Max. 24 hour 30-day Aver. MT of Metal Fluoride (total) 8.4 4.2 TSS 6.0 3.0 pH 6 to 9 units - 6 to 9.units - 261 - CONTROL AND TREMIMENT OF WASTES Air Enissions 24. The producticn facilities discussed in this document generally control and eliminate air emissions through the use of dry or liquid scrib- bers. Gases are frequently utilized in the plant, either as a fuel or as a. comp~czent of another product. Particulates are discharged with the waste- water streams, where wet collecticn methods are used, or else are utilized for other purposes within the plant. If dry collection systems are utiliz- ed then the particulates are dumped on land if they have no recovery value. Liquid Effluents 25. Housekeeping practices should be critically examined and improved as a first step in the control of liquid effluents. Process changes, moni- toring of water use, by-product recovery, and recycling are among the meas- ures that can significantly reduce the volume of wastes requiring treatment and disposal. 26. Whstewaters from secondary silver processing from both photogra- phic and non-photographic wastes can be treated by steam stripping of the high ammcniia streams, and applying chemical precipitation - and filtration to the ombined stream. Treated effluents may he recycled at discharged. 27. In the productici of primary tungsten metal, both in the ore to salt phase and in the salt to metal phase, high amnonia streams can be stripped to remtve and possibly recover the amnonia. The residual can be conbined with other streams and receive chemical precipitation and filtra- tion. The resulting effluent may be recycled or discharged. 28. - In the wastewaters frcm the producticn of the salt fron the ore concentrate, steam stripping provides a high degree of amonia removal and recovery. Lime precipitation is effective in renoving the fluoride ions and results in the precipitation of metals dissolved in the waste streams. Suspended solids are removed by sedimentaticn. 29. Effluents frcm the producticn of the metal frm the purified salt can be treated by lime precipitation to renove the fluoride ion and dis- solved metals. Sedimentation renoves the suspended solids. Solid Wastes 30. Sludge disposal is a problem in these industries. These waste streams may contain large quantities of one or more heavy metals, and these are nost cirnonly renoved from liquid effluents by chemical precipitation. Consequently, the sludges contain large concentrations of the .metals. 31. Sludges are disposed of by contractors or are sold to reprocess- ors. They may also be transferred to drying beds, lagoons, landfills, or incineration. -262- 32. Other solid wastes, such as wet scrubber residuals, are added to the waste streans receive the same treatment and disposal and hence add to the sludge loads. Particulate natter from dry scrubbers is burned, dunped cn land, or is recycled for by-product recovery. BIBLIOGRAPH 1. United Nations Industrial Develcpnent Organizaticn. "Non-Ferrous Met- als - A Survey of Their Production and Potential in the Developing Countries." Vienna (1972) 2. Atkins, M.H. and J.F. Lowe, "The Econcmics of Polutic Control in the Non-Ferrous Metals Industry." Pergamon Press. Oxford (1979). 3. Boodscn, K. "Non-Ferrous Metals - A Biographical Guide." Macdonald & Co. (Publishers) Ltd. London (1972) 4. Powers, P.W. - "How to Dispose of Toxic Substances and' Industrial Wastes." Noyes Data Corporation, Park Ridge, N.J., and London (1976). 5. "Standard Methods for the Examination of Water and Wastewater." 15th Edition. American Public Health Association. New York (1980). 6. "Chemical Engineers Handbook." Ed. by Robert H. Parry and Cecil H. Chiltcn. Fifth Edition. McGraw Hill Book Co., New York (1973). 7. U.S. Environmental Protection Agency. "Development Document for Efflu- ent Limitations Guidelines and Standards for the Nonferrous Metals Man- ufacturing Paint Source Category." Doc. EPA-440/1-79/019a. Washing- ton, (September 1979). - 263 - The World Bank November, 1981 Office of Environmental Affairs ENVIRONMENTAL RECONNAISSANCE OF OFFSHORE HYDROCARBON EXPLORATION AND PRODUCTION PROJECTS 1. Background The objective of an environmental reconnaissance to be carried out in con- nection with a proposed offshore energy project is to determine, in a general way, the possible impact of the project, its presence and opera- tion, on the environment, worker health and safety and the social well- being of peoples to be affected by the.project and to make recommendations to eliminate or mitigate adverse effects of the project. The reconnaissance-type study should include; but not necessarily be limited to, the following considerations. (a) Biota The nature and extent of the biotic community resident in or transiting the area likely to come under the influence of the project; e.g., shellfish beds, benthic organisms, offshore fishery, spawning grounds, finfish nursery area, etc., during the exploration, construction, and operation phases. Especial attention should be paid to those members of the biota forming part of the food chain for economically important species, ecologically unique life forms or endangered species. The poten- tial adverse impact on lishery, marine mammal, bird and other natural faunal/floral resources, including their presence, abundance, area depend- ence, and distribution should be carefully noted. (b) Facility Integrity The potential, and possibly dangerous, effects of environmental phenomena on the structural and operational integrity of the facility, in- cluding those related to unusual but recorded weather, wind, swell, seismic and related conditions. (c) Waste Handling The proposed plans for liquid, gaseous and solid wastes manage- ment, transportation and disposal, taking into consideration the likely dangers posed to the ecological systems, public health, environmental amenities and aesthetics. (d) Contingency Plans for Blowouts, Spills and Fires The appropriateness and adequacy of contingency plans, equipment, supplies, personnel, and response-time to cope with blowouts, major spills, fire, structural failure and/or other major emergencies. These should be noted with regard to the probable diseconomies and environmental damage. - 264 - (e) Occupational Health and Safety The plans, regulations, codes, practices and their monitoring and enforcement relating to the protection, safety and health of the workers. Offshore facilities pose special problems of prevention, control, treat- ment, and evacuation. (f) Scenic,.Touristic and Aesthetic-Considerations The scenic and aesthetic qualities of the area likely to be affected by the project's presence and operation, including visual and acoustic considerations. Present and potential tourtsm values that may be prejudiced should receive consideration. (g) Project-associated Environmental Impacts Activities associated with the project, including transportation and shipping, may generate problems; e.g., ships' wastes, bilge discharges, spills during transfers, collisions, and touristic detraction. (h) Onshore Facilities and Activities The adequacy, relevance, timing and funding of plans and prac- tices designed to cope with induced onshore development associated with the offshore scheme. Likely social and. important environmental conse- quences should be identified, with particular reference to industrial and port-related developments. (i) Existing Laws, Regulations and Codes Governing Offshore Projects Identification of existing national and/or applicable local juris'- dictional laws, regulations, codes, ordinances relating to offshore energy exploration and production operations. (j) Future Expanded or Associated Offshore Development If the project is one of several being planned or presently existent in the area or field being developed, a general assessment of the combined impact is important; i.e., aggregate impacts may have consequences differing in nature or magnitude from those identified with each incre- mental project. When-a hydrocarbon field is expected to be exploited, the area of which may be large or configured in a manner to suggest an extended impact zone, a coastal zone management plan should be considered to ensure orderly and environmentally sound development. - 265 (k) Report of Findings and Recommendations A full report of the reconnaissance findings should be prepared to include appropriate detailed information on the anticipated environ- mental, worker health and safety, and social consequences of the proposed project; the nature, scope, and. timing of any additional studies required; the nature, dimensions, timing, and severity of important problems should be highlighted, along with recommendations as to how they might be preven- ted or mitigated. In preparing the report and detailing the measures to be taken, appropriate utilization should be made of the General Environmental Guide- lines for Offshore Hydrocarbon Exploration and Production Projects which follow. -266- The World Bank November, 1981 Office of Environmental Affairs General Environmental Guidelines for Offshore Hydrocarbon Exploration and Production Projects 1. Background In considering the environmental implications of offshore energy projects, the general policies of the Bank relating to the environment pro- vide useful guidance (see Bibliography Nos. 1 and 2). However, the unique nature of offshore energy development re- quires its own specific guidelines. -In this endeavor the Bank has relied heavily on guidelines and regulations in force in the Commonwealth of Australia and Canada; and, practices recommended by the American Petroleum Institute, the Intergovernmental Maritime Consultative Organization, the Norwegian Petroleum Directorate, and others. These concern themselves with exploration, production, transportation, sensitive environments, special circumstances, environmental damages and legal liability, and related matters (see Bibliography Nos. 3-7). These materials have been included to address the spectrum of considerations and requirements seen as necessary to the Bank's financing of such type projects. 2. Procedure Borrowers and/or their engineering consulting firm(s) 'serving them must satisfy the Bank that their approach to protecting the environ- ment and its biota, accident prevention, blowout prevention, contingency preparedness, wastes management, worker health and safety, meet these, or equivalent, requirements and/or is adequate under anticipated prevailing and worst recorded offshore conditions. 3. Rigid standards, rules, regulations are not promulgated herein and are otherwise judged unwise and impractical given the varied project environments to be encountered world-wide. What is sought is a practical, eminently doable approach to the environmental dimensions of offshore energy activities tailored to the specifics of the total milieu; i.e., environmental, economic, political, and social. 4. It must be emphasized and highlighted, however, that blowout prevention. (BOP) constitutes the highest priority in any setting. De- tailed technical BOP recommendations are, therefore, included in the guidelines. Experience has shown that accidents will occur even when these precautions are practiced. It is realistic to expect a blowout frequency of 'roughly one in twenty-five even with the best prevention. In recog- nition of this, the Borrower must satisfy the Bank as to the adequacy of its contingency plans and preparedness for dealing with these situations. - 267 5. The Bank recognizes that some of its member countries are poorly equipped to plan, oversee and enforce a program of coastal zone protec- tion.. It is prepared, therefore, to assist governments in this regard while assuming, inter alia, environmental oversight responsibility for projects it is financing in the coastal waters of such countries. In -this regard, the Bank will, in cooperation with governments and in keeping with its project supervision activities, carry out a monitoring of those envi- ronmental, health and worker safety considerations incorporated into the project. Technical assistance will also be provided where appropriate. 6. Project Design Checklist and Related Bibliography The brief design checklist and related bibiiography* (which fol- low) include those major considerations to be addressed in Bank-financed offshore energy projects. The task is that of demonstrating to the Bank's satisfaction that offshore energy projects proposed for financing will not present unacceptable risks to the environment. The Borrower will be expec- ted to recommend environmental protection and management measures that rep- resent a balanced consideration of the benefits and risks entailed. The checklist is intended to serve principally as a guide to the essential elements of the environmental provisions. Environmental Checklist Waste management program (at site, in transport, on shore); 1) Of solids 2) Liquids 3) Gases The resources and environment at risk: 1) At site 2) In transport 3) On shore 4) In emergencies Environmental threats to projects: 1) Weather-related 2) Fouling 3) Geological (drilling, completions) 4) Other *NOTE: All documents listed in the bibliography are available in the Bank"s Energy Department Library. - 268 - Emergency preparedness: 1) Available emergency equipment and finance (see para. 4) 2) Trained personnel 3) Response time 4). Worker safety 5) Medical facilities. Other 1) Relevant national legislation and institutions 2) Monitoring and enforcement 3) Costs, benefits and social impact .~..,.....*. -269- BIBLIOGRAPHY (All documents listed are available from World Bank Energy Library.) 1. a) Environment and Development, 1979. World Bank. 33 pages. b) Environmental, Health and Human Ecologic Considerations in Economic Development Projects, 1974. World Bank. 142 pages. c) Industry: Environmental Control, 1978. World Bank. 128 pages. 2. International Bank for Reconstruction and Development (IBRD), International Development Association (IDA), International Finance Corporation (IFC). 3. General Regulations (see Annex, page 1 for details) Exploration: i) Marine Operations, Directions as to, - Commonwealth of Australia, State of Victoria. Schedule 1. 23 pages. ii) Drilling Operations, Directions as to, -- Commonwealth of Australia, State of Victoria. Schedule 1. 16 pages. Production: iii) Petroleum Production, Directions as to, - Commonwealth of Australia, State of Victoria. Schedule 1. 8 pages. (In arctic/antarctic environments use Canada Oil and Gas Production and Conservation Regulations, 1979. 359 pages.) Transportation: iv) Recommended Practice for Design, Construction, Operation and Maintenance of Offshore Hydrocarbon Pipelines. American Petroleum Institute (API), RP 1111. 22 pages. v) International Convention for the Prevention of Pollution from Ships, 1978. Inter-Governmental Maritime Consultative Organization (IMCO). 171 pages. 4. Supplementary Regulations (see Annex, pages 1 and 2 for details) Exploration: vi) Recommended Practice for Blowout Prevention Systems. API, RP 53. 58 pages. -270 vii) Testing of Drilling Fluids. API, RP 13B. 35 pages. viii) Oil, Gas, and S-Leases in the Outer Continental Shelf Area. US Geological Survey (USGS), OCS Order #2, Section 5. 10 pages. ix) Recommended Practice for Safe Drilling of Wells Containing H2S API, RP 49. 11 pages. Production: x) Recommended Practice for Planning, Designing and Constructing Fixed Offshore Platforms. API, RP 2A. 86 pages.. xi) Recommended,Practice for Production Facilities on Offshore Structures. API, RP 2G..15 pages. xii) Recommended Practice for Design, Installation, and Operation of Subsurface Safety Valve Systems. API, RP 14B. 27 pages. xiii) Recomended Practice for Analysis, Design, Installation and Testing of Basic Surface Safety Systems Offshore Production Platforms. API, RP 14C. 85 pages. xiv) Outer Continental Shelf. US Geological Survey, Order No.11 (Sec. 1OA-10D). 1 page. Order No. 7 (Sec. 4). 5. Sensitive Environments (see Annex, page 2 for details) Exploration: xv) International Conventidn for the Prevention of Pbllution from Ships, 1973. IMCO (Sec. 10-12). 5 pages. xvi) Oil and Gas Production and Conservation Regulations, 1979. Canada. 359 pages. 6. Special Circumstances (see Annex, page 2 for details) xvii) The Onshore Impacts of Offshore Oil and Natural Gas Develop- ment In the West African Region, 1981. UNEP. 50 pages. xviii) World Directory of National Parks and Other Protected Areas, 1977. IUCN. 2 volumes. (Note: For working conditions and working environment in the petroleum industry - offshore - see Bibliography No.7, xzviii.) - 271 - 7. Additional bibliographic information related to offshore energy devel- opment activities: xix) Provisional Regulations for Diving on the Norwegian Continental Shelf, 1978. Norwegian Petroleum Directorate (NPD). 39 pages. xx) Provisional Regulations Concerning Littering and Pollution Caused by Petroleum Activities on the Norwegian Continental Shelf, 1980. NPD. 8 pages. xxi) Guidelines for the Inspection of Primary and Secondary Structures of Productinn - and Shipment Installations and Underwater Pipeline Systems, 1978. NPD. 17 pages. xxii) Development Document for Interim Final Effluent Limitations Guidelines and Proposed New Source Performance Standards for the Oil and Gas Extraction Point Source Category, 1976. US Environmental Protection Agency. xxiii) Study of Offshore Mining and Drilling Carried Out Within the Limits of National Jurisdiction - Safety Measures to Prevent Pollution, 1980. UNEP Working Group of Experts on Environ- mental Law. 55 pages. xxiv) Guidelines for Preparing Outer Continental Shelf Environ- mental Reports, 1980. US Geological Survey. xxv) Guidelines for Preparation of an Environmental Impact Statement, 1980. Canada. 28 pages. xxvi) Drilling Mud Toxicity:' Laboratory and Real-World Tests, 1978. Ocean Resources Engineering. 5 pages. S zxxvii) Programmatic Environmental Impact Statement: US Lake Erie Natural Gas Resource Development. US Army Corp of Engineers and EPA. 282 pages. xxviii) Working Conditions and Working Environment in the Petroleum Industry, Including Offshore Activites, 1980. ILO, Geneva. 116 pages. xxix) Guidelines on Means for Ensuring the Provision and Main- tenance of Adequate Reception Facilities in Ports, 1976. IMCO. 16 pages. - 272 - xxx) Reports from Working Groups I and II and III under the 1978 Hague Conference of Safety and Pollution Safeguards in the Development of N-W European Offshore Mineral Resources, 1980. IMCO. 40, 130, and 60 pages, respectively. xxxi) Study of Offshore Mining and Drilling Within the Limits of National Jurisdiction - Liability to Pay for - Compensation for Environmental Damage - Conclusions, 1980. UNEP Working Group of Experts on Environmental Law. - 273 - ANNEX Page 1 i. Marine Operations: These regulations concern issues relevant mainly to mobile platforms, anchoring, construction, certification, fixed equipment, general requirements, stairways, lighting conditions, life- jackets, evacuation facilities platform, population densities, fires, safety provisions, rescue crafts, helicopter landing decks. Schedule 1 is a regulatory document concerned with application for consent to "Designated Authority." For Bank purposes the authority in question will occasionally be the Bank itself. ii. Drilling Operations: These regulations similarly consider chn- sent requirements for equipment to comply with ceTtain standards, (well, casing, blowout preventers, etc.). They also consider abandonment of wells, inflammable and toxic gases, and production tests. iii. Petroleum Production: These regulations consider requirements for production equipment and recovery of petroleum, pressure valves, con- trol mechanisms, safety devices, flaring, accidents, toxic gases, pollu- tion, (waste oil, oil sludge, emulsion disposal, petroleum effluent dis- charge limitations). (Oil and Gas Production and Conservation Regulations. This 'very detailed document covers, inter alia, drilling program approvals, equipment standards, operator safety, medical facilities, firefighting, alarm systems blowout prevention, casing, operational manuals, contingency plans, inspec- tions, safety zones, safety valves, monitoring, waste materials, personnel training, records, abandonment.) iv. Recommended Practice for Design, Construction, Operation and Main- tenance of Offshore Hydrocarbon Pipelines: A technical document covering design, safety systems, inspection and testing, operation and maintenance, corrosion control. v. Internatignal Convention for the Prevention of Pollution from Ships: (70 countries). A regulatory, technical, and administrative protocol covering, inter alia, regulations for prevention of pollution by oil, by sewage, by garbage, by hazardous substances. vi. Recommended Practice for Blowout Prevention Systems: A tech- nical document of recommended practices for blowout prevention equipment systems.The document covers, inter alia, diverter systems, preventer stack arrangements, choke main folds, kill liner, closing units, auxilliary equipment, testing, sealing, blowout preventer modifications for hydrogen sulfide gas environments, pipe stripping. All of the above are considered for both surface and subsea installations. vii - ix. These documents consider safe practices related to title texts. - 274 ANNEX Page 2 xiii. Considers practices related to H2S. x. Recommended Practice for Planning, Designing and Constructing Fixed Offshore Platforms: A document covering planning, design criteria, welding, fabrication, installation, inspection, and surveys. xi. Recommended Practice for Production Facilities on Offshore Structures: A document covering codes, rules, regulations, design con- siderations, production equipment arrangements, and fire protection. xii. Recommended Practice for Design, Installation, and Operation of Subsurface Safety Valve Systems: A set of technical recommendations covering design, installation, operation, testing, and maintenance of sub- surface safety valve systems. xiii. Recommended Practice for Analysis, Design, Installation and Testing of Basic Surface Safety Systems on Offshore Production Platforms: A comprehensive, technical coverage of basic surface safety system on off- shore production platforms. xiv. US Geological Survey: No. 11 cousiders Flaring and Venting of Grs; No. 7, Spill Control and Removal. General and non-technical recom- mendations. xv. International Convention for the Prevention of Pollution from Ships: (70 countries). A regulatory, technical, and administr4tive protocol covering, inter alia, regulations for prevention of pollution by oil, by zewage, by garbage, by hazardous substances. zvi. Petroleum Production: These regulations consider requirements for production equipment and recovery of petroleum, pressure valves, con- trol mechanists, safety devices, flaring, accidents, toxic gases, pollu- tf , (waste oil, oil sludge, emulsion disposal, petroleum effluent dis- charge limitations). xvii. Onshore Impacts: , Summary of Conference on Cooperation in the Production and Development of the Marine and Coastal Environment of the West Afri-can Region. Non-technical. xviii. World 'Directory: Includes legislation and administration, country by country, as known by the IUCN, 1977. Office of Environmental Affairs 1981 - 275 TE WORLD BANK JUNE 1980 OFFICE OF ENIRONMNTAL AFFAIRS OIL PIPELINES 1. A wide variety of commodities and resources (gaseous, liqui. and solid) are presently transported by pipeline, over distances varying fzom a few. meters to several bundred kilometers.. This document will confine itself to pipelines designed for the bulk transportation of oil products over long distances, as opposed to piping necessary in the local handling, industrial processing, and marketing of crude oil and its by-products. 2. Pipelines are used for transport both between crude product and processing installations entirely on land, as well as between offshore wells and onshore transfer or processing facilities. In Europe, for example, trans- portation of crude oil has been mainly between ocean terminals and inland re- fineries, which are usually near the centers of consumption. In the United States pipelines have been used primarily to transport crude oil from pro- duction fields to refinery centers. Pipelines constitute an important ele- ment in the transfer of crude oils, both in terms of economics and time, as opposed to transfer by tankers. The development of supertankers has changed the economics of pipeline versus tanker transport. 3. Both crude oil and nearly all finished petroleum products can be transported by pipelines. Heavy fuel oils (residual fuel), used widely by industry and power stations, generally cannot be pipelined except at consid- erabl. extra cost and over limited distances. All the lighter products can be handled through a pipeline. A single line, by transferring batches in correct and properly scheduled sequences can be used to supply a large part of the variety of oil requirements of a specific area. Pipelines to date have the best safety record among the various methods used to transport crude oil. PIPELINE CONSTRUCTION AND OPERATION Pipelines do not have the flexibility of tankers. They are permanent fixtures and, once installed, cannot be rerouted even if conditions change or a different means of transport becomes more advantageous. Therefore, they are initially designed and constructed on the basis of the ultimate estimated capa- city. The construction of a pipeline must be based on broad forecasts as to the flow of oil over a specific route for many years in the future. 5. Offshore pipelines, located in waters as deep as 350 to 450 meters, are frequently used to transfer oil from ocean production sites to onshore storage, handling, or processing facilities. Pipe sizes will range up to 90 cm or more in diameter, depending upon water depth as well as the flows to be carried. - 276 - 6. Ocean pipelines are usually installed in one of three ways: (a) sections are assembled and joined onshore, and towed out to sea as assembly proceeds; (b) sections are joined at or near shore, towed out to sea as units, and sunk at the proper location. Sections are joined by divers after being put in place at the sea bottom; and (c) pipe sections 15 to 30 meters in length, depending upon diameter, are taken to sea on "derick-lay" barges, welded to- gether on the barge, section by section, floated out along the end of the barge, and then allowed to sink to the bottom. Regardless of the laying technique used, all pipe ends are joined together by welding at some stage of the instal- lation. 7. Where depths permit the pipeline rests in previously prepared trenches on the sea bottom, and these are back-filled after the pipe is in place. In other situations, the line rests on the bottom but care must be taken to assure that it lies flat and avoids laying on large boulders or other obstructions. The pipe must be weighted to minimize or eliminate shifting after it is set in place. This can be accomplished by providing a heavy concrete outer coating on the pipe, some 10 cm. in thickness, before it is set in place; anchoring to cement filled bags; attached to the seabed by means of drill-in expandable rock anchors; or other similar techniques. 8. Laying pipes on land is considerably less complicated than in the case of marine installations. Once the route is established and rights-of-way cleared, the pipe is laid in trenches, specially prepared according to the soil conditions, topography and other factors. Sections of pipe are laid in the trench, and welded end-to-end at the site. 9. Pumping is required for transport of the petroleum over long distances. Centrifugal pumps, provided with variable speed drives, are most frequently used. Where only one product is to be moved at all times constant speed units are suit- able. Pump design selections, and location are based on a number of factors such as viscosity of prod=cts to be transported, topography, distances, pressure gradients, and other characteristics. Power for pumping facilities is from diesel fuels and usually generated at the site, since locations are generally remote from population centers. 10. Once installed, pipelines can operate with relatively little attention. Constant inspection and maintenance must be provided, however. The major costs are those for installation, including construction, burial, materials and pump- ing equipment. Total operating costs, including direct operations and capital charges, will average about 10 percent of the total capital costs. SOURCES OF POLLTON 11. The p-incipal source of pipeline pollution is from leaks which can result from a number of causes. Assuming a "zero percent loss" at time of in- stallation leaks can arise from corrosion, damage from eztarnal forces or factors, and carelessness. 12. Pipe corrosion may occur both externally and internally. With modern techniques, this is no longer considered to be a significant problem. Cathodic protection enables advance detection of weak points. - 277 - 13. Damage from external forces is considered potentially to be the most serious source; particularly when lines pass through or near large industrial or building sites. Lines in areas subject to operation of heavy agricultural equipment may also suffer damage. Ships anchors catching on lines laid in shallow waters are another potential source of damage. Leaking pumps and valves can also contribute pollution. 14. Carelessness is generally the result of human errots, and is the cause of spills in connecting to or delivery from the pipelines. 15. In the case of pipelines on land, soil erosion and discharge of sedi- ment to surface waters can occur during the trenching required as part of the construction phase. The construction of necessary access roads and landing strips are also potential sources of sediment from runoff. POLLTION CONTROL MASRES 16. Pipeline pollution can be prevented or minimized by various means, both before and after operations are started. During the construction phases (a) all materials should be carefully inspected for manufacturing defects; (b) all welded joints should receive careful inspection; (c) hydrostatic tests, at pressures above normal working pressures,should be made; (d) corrosion con- trol technology should be applied; and (e) alarm systems, capable of providing advance or- inediate warnings of failures or breakdowns, should be included. After the line is operating, an effective inspection and maintenance program will be required. 17. Hydrostatic tests are made on each pipe length to detect the presence of wall cracks, pinholes, or -other defects which might cause leakage. Welding edges and pipe surfaces are inspected by visual and ultrasonic methods for material defects before welding. When completed,all welded joints should be inspected by I-ray techniques. Pressure relief valves are included in the system to provide for a rise in the internal pressure due to a temperature rise, or other occurrence which might cause a blockage. 18. Protection against external corrosion may be provided by coating with such materials as asphaltic mixtures, coal-tar enamels, or epoxy compounds. Pipelines should be electrically insulated from platforms and. land- structures. These measures protect against the loss of metal that could endanger the strength and safety of the lines. Internal corrosion may be controlled by addition of corrosion inhibitors to the materials passing through the- lines. 19. Cathodic protection methods can also be used to minimize or eliminate external corrosion in land-based lines. The sacrificial-anode method, most often used, depends upon making the metal to be protected (the pipeline, in this case) the cathode in the electrolyte involved. The soil functions as the electrolyte. Zinc, magnesium, or aliminum are used as the metal anode and provide the extra (or sacrifical) metal which can be "sacrificed" in the corrosion process. The metal anode "bracelets" are attached to the steel pipe, - 278 - at distances of 100 to 200 or more meters, and are generally of sufficient size to last for the projected life of the pipeline. 20. Inspections along the length of pipelines, for land installations, are necessary to detect major leaks or losses. Helicopters are well suited for this purpose, particularly in marsh or sparcely populated areas. The inspection should cover not only possible leaks but also irregularities which might endanger the line such as places where the pipeline has been exposed, conditions of river banks intersected by the line, damages to com=unications lines adjacent to or part of the pipeline operation, and extraneous work under- way near the pipeline. 21. In the case of pipelines running through the ocean and other waters, measures to control pollution should include: (a) Providing all pipelines leaving a structure and receiving production from the structure with a high- low pressure sensor to shut off the wells. (b) Providing all pipelines delivering products, to either offshore or onshore production facilities, with a shut-off valve at or near the receiving facility, connected to an automatic, or remote shut-off system. (c) Providing sensors and automatic shut-off valves or devices on all pipelines crossing a structure, to avoid uncon- trolled flow at the structure. (d) Equipping all oil pu=mps with automatic high-low pressure shut-off devicesi (e) Providing a metering system to give continuous comparison between input and output on all lines, and thus detect any line leaks. (f) Providing protective coatings, cathodic protection, or other measures to avoid loss of metal and weakening of the pipe. (g) Assuring that all pipelines are installed and maintained so as to be compatible with trawler operations. () Installing and maintaining pipelines to assure protection against water currents, storm scouring, soft bottoms, and other environmental influences. (i) Inspecting the ocean surface above the pipeline at least once per week for indications of leakage. Aircraft, float- ing craft, or similar means may be used for this purpose. - 279 - (j) Conducting an external inspection of all lines by side scan sonar or other acceptable means, at least once per year, to identify exposed portions of the pipeline. Exposed sections are then inspected in detail by photographic or-other means to determine if any hazards exist to the line or to other users of the area. 22. An acceptable, fully detailed system for operation, inspection and maintenance of the installation should be established before the start of operations. Once operations begin accurate records of all inspections, events, unusual incidents, actions taken, etc. should be maintained as part of the overall records system. Good operation and maintenance constitute the most effective method for controlling pollution from oil pipeline installations. STANDARDS AND REGULATIONS 23. National standards and codes of practice exist or are under consid- eration in many countries thrcughout the world. Generally these cover minimu standards and requirements to assure design, construction, operation and main- tenance of pipelines according to internationally accepted and proven engineer- ing safety practices. While these standards may or may not have legal status, they are widely recognized and are sponsored by reputable engineering or standards organizations. 24. Standards promulgated by the United Kingdom Institute of Petroleun, the American Petroleum Instituite, and the USA Standards Institute have received wide acceptance. The Economic Commission for Europe (ECE), Organization for Economic Cooperation and Development (OECD), and other international agencies have also promulgated codes and standards dealing with oil pipelines. BIBLIOGRAPE! 1. Organization for Economic Cooperation and Development "Pipelines- The United States and Europe - Their Legal and Regulatory Aspects", Paris (1969). 2. Abrahamson, Bernhard J. and Joseph L. Steckler "Strategic Aspects of Seaborne Oil", International Studies Series No. 02-017, Vol. 2. Sage Publications, Beverly Hills/London (1973). 3. Hubbard, Michael. "The Economics of Transporting Oil to and within Europe". Maclaren & Sons Ltd. London (April 1967). 4. "Pipeline Design and Construction". Manual Compiled from 1976 issues of Oil and Gas Journal. Petroleun Publishing Co. Tulsa (1977). 5. Economic Commission for Europe "Proceedings of the Seminar on the Protection of Ground and Surface Waters Against Pollution by Crude Oil and Oil Products". Geneva, 1-5 December 1969. 2 Vol. United Nations. New York (1970). - 280 - 6. U.S. Department of the Interior, Geological Survey. "OCS Orders 1 through 14 Governing Oil, Gas, and Sulphur Leases in the Outer Continental Shelf and the Gulf of Mexico Area". Washington (January 1977). 7. U.S. Department of the Interior, Geological Survey. "Notice to Lessees and Operators of Federal Oil and Gas Leases in the Outer Continental Shelf Pacific Area". Washington (June 1, 1971). - 281'- THE WORLD BANK JANUARY 1982 ENVIRONMENTAL CONSIDERATIONS IN OIL SHALE PROJECTS. BACKGROUND INFORMATION Introduction: 1. Shale oil production will combine a number of processing opera- tions on one site: mining, ore preparation, retorting, gas treatment, refining, and solid waste management. The scale of operation will be mas- sive. Consequently, the rates at which point source and fugitive pollu- tants are generated will require strict control. Potentially applicable control technologies employed in related industries-such as petroleum production, stone crushing, cement manufacture, and electric power opera- tion--may not be directly transferable to shale oil production because of process mixes and integration. General Overview of Environmental Problems 2. The environmentally problematic effluents and wastes from oil shale operations have not been thoroughly characterized. In some cases, adequate sampling and analysis methods have not been developed, validated, and standardized. In a commercial operation the byproducts of retorting will usually be processed in some further way before their characteristics as potential pollutants can be identified and control technology devel- oped. Site and process-dependent pollutants, particularly trace organics and inorganics, may have the greatest potential impact on health and wel- fare. Finally, rufining shale oil into end use products may result in in- creased emissions of toxic compounds. 3. Control technologies for treatment of off-gases are generally believed to be adequate, but they need to be demonstrated for key pollu- tants in off-gas streams. Additional studies are needed, however, to characterize off-gases from both in situ and surface retorting processes because of the potential for release of toxic trace elements. 4. It will be especially important to control particulates from mining and handling operations by use of suppression systems. Water sprays, along with wetting agents and organic binders, need to be eval- uated for use at the points of emission as well as on haulways and ore piles. In-mine localized particulate removal by modular wet scrubbers, electrostatic precipitators, or baghouses needs to be evaluated. For ex- ample, whether electrostatic precipitators can be used to control partic- lates from mining and crushing operations will depend on characteristics of the dust. Raw oil shale dust resistivity has not been adequately in- vestigated. Additional studies are needed, especially with respect to fine particulate control. -282- 5. Because of the absence of a full scale oil shale industry, the adequacy of control technologies for handling oil shale wastewaters is still questionable. Some oil shale developers contemplate using retort water to moisten retorted shale for dust control and to aid compaction. If the retort wastewater is used in this manner, the hazardous and toxic constituents might migrate to local surface and ground water supplies. 6. Modified in situ oil shale processing will generate more waste- water than can be consumed by process reuse. Subsurface injection or sur- face discharge may be necessary. Wastewater constituents may include haz- ardous organics (polycyclic materials, phenolics, amines) and inorganics (arsenic, molybdenum, vanadium, boron, among others). Control techinques must be developed, therefore, to ensure effective removal of these constit- uents before wastewater disposal. 7. Little is known about the movement of ground water into and through abandoned chambers of modified in situ operations. To date, only speculations have been made about the leaching of such chambers by ground water. Consequently, laboratory studies should be conducted to determine probable leaching rates and concentrations of organic and inorganic con- stituents. These studies should be supplemented by field monitoring of ex- isting and near-future in situ retorting operations. 8. The disposal of solid wastes resulting from oil shale mining and processing is a major environmental concern. Retorted shale could present problems of surface and ground water degradation if pile stability and im- permeability are not maintained. All research and monitoring programs to date have dealt with relatively small quantities of retorted shale. Poten- tial problems, such as mass stabilizations of shale piles and maintenance of an impervious layer below plant root zones, can likely be identified and solutions found only by creation of a large pile from commerical scale pro- cessing. SPECIFIC. ENVIRONMENTAL IMPACTS Atmospheric Emissions 9. Atmospheric emissions will arise from several activities or op- erations during oil shale processing. -The major source of S02, oxides of nitrogen (NOx), and carbon monoxide (CO) will be fuel combustion for pro- cess heat; S02 will also be emitted in the tail gases of sulfur recovery operations. The use of fuel oils in mobile equipment and explosives will result in emissions of CO and NOx. Hydrocarbons will be present both in combustion emissions and in product storage tank vapors. Emissions of par- ticulate matter will result from blasting, raw and spent shale handling and disposal, raw and spent shale dust in process gas streams, fuel combustion, and other site activities that generate fugitive dust. 10. Potentially hazardous substances may be emitted during the ex- traction and processing of oil shale. Silica (quartz) may be present in dust derived from oil shale and associated rocks and in fugitive dust. Particulate emissions from fuel combustion and fugitive dust from spent shale handling and disposal may contain polycyclic organic material (POM) -283- and. certain trace metals. Gaseous ammonia (NH3), hydrogen sulfide (H2S), and volatile organics may be released during moisturizing and subsequent cooling of retorted shale. Catalyst materials may release particulate matter containing trace metals to the atmosphere during regeneration, hand- ling, and final disposal. 11. Pyrolysis of essentially any type of organic material produces some POM, and oil shale is no exception. In general, POM compounds have low volatility and are associated with solids or high boiling liquids, or with particulates. Although POM is known to be present in carbonaceous re- torted shales, its biological availability and potential hazard in this form are not well known. POM compounds could be released to the atmosphere during shale retorting, during handling and disposal of retorted shales, or during combustion of shale-derived oils. 12. Temperature and oxidation-reduction conditions during retorting are not severe enough to volatilize most metallic and heavy elements. With notable exceptions such as arsenic, mercury, and possibly antimony, most trace elements (for example, nickel, vanadium, and molybdenum) will proba- bly remain with the spent shale or be found as components of raw and spent shale solids entrained in retort gases and in raw shale oil. Arsenic in raw shale apparently forms a range of volatile oil-soluble compounds (per- haps organic .arsines) during retorting. It appears in raw shale oil and in all condensible oil fractions. If not removed during upgrading, arsenic will be present in shale oil combustion products. If nickel is present and process conditions favorable, nickel carbonyl, a highly toxic gaseous com- pound can be formed. 13. Actual emissions of nonvolatile trace elements will be in approx- imate proportion to raw and retorted shale particulate emissions from oil shale extraction and retorting. These emissions may not be different in nature or magnitude from those associated with the extraction and process- ing of other ftel and nonfuel minerals (coal, limestone, phosphate rock, and so forth). Further, the dolomitic or alkaline nature of some oil shale immobilizes many elements as relatively inert oxide, carbonate, or silicate salts. Trace element mass emission rates give no simple indication of bio- availability-'chemical reactivity, or physical properties. 14. Metals (nickel, cobalt, molybdenum, chromium, iron, zinc) and their compounds are used as catalysts for hydrotreatment, dearsenation, sulfur recovery, and trace sulfur removal. Particulate matter containing catalyst metals could be emitted either during on-site regeneration or dur- ing handling and disposal. Catalyst use is, of course, not unique to shale oil processing, and most information and experience in preventing hazardous emissions can be borrowed from the petroleum and related industries. 15. The refining of crude shale oil will produce a number of potent- ially adverse environmental effects, primarily as a result of atmospheric emissions. Data have not been developed on the quality and quantity of these emissions. - 284 - Water Quality: 16. Water is necessary to the development of an oil shale industry. Water will be needed- for dust control during mining and crushing, for gas cleaning and air pollution control, for cooling, and for moisturizing re- torted shale. Upgrading crude shale oil, on-site power generation, and re- vegetating disturbed land and retorted shale disposal areas will also con- sume large quantities of raw water. The water needs per unit of net pro- duct will necessarily depend on the mining, retorting, and upgrading methods used. In general, in situ methods are expected to consume less water than conventional mining and retorting. 17. Most major developers in the United States have indicated that they intend to discharge no wastewaters directly to surface streams. Sur- face retorting process waters would be reused, and perhaps ultimately ap- plied to retorted shale. Effects of extraction and processing activities on local hydrology and water quality are therefore likely to be indirect or incidental. The water pollution implications of mine dewatering, of creat- ing large retorted shale disposal piles, and of abandoning in-ground re- torts have not been determined; these actions could create major environ- mental impacts. 18. Because of the low concentration of compounds in discharge waters, no acute or chronic effects on aquatic biota in surface waters may result; however, compounds of low solubility may be bioaccumulated by some aquatic organisms and become toxic to other aquatic organisms, birds, and man. Oil shale process waters contain single-ring and polynuclear aroma-- tics that contain suspected carcinogens. If process waters are discharged into the aquatic environment, sediments may accumulate these compounds and later release them slowly. More information is needed on the degradation of these compounds and on their potential for bioaccumulation in aquatic organisms. Effects of extraction and processig activities on existing water quality in the oil shale region will vary with the geography and the season. 19. Aqueous wastes from oil shale processing can be categorized broadly as originating from direct or indirect sources. Wastewaters from direct sources are those generated by unit operations or processes, includ- ing: -Retorting --Upgrading -Some air emission control and gas cleaning processes -Cooling and boiler water blowdowns --Water Treatment -Mine Dewatering --Sanitary Disposal 20. Wastewaters from indirect sources include: --Leachate from retorted shale disposal areas -Runoff and erosion resulting from construction and site use -Runoff resulting from mining and transport activities -285- 21. Some water vapor will condense with crude shale oil during separation of the oil from retort gases. The condensate can partially separate from crude shale oil during storage, or it can appear in aqueous waste streams of shale oil upgrading operations. Water vapor remaining in retort gases after oil separation can be condensed during cooling or gas cleaning or it.. can appear in the flue gas stream for retort gas combustion. Water separated from crude shale oil will contain ammonia, carbonate and bicarbonate, sodium, sulfate, chloride, and dissolved or suspended organic compounds (phenolics, amines, organic acids, hydrocarbons, and mercaptans). Smaller quantities of calcium, magnesium, sulfides, and trace elements may also be present, along with suspended shale fines. Water condensed from retort gases will contain primarily ammonia and carbonates, with traces of organic substances and sulfur-containing compounds. 22. The quality of the wastewaters from upgrading operations will vary with the level of on-site upgrading or refining.- In general, a full- scale refining operation may include any of the following wastewater streams: oily cooling water, process water, and wash water. These waste- waters will contain high concentrations of ammonia, bicarbonates, sulfides, phenols, total dissolved solids, oil, and grease. 23. Wastewaters from some air emissions control and gas-cleaning systems will contain shale dust particulate matter, hydrocarbons, hydrogen sulfide, ammonia, phenols, organic acids, and amines. Thiosulfate and thi- ocyanate may also be present in these wastewaters. 24. Because of evaporative losses, a constant buildup of dissolved solids in cooling water will necessitate discharge of part of this recircu- lated water as blowdown from cooling water systems. Similarly, part of the boiler water will have to be discharged as blowdown to minimize boiler scaling. Both the cooling water and the boiler blowdown water will dontain high concentrations of dissolved solids and substances such as hexavalent chromium used for corrosion control. 25. Raw water treatment systems will have to supply water of good quality for processing operations, cooling towers, steam generation, and other miscellaneous uses. Water treatment wastes will usually consist of chemical sludges, backwash water from filtration systems, and blowdown from zeolite softening systems. Most of the waste will be lime sludge high in hardness and dissolved salts. 26. Aquifers encountered during mining must be dewatered. Unless ground water is prevented from entering the mine, however, dewatering could produce large quantities of low-quality water; quality and quantity will vary with location and processing technique. During full-scale surface re- torting, most of this water will be used in wetting and compacting retorted shale. Major constituents of mine water are sodium, carbonate, bicarbo- nate, chlorides, fluorides, and boron. Reinjecting this water into the aquifer may increase ground water salinity. 27. Sanitary wastewaters from operational facilities will include domestic sewage from kitchens, bathrooms, and laundries. Because these wastewaters contain unstable organic matter and enteric micro-organisms, they will require treatment before disposal. - 286 - 28. Perhaps 45 to 50 percent of the water needed for an oil shale plant will be used to moisturize retorted shale. Much of this water could possibly be supplied by mine water and process wastewaters. Because of the large quantities of water used and the exposure of retorted shale to rain and snowfall, indirect water pollution may result from leaching or runoff from retorted shale piles. Some of the water applied to retorted shale is expected to be bound to the shale in the form of simple hydrates. The sus- pended and dissolved constituents of wastewaters applied to retorted shale may affect the solubility of potential contaminants in the shale. Experi- ments in the laboratory and with small plots indicate that inorganic salts (sulfate and salts of sodium, magnesium, and chlorine) may be leached from retorted shales. Small quantities of organic substances and trace elements are also water soluble. 29. Construction, mining, and site use may increase sediment and dis- solved solids loading in surface runoff and receiving. streams. This indi- rect source of potential water pollution is not unique to oil shale extrac- tion and processing, but may require careful control because of the magni- tude of site activities. Collection and impoundment of runoff will likely be necessary. Solid Waste 30. The solid wastes resulting from oil shale processing present one of the major environmental problems associated with commercial develop- ment. Shale-derived solid wastes will include fines from raw shale crush- ing and conveying, mined raw shale waste, and processed (or retorted) shale. Together these wastes constitute most of the process solids requir- ing disposal. Other solid wastes will depend primarily on the pollution controls employed and on the extent to which crude shale oil upgrading is carried out in conjunction with retorting. These wastes may include shale oil coke, treatment sludges, and spent catalysts. 31. Disposal of surface retorted shale will involve transport and surface emplacement of large quantities of solids on a scale only rarely attained to date in the :,ining industry. The spent shale will contain po- tentially leachable salts and, in some cases, a carbonaceous residue from retorting. If shale oil is upgraded in conjunction with retorting, a dis- posal pile might also contain spent catalysts, sludges, atsenic-laden solids, and other plant wastes. 32. In light of the foregoing, it would appear that potential hazards exist relating to: -Pile stability --Airborne particulates, odors, and organic vapors -Leachates, organic and inorganic, caused by precipitation and ground water movement -Transfer of possible hazardous organics or trace elements to the biosphere -Translocations of toxic substances to vegetation - 287'- 33. Mass movement of disposal piles could adversely affect water quality. Sediment and salts could be added to local surface waters, or to catchment structures. Changes in pile drainage systems caused by slumping, and so forth, may encourage infiltration. 34. Vegetation may be difficult* to maintain on a destabilized pile surface; as a result, surface wind and water erosion may increase. 35. Because no large disposal piles have been constructed to date, little is known about pile stability in real situations. Further, most of the work to date has dealt with carbonaceous shales; decarbonized shales, from which the organic content has been burned off, are likely to differ significantly in stability and leaching properties. 36. To control fugitive dusts, and to provide moisture for compaction and stabilizing the disposal piles, retorted shale will be wetted before transport and disposal. It is not known whether wetting will be sufficient to minimize particulate emissions at the scale of operations contemplated at each site. The characteristics of the spent shale and the micrometeor- ology at a given site are among the pertinent variables. 37. Runoff from, and infiltration into, disposal piles may result in water pollution. It is planned to route natural drainage at each disposal site around the pile or through the pile in conduits. Provisions must be made to drain side gullies, if present, and to protect ground waters from leachate contamination. It is not clear whether the absorptive properties of the individual spent shales and the catchment basins planned by most developers are sufficient to ensure environmental protection against water quality degradation. 38. The surface of a disposal pile is subject to natural eros.ion by wind and water. In principle, it is possible to protect or stabilize pile surfaces by means other than vegetation; the large areas involved in com- mercial shale oil operations, however, may make vegetation the preferred or economic alternative. Moreover, successful vegetation can create a biotic habitat similar to or consistent with that of surrounding areas. 39. True and modified in situ retorting will leave the retorted shale below the ground. There, the retorted shale may create high potential for ground water pollution. Subsidence that may occur could fracture overlying aquifers and result in water movement between aquifers and reduction of ground water quality. Substantial quantities of raw mined oil shale brought to the surface by modified in situ mining may be permanently dis- posed of as raw shale or may be surface retorted. In either case, leach- ates may affect surface and ground water quality. PUBLIC HEALTH 40. Waste streams associated with shale oil processing, crude shale oils, and upgraded or refined shale oil products may contain carcinogens or other hazardous trace substances from which industrial workers and the gen- eral population should be protected. - 288 - 41. Various known and suspected carcinogens belonging to the POM class have been identified in crude shale oil and shale oil products, in- cluding benzo(a)pyrene (BAP). Other carcinogenic compounds in the POM class have been tentatively identified in shale products including 3-meth- ylcholanthrene and an isomeric mixture of dimethylbenz(a)-anthracenes. In general, P0M compounds have high boiling points, about 570oF (3000C), and are found in the higher boiling distillates or residues of shale oils, in- cluding shale oil coke and carbonaceous residues associated with processed shale. 42. Some of the controversy about the carcinogenicity of shale-de- rived materials arises from using BaP content as an indicator of activity. Levels of BaP in shale oils are usually in the same range as levels- in petroleum oils havings a similar boiling point, suggesting that shale oil presents no more hazard than petroleum. Experimental tests with crude shale oil and various distillate fractions have shown, however, that the carcinogenic potency of these oil shale products measured by nonhuman bio- assay techniques cannot be attributed to BaP alone. Other carcinogenic or co-carcinogenic compounds may be present. Conversely, high measured levels of BaP in a material do not necessarily indicate biological availability. 43. In general, little is known about the hazards of shale-related waste streams; retorting and refining operations conducted to date have been limited in scope and size, and have been aimed primarily at demonstra- ting technology rather than determining effluent quantities and proper- ties. Preliminary biological studies of the oil shale industry have not demonstrated unmanageable problems of toxicity. Studies now in progress will further delineate potential toxic profiles gind possibly confirm pro- visional data now available. Continued research is needed to expand exist- ing data and to develop data on various refinery cuts, including residual oil, emission products from retorting and refining, and emission products from combustion of fuels for power production. Data are also needed 'on the health hazards that may be associated with the contamination of stream est- uaries or undergrond water by various leachates from shale oil technolo- gies. Although results thus far are encouraging, it would be prudent to reserve judgdment on the potential toxicity of oil shale development and shale oil production and use until the data base is extended to other para- meters and until other investigators confirm the results. ASSOCIATED EFFECTS Radioactivity 44. Some radioactivity will be released to the atmosphere during oil shale mining and processing. Radioactive elements will be contained in dust emissions, fine particulate emissions, process water discharges, and leachate from spent shale disposal piles. Some radon gas will be released directly. Noise 45. Noise will be created during oil shale development by processing plant construction and operation, community expansion, mining, and water reservoir operation, and by construction and operation of pipelines, - 289 - transmission lines, roads, and railways. Because oil shale development sites are, characteristically, a reasonable distance from population cen- ters, the impacts of noise are expected to be negligible. Social and Economic 46. Social and economic impacts of development are expected to be fairly severe because many oil shale sites are remote and sparsely populat- ed. Population centers in the oil shale area are basically rural. The in- troduction of nil shale development will significantly increase the numbers of people who use the towns, creating higher demands on local municipal services such as fire and police protection, schools, hospitals and health care, and on local utilities such as electricity, water, and sewage treat- ment. ARCHEOLOGICAL, HISTORIC, SCENIC AND OTHER VALUES POLLUTION CONTROL TECHNOLOGY 47. In planning for an oil shale operation, cAre should be taken in the initial stages to determine if the site contains any historical, arche- ologic, geologic, religious, paleontologic, biologic anV/or cultural values that should be considered in the site preparation. Often a reconaissance will serve to uncover evidences of such values resulting in a subsequent decision with the proper authorities regarding their disposition. Air Emission Controls 48. Particulate matter and dust emission sources will include raw shale mining, blasting, conveying, crushing, and screening. Dust from spent shale will result from transfer, conveying, and disposal operations. Particulate and dust emissions will vary about threefold, depending on mining and processing techniques and the richness of the shale. Open-pit mines will generate large quantities of dust simply as a result of the large quantities of shale and overburden to be handled. In situ retort op- erations will release much less particulate matter: however, rubblizing from in situ operations,may be a greater source of dust than conventional underground mining. 49. Water spray has potential for suppressing dust at open conveyors, crushers, or transfer points. Continous sprays would be needed, but at properly adjusted rates so that no runoff would result. Without-additives, water spray efficiency would be adequate (above 80 percent) for particles 5 micrometers and larger: however, efficiency drops to 43 percent for 3 mi- crometer particles and to 25 percent for 1 micrometer particles.Adding steam to the spray increases performance to 68 percent for 3-micrometer particles and to .40 percent for 1-micrometer particles. A more common method of increasing performance is addition of a wetting agent to reduce the surface tension of droplets on the particles. Overall mass effic- iencies on the order of 95 percent can be achieved. 50. Water spray may be effective in controlling open-pit mining dusts. Chemical binders may also be applicable to these dusts, as well as to storage piles unprotected from wind erosion. Moisturizing techniques may be used to reduce dust emissions from spent shale handling. -290- 51. A wide selection of control equipment is available for removal of fine particulate matter from gas streams and other closed operations. The performance efficiencies of baghouses, electrostatic precipitators, and scrubbers are all very high, even for fine particulate matter. The large quantities of particulate matter collected will probably be water slurried, then used to moisturize the spent shale. 52. Oil shale retorting will yield large quantities of low-Btu off- gas. Hydrogen sulfide and ammonia are the main constitutents to be removed from gas streams before the gas is used as fuel. The presence of other sulfur contaminants, such as carbonyl sulfide.or carban disulfide is sus- pected but has not been confirmed by experimental work. The presence and concentrations of these constituents will affect the selection of desulfur- ization schemes. 53. Over 99 percent of the ammonia and a small percentage of the hydrogen sulfide will separate in the condensate from the vapor product cooling unit following the retort. 54. Sulfur emissions associated with oil shale operations will origi- nate from retort off-gases (either burned for fuel or flared), tail gases from sulfur recovery operations, and the combustion of the produced shale oil. These emissions, primarily H2S and SO2, must be removed before the gas streams are released to the atmosphere. As an alternative, combustion- generated sulfur emissions can be controlled by the use of clean (desulfur- ized) fuels. 55. Over the years, the petroleum, chemical, and gas industries have used various processes for concentrating and removing hydrogen sulfide from gas strams, and new processes are under development. The choice of -an H2S removal process depends on gas stream characteristics and economics. Re- tort off-gases and shale oil refinery gases contain sulfur dioxide, but in small quantities that may not need treatment; however, if a Claus unit is used for H2S removal then the resultant tail gas will be rich in SO2 and will need treatment. A number of SO2 removal processes could conceivably be used. 56. If the retorting and refining gases are desulfurized, it is un- likely that further sulfur emissions control would be necessary to produce clean gases for use as fuel in process heaters and boilers. Trace amounts of ammonia in the gas would be converted to oxides of nitrogen on combust- ion; however, these quantities would be only a few parts per million com- pared to quantities of thermally generated NOx. Thermally generated NOx can best be controlled by demonstrated combustion modification techniques. If crude shale oil is used as process fuel, control of both SO2 and NOx emissions could be necessary. Full hydrotreating would be more cost effec- tive than flue gas treating, if on-site refining is included in the shale oil facility. 57. Hydrocarbon emissions will result from direct preheating of raw shale, and will need control. Thermal incineration is probably the method of choice. - 291 - 58. Hydrocarbons and carbon monoxide resulting from incomplete com- bustion will be emitted by the boilers, furnaces, heaters, and diesel equipment associated with oil shale development. With proper maintenance, emissions from these sources are not considered large; however, high back- ground levels have been reported in some areas, and any additional contri- butions from process operations will be a cause for environmental concern. Hydrocarbon and carbon monoxide emissions can be held to a low level by proper design, operation, and maintenance of external and internal com- bustion equipment. Wastewater Treatment 59. The quantity and quality of water ava1lable, methods of water use, and disposal criteria will dictate the pretreatment, internal con- ditioning, and wastewater treatment necessary at each oil shale processing site. Wastewaters from oil shale processing will contain dissolved and suspended solids, oil, trace elements and metals, trace organics, toxics (carcinogens), dissolved gases, and sanitary wastes. 60. Individual waste streams have not been characterized adequately to make firm treatment or control technology judgmpnts regard'ing which unit processes should be applied to which waste streams. Nonetheless, so-me ideal processing schemes have been envisioned and discussed. The size of the treatment unit will depend on the wastewater volume to be treated at a specific site and on the concentrations of pollutants to be removed. The basic operating approach will be to concentrate the pollutants for ultimate disposal or containment so that clean water can be recycled or discharged. 61. Wastewaters that contain dissolved solids (more than 1,000 milli- grams per liter) and suspended solids, and that are essentially free of oil and trace organics, can be collected and flow-equalized in large holding lagoons before treatment. Oily wastewaters (more than 10 milligrams of oil per liter) from all wastewater sources should be collected and processed by separators or similar equipment before receiving further treatment. Waste- waters contaminated with trace elements and metals should be essentially free of oil and dissolved solids to allow them do be treated separately. Trace organie wastewater volumes are not expected to be large, but these wastewaters will contain highly diverse types of organic pollutants. Toxic wastewater volumes are expected to be small, but advanced treatment and control will be needed for the concentrates collected. Specific controls and treatment will be necessary for wastewaters from scrubbers that absorb common oil shale process gases-such as hydrogen sulfide, ammonia, and car- bon dioxide-before the water is reused or discharged. Sewage and water treatment plant releases should be considered for separate treatments and disposal. 62. The amounts and qualities of water to be expected from mine de- watering are not known, and they will depend on the site. In contrast to some earlier characterizations of surface retorting operations as large water consumers, true and modified in situ developments may produce a sur- plus of water that will have to be treated and discharged or reinjected in- to aquifers. -292- Solid Waste Controls 63. A commercial oil shale industry will produce tremendous quanti- ties of spent oil shale, as well as smaller amounts of overburden, lean shales, raw shale fines, and chemical solids. Modified in situ operations may also produce large amounts of raw shale waste. For -ining, handling, and disposal of overburden, techniques used in the surface mining of other minerals should usually be applicable to surface mining of oil shale. These techniques include disturbing the minimum area necessary, using water sprays and chemical binders to control dust, conserving soil, and using arid area vegetation methods. 64. Except in a true in situ oil shale operation, some raw or spent shale will have to be disposed of onthc surface, either in disposal piles or as canyon fill. Any surface disposal of spent or raw oil shale will probably produce some leachate, which may adversely affect surface and ground water quality. It will likely be necessary to provide for collect- ion, treatment, and reuse of this leachate. 65. Process-generated solid wastes-such as spent catalysts, lime sludges, coke,- and other solids from water and wastewater treatment sys- tems--may contain toxic substances. Disposal of these wastes by burying them in the spent shale pile would be likely to increase the levels of tox- ic pollutants in the spent shale leachate. It may be possible to dispose of some process wastes along with the spent shale if it is demonstrated that the wastes do not themselves produce a leachate or promote production of additional pollutants in the spent shale leachate. A preferred method of handling potentially toxic spent catalysts would be to return them to the manufacturer for regeneration and subsequent reuse, 66. It may be possible to dispose of surface-retorted spent shale by returning it to the mine, backfilling either with dry spent shale or with a spent shale slurry. Because of the potential for chronic leaching, it is recommended that spent shale not be returned to a wet mine; leachate prob- lems would be more easily controlled on the surface than in a subsurface environment.- Returning dry spent shale to a dry mine, however, would cre- ate support, decrease subsidence potential, and reduce surface spent shale storage by about 60 percent. In any case, mine disposal of *spent shale should not be considered viable until it has been critically investigated to ensure that leachates will not degrade ground or surface waters. 67. Leachate will contain water-soluble organic and inorganic solids. Because of its expected poor quality, leachate from surface dis- posal piles will probably be collected behind dams constructed for the pur- pose and located slightly downstream of the toe of the pile. An imperme- able base should underlie the pile, and drains should be included to pick up the leachate and discharge it at the collection point. For modified in situ oil shale operations, it will probably be necessary to minimize water flow through the retorts and collect and treat as necessary any leachate. Most of the ions present in leachate are also present in various flue gas desulfurization process liquids; therefore, it could be possible to use the leachate on site for removal of sulfur dioxide from flue gas streams of surface retorts. The leachate problem could also be reduced by leaching - 293 - the soluble minerals from the raw shale feed before retorting and passing the retorted shale through a spent shale burner to remove residual carbon and organics. 68. Modified in situ retorting, conventional underground mining, and possibly true in situ retorting may pose fracturing and subsidence problems unless subsidence control technology is provided. For conventional under- ground mining, some control technology exists that could probably be modi- fied and applied to the specific hydrologic and geologic environment of a particular underground oil shale mine. Backfilling mine voids with spent shale could provide additional support'though ground water pollution could be a concern. Special attention would be needed to avoid long-term prob- lems from weakening of pillar strength by spalling and weathering. For modified and perhaps true in situ retorting, the key to controlling subsi- dence or fracturing of surrounding strata will probably lie in learning to control rubblization and in developing a technology that wl provide pill- ars adequately sized and appropriately spaced to support overlying strata. Other Controls 69. Other process controls include those necessary to reduce storage tank emissions, biological sludges, tank bottom sludges, and separator sludges. Floating-roof tanks and internal floating covers reduce both diurnal breathing losses and filling losses associated with fixed-roof tanks. Thp technology is well developed, having been used in the petroleum and chemical industries. Internal floating covers are preferable in.sites having high wind, rainfall, or snowfall because they are protected from the weather. 70. Refineries limit or reduce sludges and other solid wastes primar- ily through source control techniques involve identifying and monitoring sourqges of oil, water, and other contaminants and then implementing inplant operating procedures to introduce less water into drains, to recover oil and water from solid wastes, to decrease the amount of contaminants in oily drainage, and to reduce the oil content of separator solid waste. SAMPLING, ANALYSIS AND MONITORING 71. One p.oblem facing developers is sampling and analysis of product and waste streams associated with producing oil from oil shale. The methods that have historically been used to analyze air and water samples have been applied to oil shale effluents, but without the straightforward results expecte.. Extraordinary interferences and matrix effects appar- ently make some methods ineffective. Many workers in the field are add- ressing the problem of standardization of methods for collecting, shipping, storing, and analyzing samples. Interlaboratory studies on many different types of environmental samples will be needed to validate those methods best suited for consistent analysis of oil shale pollutants. 72. Effective monitoring through sampling and analysis is expected to provide: -A baseline evaluation of conditions before development --A record of changes from baseline conditions -A continuing check of compliance with environmental regulations and laws - 294 - --Predictive capability for timely notice of developing problems -A check on the effectiveness of mitigating procedures 73. A monitoring program shou].i include sampling of point source ef- fluents at and around the facility, non-point source effluents resulting from activity at the mining, processing, and disposal sites, and accidental discharges. Monitoring should begin with a baseline survey. 74. An air-monitoring program should include on-site gas and particu- late analyses and a network of meteorological and air quality measurement stations remote from the processing site. 75. Surface water monitoring should incorporate biological monitoring as well as physical and chemical analyses. Changes in aquatic biota may indicate subtle changes in water quality characteristics before they are detected by physical-chemical analyses for specific pollutants or by indi- cator parameters such as dissolved oxygen, pH, and hardness. Water moni- toring should be done both upstream and downstream; wet and dry surface streams and springs and observation wells should be monitored to detect ground water changes. 76. In a water-monitoring program, non-point-sources will probably receive greater attention than point sources beause of the difficulty of monitoring pollutants emanating from shale pile, construction sites, access roads, unlined catchments, and evaportation ponds. Adding to this problem will be the possible discharge of saline ground waters. Moreover, site ac- tivities may result in reduced water flows and, therefore, may affect al- ready limited supplies of water for agriculture, livestock watering, and other beneficial uses. 77. In addition to spent shale, disposal sites will probably contain raw shale fines, spent catalysts, sludges, and process wastewaters. Sur- face erosion and leaching of soluble salts and organic compounds will necessitate extensive disposal site monitoring, particularly of revegetation trenches, of the alluvium, and at the toe of the pile where pollution is most likely. The spent shale monitoring program particularly should be designed to identify environmental problems in time for corrective measures to be taken. NOTE: It is the intention of the Office of Environmental Affairs to make available two guidelines dealing with mining and retorting. These forthcoming guidelines will supplement those presently dealing with certain environmental problems also associated with oil shale; namely, Sulfur Dioxide, Dust, Noise, Effluent Disposal, Strip Mining, Underground Mining, Coke Oven Industry (retorting), and, Secondary Environmental Effects. 295 - THE WORLD BANK AUGUST 1982 OFFICE OF ENVIMEAL AFFAIRS PALM OIL INDJSTEd' GUIDELINES 1. The oil palm is found in a wild, seni-wild, and cultivated state in several equatorial tropical areas, but principally in Southeast Asia, Africa, Central America, and the Caribbean. By 1976 Malaysia had increased its oil palm plantings to the point where it had become the world's leading producer of palm oil. 2. The fruit of the oil palm is a mne-seeded fruit (drupe) whose outer pulp (mesocarp) provides the palm oil of Commerce. A hard-shelled nut within the mesocarp contains the palm kernel, from which are prodhced palm kernel oil (similar in composition to cocoanut oil) and palm ketnel cake (useful as a protein source for livestock feed). 3. Both palm oil and palm kernel oil are used primarily in the manu- facture of margarine, cooking fat, and soap. 'Ib a lesser extent they are also used for producing candles, glycerine, mayonnaise, bakery goods, and other edible and non-edible products. INDUSTRIA4 PROCESSES 4. The fruit of the oil palm grows in clusters, called fresh fruit bunches (F.F.B.), in which form it is harvested fran the tree. Some loose fruit is trapped between the leaf and the stem, and is collected with the bunches. The bunches and loose fruit are transferred as quickly as poss- ible to the factory for processing. Since maximum factory efficiency is achieved by maintaining a constant input of raw material, the fruit is sanetimes placed in storage prior to processing. 5. In a typical operation the fruit is accurately weighted upon re- ceipt and then either temporarily stored or transferred to processing. The fruit is processed as quickly as possible in order to minimize oil quality degradation. The initial processing step is sterilization, usually by steam injection, done to loosen the fruit in the bunches, and facilitate the stripping as well as other operations which follow. 6. After sterilizaticn the fruit is fed to strippers to separate it from the leaves. The fruit falls through the slats of the strippers to a conveyor, and to the digesters.* The empty fruit bunches are removed from the strippers for separate disposal. The bunches contain significant quantities of nutrients. 296 7. The purpose of digestion is to release oils fron the pericarp cells, raise the temperature of the mass to facilitate subsequent pressing, and drain away free oil to reduce the volume of material to be pressed. The pericarp cells are the main oil-containing tissue in oil palm fruit. The digester is provided with rotating knives or beater arms, which serve to stir and pulp the fruit into a mash. The wet mash is then drawn off for the crude oil extraction. 8. Oil is extracted either by centrifuging or by squeezing the di- gested pulp. Centrifuging has been used mostly in factories having a low output. Ram presses (manually or hydraulically operated) and screw presses are most frequently used for the larger plants. Solvent extraction has been attempted, but to date its use has been limited to extraction of oils frcm palm kernels. 0 9. The liquid drained from the digesters and extractors is the crude oil product, and consists of a mixture of oil, water and cell debris. The mixture is passed through vibrating fine screens to remove particles of fiber and shell ends and, after heating, goes to the clarifiers. * The screenings are returned to the digesters. 10. Static clarification is the method most frequently used to purify the oil. In this process, the oil and water mixtures go through a funnel to the bottom of a drum, one-fourth filled with hot water. Clean oil rises to the top and overflows, while the dirt tends to fall to the bottom. Cen- trifuging is used to remove oil fran the settled dirt. The purified oil is then run through a high-speed- centrifuge to remove the bulk of the re- maining water and impurities. Fran the purification system the oil passes to storage tanks. 11. The residues from the extraction presses, containing the whole and broken nuts and shells, is dried and passed through an air stream to separate the lighter fibers. The nuts are further dried to shrink the ker- nel within the shell, allow easier separation after cracking, and reduce the amount of broken kernels. After drying, the nuts are passed through a nut cracker and then to a screen for separating the uncracked nuts from the kernels and shell fragments. The shell and kernel are then separated, by a hydrocyclone. The kernels are dried, bagged and stored for subsequent pro- cessing. The separated shell material may either be burned or used as fill material. 12. Generally, palm kernel oil is not produced at the site producing the crude palm oil. The conditions for release of kernel oils are differ- ent from those of palm oil but are similar to those of copra and hard oil- bearing seeds. The kernels must be crushed to a very fine meal before the oil can be extracted under pressure. Steam cooking releases the oil still further, and it is then extracted by hydraulic batch presses, continuous screw presses, or by solvents. 13. A typical system for the production palm oil and kernels is shown in Figure 1. Cracked Nut rnixture Figurei.gTypicalSystem fr h P utio ofpamilr aNd K ra eparator S (riliser Firbr dinG s FEmPty Crude oil' bunJhus oily Sludge Parcheatiu8 o Dry lihlt$&:et tank lto ilers to twilers Puas (bil io SlUdgle water to drain Storag tankOil Paurifier C61n1inuo1us Shidve Stud414 drier clarification lank c.nitrtuse . tank Figure 1. Typical System for the Production of Palm Oil and Kernels. (From Turner and Gillbanks) . -298- WASTE SOURCES AND CHARACTERISTICS 14. Wastes originating from palm oil processing Nperations are gener- ally limited to solids and liquids. The solid materials are readily amen- able to separation and disposal. 15. The empty bunches, following the stripping operation, create a major disposal problem. They contain quantities of recoverable nutrients which are lost if the material is merely dumped. Dumping also creates con- ditions favorable for fly breeding, giving rise to nuisances. Use of the empty bunches for mulching has been found to be unecomonical. Separated shells are another solid waste for which provision must be made for dispos- al. Uncontrolled incineration of these residues, where utilized, could create air pollution problems. 16. Liquid wastes originate principally from (a) the sterilizdrs, where the fresh fruit bunches are heated under high pressure steam, and (b) the oil clarification step, in which the oil is separated from the sludge coming from the digester. 17. The most significant pollution parameters for palm oil processing wastes are 5-day biochemical oxygen demand (BOD5), chemical oxygen demand (COD), total suspended solids (TSS) , and hydrogen-ion concentration (pH). Other parameters may also be of significance at individual plants. Charac- teristics of a typical palm oil mill waste effluent are presented in Table 1. EFFLUENT LIMITATIONS 18. The work done towards establishing effluent limitations for the wastes fran this industry has been very limited, and much of it has been inconclusive. Considerable further development is needed on the chemistry and other characteristics of palm oil effluer.s under a variety of condi- tions. 19. It has been observed that waste effluents from palm oil process- ing are very similar in characteristics and behavior to effluents from the production of olive oil and by-product cake or meal from raw olives. The limitations and handling of wastes related to palm oil processing are based to sae extent on accepted practices in the olive oil industry. 20. It is feasible to achieve 100 percent reduction of pollutant and waste effluent discharges to surface waters by onei of the following meth- ods: - 299 Table 1. Typical Palm Oil Mill Waste Effluent Parameter Average Range pH 3.7 3.5-4.5 BOD5 - mg/L* 25,000 20,000-35,000 COD - mg/L 45,000 30,000-60,000 NH3N - mg/L 30 20-60 Org.N - mg/L 600 500-800 NO3 - mg/L 30 20-60 Tot. Sol. - mg/L 35,000 30,000-40,00b Susp. Sol. - mg/L 25,000 20,000-30,000 Ash - mg/L 4,500 4,000-5,000 Oil/Grease - mg/t 7,000 5,000-10,000 Starch - mg/L 2,000 Protein - mg/L 3,000 -- Tot. Sugar - mg/L 1,000 Flow - kg/kg. FFB 0.6 Empty Bunches - kg per kg FFB Processed 0.25 a/ From Sinnappa. * mg/L = milligram per liter - 300 - - spray irrigation - land application - evaporation ponds - discharge to municipal systems 21. Where the above methods cannot be applied, the wastes are amen- able to biological treatment. However, because of the high strengths of the raw effluents, treatment efficiencies in the order of 99 percent or better will usually be required to avoid damages to the environment. Ef- ficiencies of 95 to 97 percent are the levels generally economically achievable, and in many cases these may not be adquate. CONTROL AND TREATMENT OF WASTES 0 22. As previously stated, the empty bunches present a disposal prob- lem. Because they contain significant quantities of useful nutrients it is generally economical to institute by-product recovery measures. Currently, the most effective disposal method is slow burning by incineration, which reduces the bulk and produces an ash which can be used as a source of pot- ash fertilizer. 23. The shells that have been separated fram the kernels are col- lected and may be used either as fuel for steam generation or as road fill. When used alone, this residue is not satisfactory for boiler fuel since it contains silica which volatilizes and forms a glassy coating on the fire bars and refractory lining. Consideration has been given to the use of the shells as a filler for plastics, but no significant market ex- ists at this time for this purpose. 24. The sludges originating in the sterilizer condensate and the cla- rification proccess have a high oil and solids content, and cause very strong and disagreeable odors. A common method of handling these is by means of a series of sludge pits. Water and dirt sink to the bottom of the pits, while the oil floats to the top. The oil is recovered by skimning, and used for soap manufacture in some countries. The sludge settling in the pits may be used as a fertizlizer, or the water and sludge mixture disposed of by spray irrigation. 25. Where spray irrigation is applied to disposal of the effluen.., pumping distances should be less than one kilometer. Land requirements will be about 200 square meters per cubic meter of effluent per day. 26. For land application the terrain should be terraced and graded to level. Waste effluents are then discharged to one terrace at a time, to a depth of about 8 am. As a terrace dries it is plowed in preparation for the next application. Care should be taken to avoid contamination of fresh water aquifers. -301- 27. Evaporation ponds are operated in series for maximum effective- ness, and should be- lined to prevent percolation to ground waters. One pond at a time should be filled completely, to a depth of about 0.6 meter. The next pond in the series is then filled, while evaporation is taking place in the filled units. Enough ponds should be provided to permit handling the plant's. total annual discharge. The number of ponds required will depend upon the annual waste volume, the annual net evaporation rate, and other local factors. The ponds are to be dredged periodically to remove the accumulated sludge. 28. The experience of several years in the Malaysian palm oil indus- try shows that liquid effluents are amenable to biological treatment. The anaerobic treatment is done in two steps: in the first, called the acidifi- cation phase where despite the name, the pH increases fra 4.8 to 6.0 and the BOD drops to 6000 mg/L; in the methanogenic phase the pH goes first to 7.3 and then to 7.9. After this phase, the BOD falls below 200 mg/L. 29. This can be followed by aerobic oxidation where the BOD falls,be- low 100 mg/L and the pH reaches 8.5. If ponds are used, the total rdten- tion time for the effluent is between'55 and 60 days. 30. To prevent'deposition of hard sludge on the bottom of the methan- ogenic ponds, the liquor is desludged on sand beds and the cake used as fertilizer on the estate. 31. Ponds can be replaced by agitated tanks consuming more energy but allowing for the recovery of methane gas. Odors are not a nuisance if foam is kept on top of the methanogenic ponds. Effluent Limitations 32.. Limitations for liquid effluent frau palm oil pressing plants are shown below: pH 6 to 9 BOD below 100 mg/L COD below 1000 mg/L TSS below 500 mg/L BIBLIOGRAPHY 1. United Nations Industrial Development Organization "Technical and Eco- nomic Aspects of the Oil Palm Fruit Processing Industry," Sales No. E74.II-B.10. United Nations, New York (1974). 2. "The Oil Palm". Papers presented at Conference held in London, May 3-6, 1965. Ministry of Overseas Development-Tropical Products Insti- tite, London (1965). 302- 3. Turner, P.D., and R.A. Gillbanks, "Oil Palm Cultivation and Manage- ment." The Incorporated Society of Planters, Malaysia (1974). 4. Hartley, C.S.W., "The Oil Palm." Liongmans, Gram and Company, Ltd. London, (1967). 5. Ahmad, A.A.B., and F.L.C. Ming, "Palm Oil Processing Effluent Treat- ment -- Foreseeable Technological Problems." Malaysia Factories and Machinery Department, Doc. 628-54/634-614, Kuala Lumpur (1975). 6. Sinnappa, S. "Treatment Studies of Palm Oil Mill Waste Effluent." De- partment of Chemistry, Malaysia (1977). 7. U. S. Environmental Protection Agency. "Draft Development Document Effluent Limitation Guidelines and New Source Performance Standards for the Miscellaneous Foods and Beverages Point Source Categories". Prepared by Environmental Science and Engineering, Inc., Gainesville, Florida (February 1975). 8. BUKIT Kraiong Palm Oil Mill, Highlands and Lowlands BHD, the Enginoer- ing Department, Barlow Boustead Estates Agency SDN, BHD, Malaysia Bio- logical treatment of palm oil mill effluent by ponding, using a 2 phase anaerobic digestion and facultative oxidation. 9. Division of Environment, Ministry of Science, Technology and Environ- ment, Kuala Lumpur, Malaysia. Effluent standards for palm oil industry (1982). - 303 - THE WORLD BANK OClMBER 1982 OFICE OF ENIFCMTA AFFAIRS SAFETY AND OCCUPATIONAL HEALTH PESTICIDE MANUFACTURE 1. 'This guideline will address safety of personnel working in the plant as well as health hazards inside the plant. Plant Safety: 2. Tbxic organic chemicals and highly volatile solvents are used in the nanufacture of pesticides. Danger of fire and explosion is always pre- sent; accidents can happen if process conditioas change, leaks develcp or static electricity builds up on eq:ipnent, or storage vessels. 3. Major explosions followed by fire can occur at the plant as the following exaples show. A control thernaneter not in the liquid phase of a distillation vessel recorded erroneously low tenperatures and thus caused overheating. The reaction reached explosive speed, and the vessel blew up. No injuries were reported and the equipment damage was around US$300, 000. The instrumentation equipnant was then changed and the problemn disappeared. 4. Process conditions were changed in a distillation vessel to in- crease capacity. The reaction reached explosive velocity and the distilla- tion reactor blew up. This tine, on operatot was killed and damages anounted to US$500,000. Sweeping changes were made and the process con- ditions were brought back into a safer zene. The vessel was put in a con- crete bunker and provided with a high pressure diaphragm which will rupture before the vessel does. Alarns and trips were also added to forewarn the operators of changes and to shut off the process, if necessary, before the danger point is reached. 5. A ocpany was producing Malathion at a higher temperature than is normally accepted. At this high temperture, sane of the reagents were un- stable, and an explosion resulted. Seven operators were wounded and burn- ed-three died later on. The equigent damage amounted to US$800,000. Malathia production was then discontinued. 6. Toxic or dangerous materials in the form of gases, solids and liquids, are handled by erployees. Included are raw materials, in-process materials, finished products and effluents. Among the nost toxic gases are sulfur dioxide, chlorine and phosgene. The nost dangerous liquid (and to a certain extent vapor) is mercury. Every finished product, whether solid or liquid, is toxic to a certain degree. 7. In order to decrease ndnor accidents and avoid a serious one, standing orders for safety should be issued, and the Safety Officer should make sure these regulations are implemented. The Safety Department' s main duties should be: - 304 -. Fire protection and naintenance of fire-fighting equipnent. Accident prevention. Evaluation of hazardous, toxic and flamable materials. 8. Materials should be segregated in three classes, according to their flability: Class A - Flash point */ below 6.670C. Class B - Flash point between 6.67 and 21.10C. Class C - Flash point above 21. 1cC. 9. Toxic substances should also be divided into three classes according to their LD 50 **/ Class A - LD 50 less than 100 Class B - ID 50 between 100 and 800 Class C - LD 50 over 800 10. According to their class, materials should be stored in three areas; a) in the open-non-flamnable or low flarnable products or low toxicity, b) in closed warehouses-products of medium toxicity or flamnability.. c) in trenches or in buried storage tanks-products of high toxicity of flaurability. 11. Every employee should receive instructions in safety and accident prevention and be aware of the dangers involved in handling toxic pro- ducts. Prevention measures should b- backed up by fire-fighting and toxicity fighting measures and equipnent. The water fire loop should have a sufficient number of hydrants and should deliver a flow of at least 150 m3/h at a pressure of four to six kilos fran a tank cotaining at least 500 m3. In case of power failure, a generator connected to an emergency electrical pump should make the fire loop independent frn the outside power supply. Every operator should be trained in fire-fighting and first aid. Special teams should receive additional fire-fighting training. The conpany fire-fighting brigade should train with the town fire-fighting brigade on a regular basis. Besides the water fire loop, there should be portable fire extinguishers (chemical powder or CO2) distributed in the plant and inspected regularlarly. */ The flash point is the mininun temperture at which the vapor of a liquid will ignite under certain test conditions. */ Ib 50 represents the lethal dose for 50% of the test animals. Measured as 100 mg/kg of animal body weight will cause 50% of the test animals to die. The smaller the value for ILD 50 the more toxic the material (less material will cause 50% of the animals to die) . -305- 12. Each enployee should receive a gas nask. Air packs (portable breathing equinant with a reserve of air or oxygen) should be available in each unit. A doctor should be an duty and all cases of allergy or poison- ing reported to him. Special measures should be taken for mercury pollu- tion or any other toxicant. In sane units every employee should have urine and blood tests taken every six months to detect and cure any poisoning. 13. A record of lost time by accident should be kept. The record should also include frequency and severity indexes for- each accident. 14. The safety engineer should be well experienced and enthusiastic. Every piece of safety equinnt should be -in excellent condition. The safety engineer should supervise the fire chief and be assisted in his work by one or more safety technicians. Plant Surroundings: 15. Plant wastes can be classified as liquid effluents or gas pollu- tants. Liquid effluents contain raw materials and intermediate or finished products which, if toxic, can create serious safety and polluticn prob- lems. Mbst inportant are toxicant losses. The oxpany should avoid dis- charging in the environment any toxic waste effluent, regardless of its .biodegradability. 16. Several gas pollutants are released by the different- processes. Among the most inportant in a pesticide plant are sulfur dioxide, chlorine, hydrochloric acid and nrcaptans. These pollutants should be scrubbed be- fore being discharged into the atmosphere. BIBLIOGRAPHY 1. United Nations Development Prograrne. ".Environmental Operations Guide- lines", with Attachnents 1101 through 1106. Document G3300-1/TL., New York (28 May 1981). - 306 - THE WORLD BANK FEBRUARY 1983 OFFICE OF ENVIRONMENTAL AFFAIRS PESTICIDES GUIDELINES FOR USE 1. A pesticides component is now very often incorporated in Bank agricultural projects. As a consequence, this Office has received several requests for advice an the toxicity and the use of certain pesticides. 2. In some cases, the answer given was not complete because the name mentioned was a trade name unknown in the US. To prevent this, sponsors should be asked to supply the chemical name and the- common name generally used in the pesticides trade. For instance, if the sponsor decides to use RAVYCN, there is -o way here to identify the naterial. The sponsor should give the generally accepted commn name CARBARYL, the chemical name 1-naphtyl methyl carbamate, and if possible the chemical formula. 0 0-C-NHCH3 or even the US trade name. In this case SEVIN. Choice of Presticide 3. The criteria for choosing pesticides should be based on the fol- lawing factors: Biodegradability Toxicity to Manmals and Fish Risks of Application Price 4. Biodegradability should be the most important criteria as stable chemicals will accumulate, and this accumulation can be magnified into the food chain. This is why chlorinated hydrocarbons which are very stable, chemically speaking, should be avoided and why the US Ehvironmental Pro- tection Agency banned the following products: DDT, Aldrin Chlordane and Heptachlor. 5. Using these products in Bank projects should be avoided if at all possible. If they are absolutely required, the detailed reason should be given; price differential is not a sufficient reason. - 307 6. Depending on when the chemical is used and where it will end up, toxicity for naimals and/or fish should then be taken into account. 7. Tbxicity figures show the relative toxicity of the product to laboratory animals (white rats unless otherwise specified). LD50 is the dose that kills balf of the experimental animals in any test expressed in milligrams of the chemical per kilogram of animal weight. The higher the LD50 value, the lower the toxicity. Toxicity can be oral (mouth inges- tion), dermal (skin absorption), or inhalatin dusts. Special measures should be taken when bandling products with high dermal. toxicity. 8. Risks of application depend in part cn the toxicity but also on the physical properties of the material and the way it is applied. The product can be sold as a concentrate, a soluti on, an emulsifiable concen- trate, a wettable powder, or a dust. It is for instance safer to apply a solution on the ground than a dust, but it may not be always possible to do so. Aerial spraying is potentially the most damaging. 9. Price as an element of choice between two pesticides should only be considered after the other criteria have been decided. Application of Pesticides 10. . Even the safest among pesticides will probably involve some health risks. To avoid any serious accident, the appraisal mission should make sure that the people *ging to handle or be in contact with the product (dealers - foriulators - applicators - farmers) have been properly trained in its use and known about the hazards of handling it. The product should be shipped in adequate containers with labels, clearly identifiable, show- ing bcw to use it, how to avoid any problems, and bow to give first aid in case of an emergency. 11. The use of casual (migrant) workers for applying pesticides is widespread but should be avoided for the following reasons: These workers do not have the knowledge or the experience necessary for safe application and they will have a tendency to disregard the safety rules. 12. If these workers must be employed, they must be educated and trained, keeping in mind that their schooling is most of the time inade- quate or nonexistant. Secondly, they must work under experienced super- visors doing nothing but supervising the pesticide application. 13. Disposal of containers should not be overlooked. In 1967, 16 people died in Mexico from eating flour and sugar stored in Parathion drums. 14. Conmon transportation of pesticides and food in the same vehicle should be forbidden. In Colombia 63 people died and 165 became seriously ill from eating flour contaminated with Parathion during transport by truck. ANNEX 1 - Page 1 - 308 - From US EPA INSECTICIDES SUBSTITUTE FOR PRODUCT DDT Aldrin Dieldrin Chlordane Heptachlor Phorate o o o Demeton o lethyl parathion (% Parathion a o o o Guthion o Aldicarb o Azodrin o Diazionon o o o 0 Dimethoate o Fenthion o Methomyl o Crotoxyphos o Chlorpyrifos o o o a Bux o 0 o Carbofuran o o o a Counter o o o Dasanit o o 0 0 Disulfoton 6 o0 0 Dyfonate 0 o o o Landrin o o o Trichlorfon o o o o Dacthal o Aspon o a o o . Siduron o Ethion o o o o Propoxur 0 o o o o o Acephate o o o Methoxychlor 0 0 0 Endosulfan o o o o o May 1976 긔 310 - 15. For additional details see UNIDO's book ".Industrial Production and Fo=lation of Pesticides in Developing Countries" - 2 volumes - UN - New York, 1972. 16. Amex 1 contains the EPA tables which show equivalent acceptable substitutes for banned pesticides. 17. The following pesticides should not be used: DDT, Aldrin, Diel- drin, Chlordane, Hepdachlor, 2,4,5T (2,4,5 Trichlorophenoxyacetic Acid), EBDC (Ethylenebisdithiocarbamate). all rmrcury conpounds, all arsenic com- pounds, MIREX (Dechlorane). and DBCP (Dibromchloro Propane). 18. The product Phosvel (leptcphos) an organo phosphate made, but not sold in the United Stdats should also be banned for its long range ef- fects. Chronic neurological disorders,, paralysis,, and sometimes death are associated with this chemical believed to eat away myelin,, the sheathing around the nerves. The pesticide EDB (Ethylene Dibrcrnide) is a proven car- cinogen. 19. The following pesticides are suspect of long-range d=nic ef- fects and should be avoided: endrin, toxaphene,, strobane,, 1080,, strychnine, kepone,, lindane, ca&aium, DECP, BHC,, d-Imethoate, diallates, triallates, chlorobenzilate,, ethylene oxide,, EPN,, carbaiyl, aramite,, PCP,, creosote,, chloranil,, monourea,, benomyl, DDVP, chloroform, (SST) DFF, piperonyl butox- ide, rotenone, perthane, safrole, promide and inerphos. 20. The use of DBCP and EDB should be restricted. to cases where no substitutes exist for the considered application. The use of MIPMC should be restricted to compounds where it is mixed with products enhancing its photodegradability. 21. In view of the added potential damages to the environment and of the Bank's official policy favoring "Intermediate Technologies ", aerial spraying of pesticides should be discouraged whenever it can be replaced by ground spraying - 22. Ultra low volume application (ULV) ULV techniques with quanti- ties habitually below 5 liters per hectare are ncw well proven and should be promoted in Bank projects either for aerial or ground spraying. Tb be effective this technique requires proven equipmnt,, strict control of the spray drcplets diameter (usually in the order of 30 um), and experienced supervision to take into account the weather conditions. The main pesti- cides nanufacturers will supply teennical bulletins or. ULV and also trained supervisors. ADDENDUM 1. The pesticide MIREX (Dechlorane) has been forbidden by the EPP. and the same Organization has suspended the use of the pesticide DBCP (Dibro- mochloro, Propane) 기 312 THE WORLD BANK OCTOBER 1980 OFFICE OF MY AFFAIRS ryTimEm RZFnMG The petroleum. Industry is a compl" combination Of inter-dependent operations, which-can be divided Into three major divistops: productiong re- fining, and marketing. This document.will be concerned only with refining, and thus cover only those operations necessary to convert the crude oil into consumer products, prior to marketing.- REFINERY PROCESSING 2. The production of consumer products from crude oil involves several separate processes which are fundamental to refinery operations. Each of these produces- wastes that are identifiable and must be disposed of under controlled conditions to avoid environmental damages. The principal processes are discussed below, 3. Crude and product storase Crude oil is stored in order to provide constant*supplies of feedstocks for primary fractionation runs of ec*nomical duration, Intermediate products are stored to equalAze flows within the re- finery. Finished products are stored to-await shipment, for mixing and blend- ing on or off'the premises, and to lessen the effects of changes in product de- mands. Storage is prov ded in steel tanks, permitting sufficient detention for settling of water and suspended solids. The settled water layers are drawn off periodically. 4. Crude desaltinz, This removes inorganic salts and some of the sus- pended solids from the crude oilt. in order to minimIze mechanical plugging and, corrosion in procese,equipment. Salts are separated by water washing in the presence of chem1cals-specific.to the type of salts present and,the characterfs- tics of tho'crude oll. 5. Crude oil fractionation. This is the basic refining process, by which crude petroleum is separated into intermediate fractions of specified boiling point ranges. Topping (sometimes called prefractionation or skimming) is the first step in the process, and serves to separate the economical quantities of the very light distillates from the-crude oil. 6. Cracking. Thermal cracking breaks down heavy oil fractions into lower molecular weight fractions, such as heating oils. Catalytic cracking also .breaks down heavy fractions into lower molecular weight fractions but utilizes a catalyst and runs at lower temperatures and pressures than in thermal cracking. Hydrocracking converts hydrocarbon feedstocks (including distillates, gas oils, and'residues) into gasoline, high-quality middle distillates, LPG, or low-sulfur residual fuel. HydrocrackIng consists basically of catalytic cracking in the presence of hydrogen. - 313 - 7. Hydrocarbon processing. Several operations are included in this category. Polymerization converts olefin feedstocks into higher-octane polymer gasoline, propane and butane. Alkylation converts normally gaseous hydrocarbons into high octane alkylates for use as gasoline blending compon- ents. Isomerization is also used for converting light gasoline stocks into higher-octane isomers to produce higher octane motor fuel, as well as to convert isobutane from normal butane for use as fuel-stock in the alkylation process. Reforming converts low octane naphtha, heavy gasoline, and naphthene- rich stocks to high octane gasoline blending stock. 8. Solvent refining. Used primarily to obtain lube oil fractions or aromatics from feedstocks containing mixtures of hydrocarbons and undesirable materials such as unstable acidic, sulfur, organomtallic, napthenic, and/or nitrogen compounds. Refined oils, high-octane blending components, and high- purity aromatics are produced. Dewazing which is also a solvent process, is used to remove wax from lube oil stocks to produce lubricants with low pour points and to recover wax for further processing. 9. Hydrotreating. Saturates olefins and removes sulfur, nitrogen, and oxygen compounds and other contaminants from either straight run or cracked petroleum fractions to produce materials having low sulfur, nitrogen, and olefin contents and improved stability. The process occurs in the presence of hydrogen. 10. Grease manufacture. Blends various alkali earth metal hydroxides and fatty acids for soap manufacture with lube oils, wazes and other materials to produce lubricating greases. 11. Deasphalting. Separates asphalts or resins from viscous hydrocar- bon fractions, segregates heavy or medium neutral fractions by propdne extrac- tion, and/or removes paraffinic catalytic cracking stock from distillation residues. The resulting products are deasphalted or decarbonized oil, asphalt, and heavy fuel blending stocks. 12. Wax manufacture. Takes high-oil-content wax fractions directly from crude factionation and/or waxes from dewazing of lube oils and converts them to paraffin and microocrystalline waxes of low-oil-content, high melting point, and other characteristics required for high-quality waxes. 13. Product finishing. Drying and sweetening are used to remove_sulfur compounds, including hydrogen sulfide and mercaptans, and to improve color, odor, oxidation stability, and inhibitor response to produce materials suit- able for blending, shipping or further processing. Lubricating oil finishing takes petroleum fractions that have been solvent extracted and dewaxed, and converts them to finished. lube oils ready for blending and ccmpounding. Blending and packaging are the final steps in preparation of the petroleum products which muat meet those specifications required by industries, retailers, and consmers. - 314 - 14. Hydrogen production. Produces the hydrogen needed for refining operations, such as hydrotreating and hydrocracking, and for petrochemical feedxtocks. The piimary r materials are natural gas; refinery gas, propane, ..butanes and others. 15. General Utilities. Certain utility facilities, such as supplies of steam and cooling water, generally serve several processes. Boiler feed water is prepared and.steam generated at a single location. -Non-contact steam, used for surface heating, is circulated through a closed loop, from which needed quantities are made available for specific process.purposes. The condensate is. recycled to the boiler house, with a certain portion being discharged as blowdown. Steam is used principally for: non-contact process heating; power generation in turbines, compressors, and process pumps; and as a diluent, strip- ping-madium, or vacuum source with steam jet ejectors. 16. A petroleum refinery consists of a complex combination of inter- dependent operations concerned with separation of crude molecular constitu- ents, molecular cracking, molecular rebuilding, and solvent finishing. Only the major processes have been identified above, since the intermediate and finished products are too numerous and too variable in coposition to covr in this document. Not -all of these operations are necessarily caried out ,t one refinery. The products of one or more of these operations are frequently transferred to other plants. for further processing into markatable commodities. -- SOURCES AND CHARACTERISTICS OF WASTES 17. The principal environmental problems in oil refinery operations are due to both enissions and effluents. Gaseous Emissions 18. The air pollutants emitted by refineries are affected by crude oil capacity, air pollution control measures being utilized, general level of main- tenance and hosuekeeping, and the specific processes being carried out. Table 1 presents the principal potential sources of various contaminants. 19. 0 Sulfur oxides, nitrogen oxides, hydrocarbons, carbon monoxide,and odor.are the emissions of greatest concern. Particulates, aldehydes, amonia, - and organic acids may also be present but are usually of lesser importance. Liquid Wastes 20. Refineries vary in complexity from small installations employing perhaps single atmospheric fractionation, to the, very large integrated facili- ties producing a broad spectrum of petroleum and petrochemical commodities from a wide variety of feedstocks. Basic refinery operations may be grouped into five categories on the basis of the effects on raw waste water loadings. - 315 Table 1. Potential Sources of Oil Refinery Enissions a/ jission PrIncipal Potential Sources Sulfur Oxides Boilers, process haters, catalytic cracking unit regenerators, H2S flares, decoking operations. Hydrocarbons Storage tanks, wastewater separators, catalyst regenerators, pumps and valves, cooling towers, volatile hydrocarbon handling equipment, process heaters, compressor engines. Nitrogen Ozides Process heaters, compressor engines, catalyst regenerators, flares. Particulate Matter Regenerators, boilers, decoking, incinerators. Lldehydes Catalyst regenerators Ammonia Catalyst regenerators Odors Treating units, drains, tank vents, wastewater separators Carbon Monoxide Catalyst regenerators, decoking, compressor engines, incinerators / See Raf. 1. 21. The categories used are patterned after the American Petroleum Institute (API) classification system. These categories and the rafinery operations included in each are as follows: - Topping: Topping, catalytic reforming, asphalt production, or lube oil manufacturing, but no cracking or thermal operations. - 316 - - Cracking: Topping and cracking - Petrochemicals: Topping, cracking and petrochemicals operations (first generation and isomeriza- - . tion products or second generation products). - Lube: Topping, cracking and inhe oil manufactur- ing processes. - Itegrated: Topping, cracking, lube oil maufacturing processes, and petrochemicals operations. 22. The pollution parameters of major significance in this industry are as follows: - 5-day Biochemical Oxygen Demand (30D5) - Chemical Oxygen Demand (COD) - Total Organic Carbon (TOC) -- Total Suspended Solids (TSS) - Oils and Greases (O/G) -- Phenolic Compounds - Ammonia Nitrogen (NE3-N) - Sulfides - Total Chromiun (Tot.Cr.) - Heavalent Chromium (Cr+) - Hydrogen Ion Concentration (pR) 23. The waste water flows and characteristics of refinery effluents can vary considerably according to the type of operations. Table 2 lists the median (50% of occurrences less than or equal to the values shown) raw waste flows and loadings, representing the oil separator effluents for each of the processing categories cited above. In general, all wastewaters from process- ing units discharge to large basins or ponds (API separators) which function as oil and water separators. The oil is usually recovered as a valuable by- product. Rexavalent chromium is present in r±Inery effluents, due to the addition of chromates to cooling waters in order to inhibit corrosion. ... . . . . . . . . . - 317 - . Table 2. Mad-ian Waste Flows and Loadings for Petroleum Refinery Operations, Following Oil/Water Separation. -a/ Process Category Paramster Topping Cracking Patro- Lube Inte- ChJ. grated. Net xg per 1000 z3 of Peedstock b/ 30D5 3.4 73 172 217 197 COD 37. 217 463 543 329 TOC 8.0 41 149 109 139 TSS 12. 18 49 72 58 O/G 8.3 31 53 120 75 PhenOls . 0.03 4.0 7.7 8.3 3.8 NE3- N 1.2 28 34 24 20 Sulfides 0.05 0.94 0.86 0.01 2.0 Tot. CR 0.01 0.25 0.23 0.05 0.49 Cr+ 0.007 0.15 0.13 0.02 0.30 flow C 67 93 109 117 235 / Prom EPA Doe. 44011-74-014a. b/ Feedstock a Crude oil and/or naturil gas liquids throughput. / As m3 per 1000 a3 of feedstock. EFFLUT LIMITATIONS Gaseous Emissions 24. Limitations for gaseous emissions from specific refinery processing .. . . . . . . . . . . - 318 -.. operations are given in Table 3. For processing operations not covered in these limitations, acceptable ambient air quality standards applicable to the specific pollutant are to be applied. Table 3. Performance Limitations for Petroleum Refinerr Emissions Parameter Source mitations Sulfur Fuel gas combustion Shall not burn any gas contain- Oxides davices ing over 230 mg H2S per dry m3 at standard conditions Sulfur Oxides Sulfur recovery Not over 0.025% SO2 by volum at plant zero oxygen on a dry basis,with reduction control system and incineration Not over 0.030% sulfur compounds and 0.0010% H2S by volume at zero oxygen on a dry basis, with reduction control system but no incineration Hydrocarbons Storage vessels with No discharge to atmosphere. capacity of over Equip with floating roof and vapor. 150 Mg (40,000 recovery system if true vapor Gallons) pressure is 10.4 to 76. kPa Equip with vapor recovery system if true vapor pressure is over 76 kPa Particulate Catalyst regenerator Not over 1 kg/1000 Kg coke burnoff Matter Carbon Catalyst regenerator Not over 0.050% by volume Monoxide Opacity a/ All emissions Not over 30% except for 3 minutes in any 1 hour a/. "Opacity" is the degree to which emissions reduce the transmission of light and obscure the view of an object in the background. * 1. magagram = 1 metric ton, 1 a Hg - 133.3 Pa Mg = segagra,. 1*a = kilo Pascal - - -.. ..* . *.. . . .. ... . - 319 -. Liquid Effluents 25. Table 4 presents the permissible mazinim daily discharge of various pollutants in patroleum refinery effluents. These limitations are based on --the application of best demonstrated end-of-pipe technology currently avail- able, the use of API (or equivalent)oil and water separators in the plant, segregation of non-contact wasta waters from process waste waters, and effc- tive in-plant process control and housekeeping measures. ConOL AND TREANT OF WASTES 26. The gaseous emissions and the liquid effluents are of equal import- ance in the refinery operations ani the discharges must be controlled in order to avoid environmental damage. A combination of process control, in-plant housekeeping, and treatment technology can usually be effective in achieving reduction of these discharges to acceptable levels. Gaseous Effluents 27. .It is difficult to categorize emission sources on the basis of re- finery operations, since many of them are common throughout the plant. For purposes of emissions control the refinery should be considered as an inte- grated systems of storage facilities, process heaters, cooling equipment, pamps, valves and other units and operations. 28. Hydrocarbon emissions originate principally from storage facilities, valves, pumps, compressors, waste water separators, and loading facilities. These emissions can, in most instances be collected by vapor recovery systems or ventilating systems and eliminated by burning. Disposal is most frequently through elevated flares, using steam ejection. Flares aist be so located as to avoid proximity to combustible materials, tanks and processing equipment. 29. Other measures for reducing emission discharges include high affi- ciency dust removal equipment on catalytic cracking units, waste heat boilers on catalyst regenerators, smokeless flares, and sulfu= recovery systems. Im- proved housekeeping, coupled with maintenance and employee education can also contribute significantly. Liquid Effluents 30. Technology for control and reduction of effluent loadings falls in- to three categorias: in-plant control, at source pretreatent, and end-of-pipe technology. 31. Two types of in-plant measures can greatly reduce the volume of final effluents. The first of these utilizes the .reuse of water from one pro- cess to another, such as using blowdowns from higher pressure boilers as feed to low pressure boilers or using treated effluent as makeup water whenever possible. The second approach is to utilize recycle systems that use water more than once for the same purpose, such as using steam condensate as boiler feed water or using cooling towers. Table 4. Liquid Effluent Limitations for Petroleum Refinery Wastes. Maximum Daily .ischarge - Kg per 1000 m3 of Feadstock a b Processau Category BOD5 COD TOC TSS 0/0 PHEN. N13-N SUL- TOTAL CR+6 FIDES CR Topping 6.3 32 8.2. 4.0 1.9 0.04 1.3 0.04 0.10 0.002 Cracking 8.7 61 11. 5.8 2.6 0.06 8.6 0.05 0.14 0.002 Petrochemicals 12 69 15. 7.7 3.5 0.08 11 0.06 0.19 0.003 . Lube 18 126 24. 12. 5.6 0.12 11 0.10 0.31 0.005 . Integrated 22 152 29. 14. 6.7 0.14 11 0.12 0.37 0.006 Runoff c/ 0.03 0.19 0.03 0.02 0.01 -- -- -- - - 0 Ballast d/ 0.03 0.24 0.03 0.02 0.01 -- -- - -- - a/ Feedatock - Crude oil and/or natural gas liquids throughput. b/ For all effluents p1t - 6 to 9. c/ Applies only to process area runoff treated in main treatment system. All runoff from tank fields and non-process areas shall not exceed 35 mg/1 of TOC or 15 mg/1 of 0/C when discharged. dl Applies only to ballast waters treated at refinery. -.. - 321 -.. 32. Good housekeeping will further reduce waste flows. Examples are minimizing waste when sampling product lines, using vacuum trucks or dry cleaning methods to clean up oil spills, applying effective maintenance and -Aspection in order to keep .tha refinery equipment as leakproof as possible, and providing individual disposal for waste streams (such as spent cleaning solutions) having special characteristics. 33. Process modification, in most cases applicable to both existing and new installations, could include: - - Substitution of improved catalysts having longer life and requiring less regeneration. - eplacement of barometric condensers with surface con- densers or air fan coolers to reduce a major oil-water emulsion source. * Subesitucon of air fan coolers for water cooling to re- . duca blowdown discharges. - Installation of hydrocracking and hydratreating processes designed to generate the lowest possible waste loadings. - Provision of automatic monitoring equipment, such as for TOC, to assure early detection of process upsets and avoiding exceasive discharges to severs. - aximum use of improved drying, sweetening, and finishing procedures to minimize volumes of spent caustics, filter solids and other materials requiring disposal. 34. Major at-source pretreatment measures include stripping of sour waters, neutralization and oxidation of spent caustics, ballast water separa- tion, and slop oil recovery. Gravity separators remove the major portion of the free oil found In refinery waste waters. Most of these oils can be re- processed, and hence the separtor is considered an integral part of the re- finety operation. 35. End-of-pipe control technology relies most heavily on a combina- tion of flow equalization and biological treatment methods. Equalization, which elimnates surges in flows and loadings, is particularly important for a biological treatment system since, for eample, sudden discharges con- taining high concentrations of certain materials can upset or completely kill - the organisms in the system. 36. Among the biological techniques most commonly applied are dissolved air flotation, oxidation ponds, aerated lagoons, trickling filters, activated sludge, physical-chemical methods, granular media filters, and activated car- bon. These may be applied singly or in combination, depending upon the volume and characteristics of the wastes to be treated, availability of land areas and other factors. .. . . .. - 322- - 37. The most frequently used methods for disposal of chromium bearing wastes are by reduction of the hexavalent to the trivalent form (with sulfur dioxide, sulfites, ferrous sulfate, or other reducing Agents), followed by neutralization and precipitation of the reduced chromium with alkali. 38. Sludges produced from biological treatment may be disposed of by land-filling, land farming or incineration. B7LIOGRAPHT 1. Jones, Harold R. "Pollution Control in the Petroleum Industry". Noyes 'Data Corporation. Park Ridge, N. J. and London (1973). 2. Powers, Philip W. "How to Dispose of Toxic Substances and Industrial Wastes". Noyes Data Corporation. Park Ridge, N. J. and London (1976). 3. U. S.* Environmental Protection Agency. "Development.Document for Effluent Limitations Guidelines and New Source Performance Standards for the Petroleum Refining Point Source Category". Doc. EPA-440/1-74-014-a (April 1974). 4. UN Environment Programme "Seminar on Environmental Conservation in the Petroleum Industry - 29 March to 1 April, 1977". Doc. UNEM/lss.5/10 (Final). United Nations. New Tork (June 10, 1977). 5. U. S. Federal Register, US Government Printing Office, Washington, as follows: (a) Vol. 39 (39FR9308), March 8, 1974 (b) Vol. 40 (40FR46250), October 6, 1975 (c) Vol. 41 (41FR36600), August 30, 1976 (d) Vol. 41 (41FR43866), October 4, 1976 (e) Vol. 43 (43MR10866), March 15, 1978 (f) Vol. 43 (43F21616), May 18, 1978 - 323 - TE WORLD BANK OCTOBER 1980 OFFICE OF ENVIRONMENTAL AFFAIS PLATING AND ELECTROPLATING,. FLUET GUIDELINES Process Description 1. Electroplating applies a surface coating by electrodeposition on a metal surface. Copper, nickel, chromium, zinc, tin, lead, cadmium, iron aluminum or combinations thereof can be used as coating. Precious metals as gold, silver, palladium, platinum, rhodium or combinations can also be used as. coating. Chemical plating on metals or plastics can also be done and gene- rally a plant. applies both processes. 2. A plating line is a sequence of ,tanks in which one or more coatings are applied. It may be broken down in 3 steps; preparation of the surface for coating, application of the coating and finally post treatment. 3. The pretreatment. involves cleaning, descaling and degreasing. CIeaning C.amoves oil, grease and dirt; it can be done by solvents, alkalis, emulsions, ultrasounds or acids. Salt bath descaling is used to get rid of hard to remove oxides from stainless steels or other alloys. A typical electroplating pretreat- ment is shown in Annex 1 and a typical chemical plating pretreatment in Annex 2. Wastes Characteristics 4. Annez 3 shows the pollutants occurrence in the U. S. plating industry in general and per section (common metals - precious metals - chemical plating - anodizing - coating - milling and etching - printed circuit boards). 5. All the pollutants mentioned in Annex 3 are commonly present in significant amounts and require some control in the effluent discharge. This conttol can be achieved by currently available technology. Waste Removal Reduction of Hexavalent Chromium 6. Because of its high toxicity hexavalent chromium has to be reduced to the trivalent state. This is done with any reducing agent but SO2 is most safonly used at a pH between 2 and 3. The reaction will take two to three houT and sulfuric acid may have to be added to keep the right pH. Oxidation of Cyanides 7. Any oxidation agent will do the job. Chlorine, hypochorites and hydrogen peroxide are the most commonly used but oxygen in air is also effective if there is room for an aerated pond. Cyanates being much less toxic than - 324 - cyanides, there is no need to go to complete oxidation to nitrogen as long as all the cyanides have disappeared. Metals Removal 8. This is done by pH adjustment. Lime addition to the waste water will increase the pH and promote precipitation of metal hydroxides. The maximu precipitation corresponds to a wall defined pH changing for each metal. The luxlym solubility for Cr is 0.012 mg/L at pH 8.5. ..Below and above this pf the solubilityincreases. At pH 10.5, nickel solubility is 0.001 mg/L but at the sme 10.5 chromium solubility is back up to 1 mg/L. The precipitation of metal hydroxides may consequently have to be done-in several stages. 9. The solubility figures given above are for pure solutions of the metal. Other factors can increase or decrease the solubility, among them, temperature, other salts concentration, common ions, etc. 10. In industrial practice, the precipitation of metal hydroxides is promoted by adding inorganic coagulants or polyelectrolytes flocculants in a clarification tank or pond or both. 11. The sludge collected from clarification is first dewatared and then either buried in a landfill, incinerated or hauled away. Results of Treatment 12. Although there are more sophisticated treatments that can replace or be added to the operations described, these can achieve the following results for the main pollutants: Pollutant Residual (mRiT-) Copper 0.5 Nickel 0.03 Cr Total 0.1 Cr exavalent 0.01 Zinc 1.2 Cyanide 0.01 Cadmium 0 . 02 Lead 0.03 13. These figures should be considered as World Bank guidelines for the plating industry not forgetting that effluent pH should always be between 6 and 9. Costs of Treatment 14. Anna 4, 5 and 6 taken from the EPA publication Electroplating (see bibliography) gives the investment ana operating costs for clarification, chromium reduction, and cyanide oxidation. * mg/L - milligran per liter - 325 - BI3LIOGRAPET For more information consult EPA 440/1-78/085 - Electroplating. Point source category. Publisher: United States Envirozzantal Protection Agency - February, 1978. ANNEX I PARTS A SOLVENT ALKALINE Hc1 DEGREASE CLEAN RINSE CLEAN RINSE (SOAK) ANODIC AOI ALAINE- RINSE HCL CLEAN RINSE NLKADINE CLEAN CLEAN ELECTROPLATE RINSE ACID DIP HRINSE . a FIGURE 3-7 TYPICAL ELECTROPLATING PRETREATMENT SEQUENCE ANNEX II . * PARTS VAPOR . ALKALINE COLD RINSE ACID DEGREASE CLEAN CLEAN * ~ ALKALINE* COLD RINSE ALEAN COLD RINSE ACID CLEAN .CLEAN NICKEL STRIKE TO ELECTROLESS PLATING HOT RINSE (ELECTROPLATE) RINSE FIGURE 3-9 TYPICAL ELECTROLESS PLATING ON METALS*PRETREATMENT SEQUENCE . -ANNEX III POLLUTANT PARAMETER OCCURENCE SUBPAR Pollutant . Parameter Common Metali Precious Electroless Chemical .Printed Plating a eetals ltins Anodizing Coatings Hilling - Circuit Plating Plating Etching Boards Copper 0.032-272.5 0.002-47.90 0.206-272.5 1.582-535.7 Nickel 0.019-2954 0.028-46.80 0.027-8.440 Chromium, Total 0.088-525.9 . 0.268-79.20 0.190-79.20 0.088-525.9. 0.005-38.52 Chromi n, lexavalent 0.005-334.5 0.0055.000 0.005-5.000 0.605-334.5 0.004-3.543 zinc 0.112-252.0 0.138-200.0 0.112-200.0 I Cyanide, Total 0.005-150.0 0.005-9.970' 0.005-12.00 0.005-78.00 0.005-126.0 0.005-126.0 0.002-5.333 Cyanide,00 Cyanide, 0.003-130.0 0.003-8.420 0.05- 1.00 0.004-67.56 0.004-67.56 0.005-101.3 0.005-4.645 Amenable Fluoride 0.022-141.7 0.110-18.00 0.022-141.7 0.648-680.0 Cadmium 0.007-21.60 Lead 0.663-25.39 0.044-9.701 Iron 0.410-1482 0.410-168.0 0.075-263.0 Tin 0.060-103.4 0.102-6.569 0.008-103.4 Phosphorus 0.020-144.0 0.020-144.0 0.030-109.0 0.176-33.00 0.060-53.30 0.060-144.0 0.075-33.80 rotal Suspended Solids .1-9970 .1-9970 .1-39.00 36.1-924.0 19.1-5275 .1-4340 1.0-408.7 Silver 0.050-176.4 0.036-0.202 Gold 0.013-24.89 0.007-0.190 Palladium 0.038-2.207 , 0.008-0.097 Platinum 0.112-6.457 Rhodium* 0.034 - *Only 1 plant had a measurable level of this pollutant - 329 - CLARIFICATION-CONTINUOUS TREATMENT SETLlNG TANX Flow Rate (Liters/Er) 37,850 75,700 157,708 Investment 571,363 $91,575 $130,102 Annual Costs: . Capital Costs 4,552 5,842 8,301 Depreciation 14,273 18,315 26,020 Operation & Maintenance Costs (Excluding Energy & Power Costs) 2,506 2,565 3,851 Energy & Power Costs 36 72 150 Total Annual Cost $21,367 $26,794 S 38,322 TABLE 8-7 CLARIFICATION-BATCH TREATMENT SET LING TANX Flow Rate (Liters/Er) 1,893 3,785 18,925 Investment S25,551 S28, 529 $38,032 Annual Costs: Capital Costs 1, 63 0 1,820 2,427 Depreciation S,110 5,706 7,606 operation & Maintenance Costs (Excluding Energy & Power Costs) 2,334 2,341 2,394 Energy & Power Costs 41 81 811 Total Annual Cost S 9,155 S 9,948 S13,238 - 330 - ANNE V CHROMIUM REDUCTION * CONT1UOUS TREATMENT Flow Rate (Liters/Br) 3,785 7,570 18,925 Investment $20,416 $21,538 $24,003 Annual Costs: Capital Costs 1,303 1,374 1,531 Depreciation 4,083 4,308 4,801 Operation S Maintenance Costs (Excluding Energy & Power Costs) 1,086 1,375 2,089 Ehergy & Power Costs 256 256 256 Total Annual Cost S 6,728 S 7,313 S 8,677 TABLE 8-9 CBROMIUM REDUCTION - BATCE TREATMENT Flow Rate (liters/Br) 189 379 1,893 Investment SS,493 S9,535 S14,405 Annual Costs: Capital Costs 541 608 919 Depreciation 1,699 1,907 2,881 Operation S Maintenance Costs (Excluding Energy & Power Costs) 155 295 1,415 Energy & Power Costs 256 256 256 Total Annual Cost $2,651 S3,066 S 5,471 -331 - CYANIDE OXIDATION - CONTINUOUS TREATMENT Flow Rate (Liters/E) 3,785 5,678 7,570 Investment $47,808 $51,875 $55,556 Annual Costs: Capital Costs 3,050 3,310 3,544 Depreciation 9,561 10,395 11,11 Operation & Maintenance Costs (Excluding Energy & Power Costs) 2,218 2,750 3,563 Energy & Power Costs 90 135 180 Total Annual Cost $14,920 $16,570 $18,098 TABLE 8-11. CYANIDE OXIDATION - BATCE TREATMENT. Flow Rate (Liters/Hr) 189 757 1,893 Investment $10,325 513,258 $17,069 Annual Costs: Capital Costs 659 846 1,089 Depreciation 2,065 2,652 3,414 Operation & Maintenance Costs (Excluding Energy & Power Costs) 464 1,854 4,636 Energy & Power Costs 5 18 45 Total Annual Cost S 3,192 S 5,370 S 9,184 - 332 - THE WORLD BANK FEBRUARY 1982 OFFICE OF ENVIRONMINTAL AFFAIRS PLIWOOD MANUFACTURING ENVIROCMETIAL GUIDELINES 1. Plywood consists of several layers of wood (6r veneer) joined to- gether by means of an adhes.ive. The material has many uses. It can be designed and engineered for both construction and decorative purposes, and in various shapes (flat, curved, or bent). Hardwood plywood is generally used for decorative purposes and has a facing layer of wood from deciduous or broad leaf trees. Softwood plywood is generally -used for construction and structural purposes, with the facing layers being from coniferous or needle-bearing trees. MANUFACTURING PROCESS 2. The operations required for converting logs into veneer and then into plywood are nainly mechanical. The process flow diagram for a typical veneer and plywood mill is presented in Figure 1. 3. Logs are delivered to the plant either with or without the bark, and cut to proper lengths. Where barking is required the hark is renoved by any one of several wet or dry processes. The machines most comonly used include drum, ring, bag, hydraulic, and cutterhead barkers. 4. The nost important operation in the process is the cutting of the veneer, since the appearance of a plywood panel is greatly dependent upon the nanner in which the wood layers are prepared. Prior to cutting, the log is heated or "conditioned" to improve the cutting properties, particu- larly in the case of hardwoods. When conditioning occurs prior to debark- ing then bark, renoval is greatly facilitated. With the increasing use of ring and cutterhead barkers, whose cperations are not aided by prior beat- ing, the conditioning more comnonly occurs between the barking and veneer- ing operations. 5. Twe basic methods are used to beat the logs: (a) directing steam onto the logs in a steam vat (or steam tunnel) or (b) heating the logs in a vat full of hot water, in turn beated either directly by live steam or in- directly by steam coils. 6. The cutting of veneers may be accomp).ished by (a) rotary cutting, (b) slicing, (c) stay log cutting, or (d) sawn veneering. Rotary cutting is the nost widely used method at the present time. In this method a log or ("bolt") of wood is centered and turned on a lathe against a )nife ex- tending across the length of the unit. A thin sheet of veneer is peeled from the log as it turns. Log lengths will vary from about 0.6 to 2.4 m, although lengths of up to nearly 5 m are not uncomn. Rotary cut veneers generally vary from 1.3 to 3.6 mm in thickness. LIQUID WASTE . "GREEN END" STEAM DRIER WASH OVERFLOW FROM CONDENSATE AND DELUGE I EXHAUST LOG POND WATER :GASES LOG STORAGE (LOG POND LOG LOG VENEER VENEER GLUE WASH COLD DECK DEBARKING STEAMING LATHE DRIER "WATER OR 80TH)Hr . . GLUE GASES PREPARATION SOLIDS Lo BARK GLUE RECYCLE LIQUIDS VENEER GLUE RESSIN FINISHING PREPARATION LINE I Ir I II* . I UNUSABLE I TRIM AND I I VENEER AND I SANDER I TRIMMINGS I DUST I II SOLID WASTE IS BURNED IN BOILER CHIPPED FOR REUSE OR SOLD Figure 1 - Process Flow Diagram for Veneer and Plywood Production. (From EPA Publication EPA-440/1-74-023-a) - 334 - 7. Freshly cut veneers are usually dried to a moisture content of less than 10 percent since, if not dried, they would be unsuitable for glueing. In addition, the undried materials are also susceptible to attack by molds, bluestain and wood-destroying fungi, Several drying methods are in use, the most comnra being a long chamber, equipped with fans and heat- ing coils, through which the sheets are transported under controlled temp- eratures and humidity conditions. 8. . Following the drying operatin the stock is prepared for glue- ing. Preparation includes grading and matching, redrying, dry-clipping, jointing, taping and slicing, and inspection. Except for jointing and splicing, which generally requires an adhesive, these steps are completely mechanical. 9. Adhesives may be divided into three principal categories: (a) Protein-contains various combinations of water, dried blood, soya flour, lime, sodium silicate, caustic soda, and formaldehyde. (b) Urea-formaldehyde resin-contains various com- binations of water, defoamer, wheat flour, and (c) Phenol-formaldehyde-contains various combina- tions of water, furafil, wheat flour, phonolic formaldehyde resin, caustic soda, and soda ash. 10. The phenol-formaldehyde mixture is used almost exclusively for exclusively for exterior applications, while the other two are used chiefly for interior applications. Current information indicates that urea-base glues. are the most widely used. 11. Most plants mix their own glues.. Applicaticn to the veneers is usu- ally by means of power driven rollers which spread the adhesive on the sheets. More recently sprays and curtain-coaters have been coming into wider usage. After glueing, the sheets are subjected to pressure of up to 17 or 18 atmospheres, to insure proper alignment and full contact between the glue and wood layers. 12. Following the pressing, a series of finishing steps are applied, depending upon the plant and the final product desired. Such steps include (a) redrying, (b) trimming, (c) sanding, (d) coating, (e) sorting, (f) molding, and (g) storing. WASTE SOURCES AND CHARACTERISTICS 13. Veneer and plywood production operations will produce wastes of a gaseous, liquid, and solid nature. - 335 - Gaseous Enissions- 14. Formaldehyde is the principal conponent of concern in the glues which are nost widely used today. There is little free formaldehyde in the resin mixtures. The high cure terperatures used will generally volatilize any residual free formaldehyde. 15. Volatile organic com7pounds may be emitted by evaporaticn of or- ganic solvents used in conventional coatings currently applied. Coatings are used primarily at hardwood plywood plants but, in nost cases, only a small percentage of the total production is coated. Liquid Effluents 16. The parameters of major significance in the production of veneers and plywood are 5-day biochemical oxygen demand (BODS) and total suspended solids (TSS). Other pollutants may be present but are considered to be of minor significance. The processing method, raw materials used,. and the chemicals added are the principal considerations in identifying the import- ant parameters. 17. In the log barking operation BOD5 and TSS are both of concern. The TSS concentrations from drum barkers are slightly higher than for hy- draulic barkers, but the BOD5 values are significantly higher in the drum barker. The higher values are due to the longer contact time between the bark and the water, as well as because of the grinding acticn Aich occurs in the water. BOD5 values are also affected by the species of wood barked and by the time of the year in wtch the log is cut. Drum barking waters are often recycled. The ranges of BOD5 and TSS values in log barking waters are as follows: BOD5 TSS Hydraulic 56-250 520-2360 Drm 48-990 2020-2880 18. As previously stated, log conditioning is accomplished either by steam vats (or tunnel systems) or by hot water vats. The only waste water from the steam vats is the steam condensate, which carries with it leach- ates fram the . logs and wood particles. The magnitude of flows will vary with the number and size of the vats. Typical values for wastewaters from steam vats are as follcws: Waste Volume: 1.6-3.1 L/sec. 1/ BOD5: 470-3100 mg/L TSS: 74-2940 mg/L pH: 4-6 Units 1/ For a plant with annual producticn of 9.31 million Sq. M. Plywood, 9.53 m thick. - 336 - 19. Hot water vats, because of the method of heating (steam, beating coils, etc) do not have a constant discharge, and are generally emptied only periodically. The water and solids that build up in the closed system are replaced with clean water. In many cases the wastewater is settled and then recyled back into the vats. The characteristics of these waters vary widely, as indicated by the following typical analysis: BOD5: 330-4700mg/L TSS : 70-2500 mg/L PH : 4.4-6.9 Units 20. Veneer dryers accumulate wood particles, which are renoved either by flushing with water or blowing out with air. Volatile hydrocar- bons will also ccndense cn the surface of the dryers to form an organic deposit called "pitch". It is necessary to remove these deposits period- ically, in order to avoid excessive buildup. A high pH detergent is ap- plied to dissolve nost of the pitch, followed by a water. rinse. The nature and volume of the dryer wash waters depend upcn the amount of water used, the anount of any scraping prior to application of the detergent and the rinse, condition and operating patterns of the dryer, and the species of wood being dried. 21. The water released by the veneer in the drying process is conver- ted to steam and vented to the atnesphere. The liquid discharge frcm the dryer includes spent wash water and the water from the deluge system when that system is used to extinguish fires that sometimes start inside the unit. Same plants take advantage of fires to clean the dryers. Water is also used occasionally to flood the bottam of the units in order (according to sci claims) to lessen the insidence of fires and reduce air pollution problems. For veneer dryer washing purposes a typical plant will ,discharge about 17.5 liters per metric ton of production. Dryers are generally wash- ed once in every 80 hours of operation. 22. Many plants recycle all wash, fire, and flood waters fran the dryers because the operation causes substantial evaporation of water. Thus, fresh water can be used to clean the dryers and still operate as a closed system. 23. Waste water in the glue operation originates from washing of the mixers, glue hold tanks and the glue spreaders. Discharge fron the glue washing operations averages about 45 liters per metric ton of product. 24. A typical combined veneer and plywood mill requires a certain amount of cooling water to dissipate heat fran the air compressors, as well as the lathes and presses. This is normally "pass-through" water and does not require any special handling before discharge to the environment. The discharge should be nonitored, however, to assure that temperatures do not reach unacceptable levels. - 337 - Solid Wastes 25. Solid wastes generated in the production process include (a) bark, (b) wood particles from the veneer dryers, (c) organic "pitch" frcm cleaning of the veneer driers, (d) wood trimmings from cutting veneers and plywood sheets to size and (e) wood dust fran the sanding and finishing op- erations. It is difficult to quantify these materials since they are de- pendent a the practices and products at each particular plant. EFUJE=I LIMITATIONS Gaseous Emissions 26. Gaseous emissions are not considered significant in plywood plants, except where coatings are applied as part of the production pro- cess. Volatile organic conpounds are discharged fron the coating lines. The nature of these emissions depends upcn the organic solvent used. These are normally multiconponent mixtures which may contain various combinations of nethyl ethyl ketcne, methyl isobutyl ketone, toluene, xylene, butyle acetates, propanol, and others. 27. Emissions levels of volatile organic conpounds (VOC) should be kept at or below the following concentrations: Printed interior wall 2.9 kg VOC per 100 m2 panels of bardwood plywood coated surface Natural finish hardwood 5.8 kg VOC per 100 m2 plywood panels coated surface Liquid Effluents 28. Liquid effluent limitations are presented in Table 1. These limits are considered achievable on the basis of best practicable technology currently available. CONTROL AND TREA'IMENT OF WASTES Gaseous Emissions 29. Measures for reducticn of volatile organic compounds fran coating operations includes the use of low solvent, ultra-violet curable coatings; use of wasterborne coatings; and incineration. - 338 - Table 1. Effluent Limitations for Plywood Manufacturing Plants. 330D5 - kg/m/ SS - kgm3 Waste Source 30-day Max. 30-day Max. Av. Daily Av. Daily Barking Except Hydraulic 2/ 2/ 2/ 2/ Barking - Hydraulic 0.5 1.5 2.3 6.9 Log Conditioning - Except Direct Steam 2/ 2/ 2/ 2/ Log Conditioning - Direct Steam Softwood 0.24 0.72 0 0 Hardwood 0.54 1.62 0 0 Glueing Operations 2/ 2/ 2./ 2.1 .1 Kg/m3 . Kilograms per cubic meter of wood barked or of veneer produced from conditioned logs. 2/ Zero discharge. 30. Ultraviolet curable coatings, where applicable, effect a nearly complete reduction of VOC emissions. In the . flat wood industry, UV coatings have found use as clear to semitransparent fillers and top coatings for interior printed panelling and cabinet-raking products. The advantages of UV coatings include reduced power requirements, space savings through reduced storage and oven size, very little VOC emission, and essentially 100 percent utilization of the coating. mixture. Safety precautions must be. taken to minilize personnel exposure to UV radiation and to avoid contact with the coating, since some of the raw materials can cause chemical birns. 31. The use of waterborne coatings can achieve anywhere from 70 to 90 percent reduction of emissions. This is currently the principal neasure being followed by the flat-wood industry. The primary use of these coat- ings is in the filler and base coat applied to printed interior panelling. Waterborne coatings can reduce fire hazards, fire insurance costs, and air pollution. Problems with these coatings include possible grain raining, wood swelling, poor quality finish, and longer cure times. 32. The use of control devices sudh as direct-flame and catalytic incinerators is very limited in this industry. Few data are available on control efficiency or fuel requirements. - 339 - Liquid Effluents 33. Where debarking is by a dry process, the bark chips are shredded and burned as fuel. For wet drum and bag barkers, the chips are pressed to remove the water and sent to the boiler for use as fuel. The water can be recycled. 34. Bark from the hydraulic type of unit is separated, pressed to re- move the water, and used as boiler fuel. The amount of water resulting from the process is more than can be used in other plant unit operations, and hence must be -otherwise handled. Treatment follows- the practices wide- ly utilized in the pulp industry, i.e. the use of circular heavy-duty type clarifiers or thickeners. The clarifier effluent is dewatered, by vacuum filters or other means, and then subjected to biological treatment which is normally 85 to 95 percent effective. The filter cake, containing up to 30 percent moisture, is disposed of cn land or sold for use as a mulch. 35. The major effort in the veneer production segment of this indus- try has been directed towards reducing waste water volumes by reuse and ccnservation, and by containment of those waste waters that cannot be re- used. Waste water from log conditioning is probably the largest and most difficult source to handle in a veneer mill. 36. Hot water vats, when heated indirectly through coils, will not have a continuous discharge. Any discharge results from spillage when logs are placed into or 'taken out of the units. The wastewater fron these operations can be clarified by settling in tanks or ponds and then reused for nakeup. The resulting sludge is transferred to a landfill. Some de- creased pH in the vats may occur over time. If this happens, lime or sodium hydroxide should be added for corrosicn control. 37. Wastewater from steam vats must be discharged because of the dif- ficulty of reusing the contaminated condensate. In same instances modifi- cation can be made to allow conversicn of steam vats to hot water spray tunnels which then function in a manner similar to hot water vats. 38. Either the use of hot water sprays or the use of modified steam- ing would allow mills that use steam vats to operate in a manner similar to those that use hot water vats (in which there is no steam impingement) . All of these are closed systems, requiring only solids removal and periodic "flush-outs". The relatively small volume of water produced from the "flush-outs" can be contained in evaporation ponds or used for irrigation. 39. In cases where effluents from either hot water or steam vats must be treated then biological methods, such as ordinary or aerated lagoons, have been both practicable and effective. It has been reported that BOD5 reductions of 85 to 90 percent are readily achievable. 40. Waste discharges from cleaning of veneer dryers can he reduced through various modifications in the procedure. One mill reports a signif- icant reduction by manually scraping the dryer and blowing it out with air prior to the application of water. Installation of water meters or valved hoses prcmotes water conservation and results in significant reductions. The volume of wastes fram this source is small enough to be handled by con- tainment or by use for irrigation or similar purposes. - 340 - 41. T(Bchnology is currently available to eliminate the discharge of all wastes from the glueing operations. Recycling systems are accepted technology in the industiy, and are applicable for protein, urea, and phe- nol types of glues. Hcwever, mills that use several types of glues musti have individual recycle systems to separate the different wash waters, since attempts at mixing the wastewater frcm different types of glues have not been successful. Various inplant operational and equipment modifica- tions can reduce the volume of glue wash water. 42. In addition to recycling the plant may also contain and/or evaporate the glue washwater, spray the liquid on the .bark that goes into the boiler as fuel, or use a combination of these techniques. Solid Wastes 43. Along with the bark chips previously mentioned, solid wastes also include veneer dryer scrapings, unusable veneer and triumings, and trim and sander dusts fron the finishing opertions. These wastes may be burned for fuel, dunped on land, or sold for other uses elsewhere. BIBLIOGRAPHY 1. U.S. Ehvironmental Protection Agency. "Developmnent Docurent for Effluent Limitations Guidelines and New Source Performance Standards for the Plywood, Hardwood, and Wood Preserving Segment of the Timber Products Point Source Category". Doc. EPA-440/1-74-023-a. Washington, (April 1974). 2. U.S. Environmental Protection Agency. "Guidance for Lcwest Achievable Emission Rates from 18 Major Stationary Sources of Particulate, Nitrogen Oxides, Sulfur Dioxide, or Volatile Organic Compounds". Doc. EPA-450/3-79-024. Washington (April 1979). 3. Nestler, F.H. and Max Nestler. "The Formaldehyde Problem in Wood-Based Products-An Annotated Bibliography". U.S. Forest Service General Technical Report FPL-8. Washington (1977). 4. Blomquist, R.F., "Formaldehyde Emissions Are No Problem With Wood Products Bonded With Phenolic Resins". American Plywood Associa- ticn, Tacoma, Washington 98411. (August 6, 1981). 5. Baker, William A., Ed. "Technical Literature Index". American Plywood Association, 'acoma, Washington 98411. (September 1980). THE WORLD BAg - 341 - OCTOBEI 1980 OFFICE OF E3YFNMENTA ARIS POULTRY PROCESSING PLATS InDUSTRIAL WASTE DISPOSAL 1. Poultry processing operations cover young and mature chickens, turkeys, ducks, geese, various other birds, and small game such as rabbits. The final product may consist of whole carcasses, pairts, cooked or canned meats, and specialties such as rolls and patties. Plants may produce one or a combination of several of these items. IDUSTEIAL PROCESSES 2. Live birds are taken to processing plants in coops, which are first transferred to the hanging area. The birds are removed from the coops and sus- spended by the feet from an overhead conveyor line. This is followed by slaught- ering, most commonly done by severing the jugular vein or by debraining. The dead bird then travels through an enclosed area, known as the "blood tunnel", for draining and recovery of free-flowing blood. Recovery may be either from the floor of the tunnel or from troughs installed for the purpose. 3. After. the blood tnnel the birds are scalded and mechanically de- feathered. Remaining pin feathers are next removed, either by hand or by wax stripping. The defeathered carcass goes to the evisceration room, where the feet are cut off, the peritoneal cavity opened, and the viscera removed. The visceral parts are separated into edible and non-edible portions. The non- edible portions are added to the offal disposal system. Next, the head and neck are removed, the carcass thoroughly washed and then inspected. The final step is chilling or freezing, and packing either for marketing or for further processing. 4. Additional processing can involve thawing, cutting and boning, dicing, grinding and chopping, batter and breading, miIng and blending, stuffing, canning, final product preparation, packaging and shipping in various combina- tions. 5. Product flows for basic and further processing plants are shown in Figures 1 and 2, respectively. SOURCES AND CEARACTER OF WASTES 6. Liquid wastes carrying varying amounts of solids are the major con- cern in this industry. Solid wastes, resulting mainly from housekeeping and screening of effluents may also be of concern but this will depend upon in- plant practices and degree of solids separation. Gaseous wastes are generally of no significance. The purely hazardous types of waste components, such as heavy metals and pesticides are not normally found in the effluents. - 342 - .PROCESSES WASTS1 PRODUCT FLOW SY-PRODUCT FLOW LIQUID SOLID BIRDS* RECEIVING AREA1 KILLINGS BLOOD RECOVERY tNOIL - -tm1 SCALDINGN PICKING * im mmm m-m..mm a , I r ROEING SEISCEAA N SOLIDG TREATMEN HAASTIN PRCSPRTRO m ~ ~ DICAG SCARCASS l WASH1Pi ALTERNATE S0LISS FLOW AS SOLIDS.7ASTE (INCLUDES DRY CLEANUP) CHILLING ...INSDI3BE, RINDKRING PACKING - -- - i. PLN. 2)I PREESWTE IM.800 SLUDGE TWEAMEN WAWASTE PLAN polr DrciPOSa ts Figure 1 - T7pical Process Flow and Wasta Sources Ao. olr rcesn lns (7rom Raf . 2) - 343 - WASTER WATER, PROCESS AND MATERIAL FLOW RELATIVE FLOW* ~ J_ RECIV-G m - - M m . THAWING - - -MED LGE SM - PERIODIC CUT-UP - - - - -- - .. OPERATIONS SM - PERIODIC BONING COOKING - - - - - MED - LGE DICING* SM - MED PERIODIC GRINDINIG, - - - BATTER AND BREADINGII MIXIiG, SM - MED PERIODIC BLENDING COOKING SM - MED * -------- m- -------m STUFFING - - ------ - -- CANNING MED - LGE EG 'COOKING qm m I MED - LGE V SM STORAGE -----** IPREPAAIN FREEZING & V SM PERIODIC PACKAGING I MATERIAL OR C01. PRODUCT FLOW STORAGEWATWTE *v SM VERY SMALL WASTE WATER SM -SMALL MED * MEDIUM TREATMENT LGE -LARGE Figure 2. Typical Process Flow and Waste Sources for Further Processing Poultr7 Plant. (From Ref. 2) - 344 - 7. The most significant parameters applicable to the liquid effluents are the 5-day biochemical oxygen demand (30D5) total suspend solids (TSS), oils and greases (0 + G), hydrogen-ion concentration (pH), and facal coliform organisms. Amonia levels may occasionally be of concern. 8. All of the steps in the poultry plant processing contribute to the waste loadings. These contributions include blood, offal, feathers, meat and fatty tissues, materials lost in processing, preservatives and caustic or alkaline detergents. In mst plants, raw wastes are subjected to "primary" treatment by discharge through catch basins, skiing tanka, air flotation systems, or other devices. The basic purpose of this procedure is not waste treatment per sa, but the recovery of by-products which can be profitably separated and marketed. 9. The strongest single pollutant is blood, generated in the killing area. Feathers, dirt and manure will also be added at this point. Those materials not removed by drains or dry scraping are flushed to the sever during cleaning. Overflows from the scalding and defeathering operations w.ll also contribute these same materials. 10. The evisceration process and subsequent washing generate a large volume of waste water. The carcass and giblet washing, worker hand washers, side-pan washers and viscera flow-away water, and clean up operations, all con- tribute to this flow. Waste waters from the evisceration procedures will con- tain tissue and fat solids, gut, grease, blood and intestinal bacteria. 11. Another waste source is the carcass and gizzard chilling operation. This is made up of chiller overflows, dumping of chiller water at the and of each day, and equipment clean-up. The chiller wastes contain greases,meat and fat particles and blood. 12. Feathers and offal are discharged to flumes and recovered by screen- ing. The flume water and the water retained by these materials and draining through the equipment eventually 'ecome a part of the total plant effluent. 13. The operations designated as "further" processing use waters to thaw frozen materials, to cook the poultry and finished products, to cool the freshly cooked products, and to clean the equipment. The birds and products come into direct contact in some of these processes and thus contribute waste components. 14. Some plants have on-site rendering facilities to produce feed grade materials from the feathers, offal, blood and other by-products. Generally, however, these by-products are taken off-site for .endering purposes. Rendering operations are discussed in greater detail in the guideline titled "Meat Process- ing and Rendering Industry". 15. Waste water effluent streams for typical poultry processing plants are shown in Figures 1 and 2. Typical raw waste flows and characteristics are shown in Table 1. These data are for effluents following the application of in-plant "primary" treatment for by-product recovery. - 345 - Table 1. Typical Raw Waste Flows and Characteristics for Poultry Industry Plants a/ Av. Live Type of Weight Flow 30D5 TSS 0 + G b/ Plant (kg) (Liters) (kg) (kg) (kg) Per Bird Per Mg Live Weight KIlled Chickens 1.74 34 9.9 6.9 4.2 Turkeys 8.3 118 4.9 3.2 0.89 Fowl 2.3 49 15. 10. 2.3 Ducks 2.9 75 7.1 4.4 1.9 Per megagram Final Product * Further Pro - 12,500 19 9.1 6.4 cassing C/ al Following application of in-plant "priary" treatment. b/ 0 + G = Oils and Greases C/ No slaughtering * 1 magagram , 1 metric ton, Mg M megagram EFFLUENT LITAIONS 16. Effluent limitations for plants which slaughter and process poultry products are presented in Table 2. The limitations are based on the best practicable control technology currently available. Where further processing or on-site rendering is carried out, it is necessary to add an adjustment, according to the factors shown in paragraph 17. 17. Adjustments to these limitations are to be made in cases where further processing or rendering (or both) may be carried out in conjunction with other operations. These adjustments are to be added to the limits shown and are as follows: 겸 347 CMqTRM AND :A7MMT_OF WASTES is. Waste loads discharged by, the poult%-7 industr7 ma7 be reduced to acceptable levels through a combination of tachniques including fficient water management, in-plantwasta controls, process control, and varrIng da- grees of biological treatment. Wastes may also be released to ymmeipal systems- provided that pretreatment measures are applied. 19. In-plant measures Include (a) monitoring flows and waste strengths in all major water use areas; (b) control and reduction-of water flows at major outlets through use of properly, sized nozzles and pressure regulation; (a) confining bleeding procedures and recou ring all possible collectable blood for rendering; (d) shutting off unnecess=7 water flown during work breaks; (e) rousing water for makeup purposes whenever possible; (f) applying d%-7 offal bandling in place of fluming; (g) close monitoring of screening and handling syste= for offal and feathers to prevent discharge of these materials; (h) using dry cleanup prior to washdown of all floors and tables; and (i) training all employe,-m in appl7ing good water management practices. 20. B7-prodUct racovery of offal and feathers, when fluming is utilized, .is accomplished by the use of screens. These may be rotary,, tibrating or static t7pes, Vibrating and rotar7 screens are most frequentI7 used in the poultry Industry. They can be useful not only for materials recovery but also for providing at least primar7 trea"mmmt for all plant wastes when screening openings are sufficiently fine. Grease and solids may also be re:moved by the use of catch basins or air flotation systa=. 21. Several biological systems may be used for treatment of these wastes, followIng the application of in-plant primar7 treatment. Anaerobic processes, aerobic lagoons, and activated sludge s7stems are commonly used. The system, used must be adaptad to the individual plant on the basis of waste water vol=a, waste loads, equipment used, required waste load reduction, sludge disposal, odor problems and other factors, 22. Where a maxim= degree of treatment is required, chemical precipitation, sand filters, and microstralners have been effective.- A no discharge condition can be achieved through the use of spray or flood irrigation where sufficient areas of relatively flat land are availabla. BIBLIOGPAM 1. Jones. Harold R. "Pollution Control in Maat, Poultr7s and Seafood Processing". Noyes Data Corporation. Park Ridge, N.J. and London (1974). 2. U.S. Enviranmmmtal Protection Agenay "Development Document for Proposed Effluent TAm4tations Guidelines and New Source Performance Standards for. the Poultx7 Segment of the Meat Product and Ran daring Process Point Source Categor7". Doc. EPA-440/1-73/031-6, Group 1, Phase II. Washing- ton (April 1975). 3. U.S. Envirortmental Protection Agency "Upgrading Poultry Processing Facilities to Reduce Pollution". EPA Technology Transfer Semd"ar Pub- lications. 3 Vols. Washington (JuI7 1973). - 348 - THE WORLD BANK JANUARY 1981 OFFICE 07 ENVIROMENTAL AFFAIRS PULP AND PAPER INDUSTRY EFFLUENT GUIDELINES 1. Paper is produced from raw materials containing cellulose fibers, which is the basic required component. While the greatest portion of the fibers are produced from wood, some are produced from recycled paper and from nen-wood sources. 2. Several methods are used for pulping wood. In some processes it is cooked with chemicals under controlled conditions of temperature, pressure, time and liquor composition, with different chemicals and combinations of chemicals being utilized. In other methods wood is reduced to a fibrous state by machanical or by a combination of mechanical and chemical means. 3. To prepare the paper stock the pulp is resuspended in water, followed by refiners to refine the individual fibers into the state required to produce the strength needed in the paper product. The degree of fiber refining is governed by the type of pulp and the and paper product desired. MANUFACTURING PROCESSES 4. Wood may be received at the pulp mill in any one of several differ- ent forms, including logs, chips, sawdust and other sawmill residues. Wood Preparation 5. In the case of logs the bark is first removed, and this may,be done either by friction with other logs (in barking drums), by mechanical tools, or by water jets (hydraulic debarking). The barking drums may be operated either with or without water, but better debarking is achieved and wood losses are lower when water is used. The clean logs are then chipped to produce wood fragments of suitable size (about 30 x 30 x 4 m). The chips are screened to separate those which are either too small or too large, and transferred to storage bins or chip piles for later use. 6. Fibers constitute the basic raw material in the manufacture of paper. These are composed mainly of cellulose, and may be derived from either wood or non-wood sources. The fibers represent some 50 percent of the dry weight of the fiber source, with the other major components consisting of hemi-callu- loses and lignina. The last two substances serve to cement the fibers together. Fibers are separated from the wood by means of the pulping operations, using mechanical pulping, chemical pulping, or a combination of both. On a world- wide basis, approximately one-third of the paper production is from mechanical pulps and two-thirds is from chemical pulps. - 349 - 7. World-wide it is estimated that 5 percent of new pulp coms from non-wood fibrous materials. Non-wood materials used for pulp, papers and paper board production include agricultural residues (bagasse, cereals), natural plants (such as bamboo and esparto grass) and cultivated fiber crops (such as jute, flas, sisal and cotton fibers). The most widely used of these are wheat straw, rice strawt bamboo and bagasse. The processes used for pro- ducing non-wood materials are generally similar to those used in the wood-based segments of the industry. Pulp Preparation 8. Mechanical pulp is also known as groundwood pulp, since mechanical action, in the form of large rotating grindstones, is used to process the whole logs. The type of wood most readily or economically available usually determines the groundwood process to be applied. Softwood generally does not require pretreatment and has therefore been the usual raw material for the stone groundwood process, as well as for some of the other processes. The high energy requirements for grinding untreated hardwood may be offset by using pro- ceases which incorporate pretreatment. Sawmill residues are also a source of raw materials for processes which utilize wood chips. 9. The principal mechanical pulping processes include stone groundwood, refiner groundwood, thermo-mechanical, cold soda, and chemical groundwood. The process selected is based on the raw material supplied, type of fiber desired, and strength of paper needed for specific uses. 10. In chemical pulping wood, the raw material is cooked in batch or continuous digesters (large pressure vessels) with solutions of various chem- icals. Digestion (or cooking) proceeds to the point at which non-cellulosic constitutents are dissolved and the fibers can be liberated by "blowing" (i.e. ejecting the chips) from the digester. 11. The principal chemical methods include acid sulfite, kraft and soda. Softwoods are the primary raw materials of the sulfite process, while both soft and hardwoods are used in kraft and soda pulping. 12. While the mechanical pulps have many desirable qualities for the manu- facture of low cost. paper (where opacity is important), they normally do not have sufficient brightness for the better grades. Brightness will also vary with the characteristics of the wood raw material. Bleaching is therefore necessary to satisfy the demands of better end paper products where mechanical pulps are used for their production. Pulp Bleaching 13. The most con bleaching agents for stone and refiner groundwoods are hydro-sulfites and peroxides, used either individually or in sequence. Zinc hydrosulfita, sodium and potassium borohydride, hydrogen peroxide and sodium peroxide are the specific chemicals particularly used. The same chemicals may also be used for cold soda and chemi-groundwood pulps. - 350 - 14. For chemical pulps the most frequently employed bleaching chemicals are chlorine, calcim or sodium hypochlorite, and chlorine dioxide. Alkalies such as caustic soda and calcium hydroxide are used to extract chlorinated re- action products. 15. Oxygen bleaching of chemical pulps is a new process developed in recent. years, and is currently used in a limited number of mills world-wide. It is said to achieve a brightness and strength equivalent to that obtained by more costly uthods. It has also been reported as being less susceptible to brightness reversion. 16. Displacement bleaching, barely beyond the pilot plant stage, has recently been installed in two U.S. plants. In this process, chemicals are displaced through a pulp mat rather than being conventionally mixed into the pulp. Very rapid bleaching occurs, due to high reaction rates. 17. A variety of waste papers are deinked to produce a variety of pulps. Before waste paper can be used for this purpose it must be carefully classi- fied into different groups, only some of which can be deinked, since (a) not all. waste papers are suitable for deinking and (b) specific types of waste papers are suitable only for specific types of reclaimed pulps. 18. Where the pulp is to be used away from the production site it is dried for market purposes.. The pulp is reduced to a thick mat, on either a Fburdrinier machine or a cylinder mold, subjected to mechanical pressure in a series of presses, and then dried to air-dry consistency (about 10% moisture content). Wet market pulp, with a moisture content of 50 percent is also produced in some cases. The process is the same as that for the dry pulp, except that the final drying step is omitted. 19. Unbleached kraft and neutral sulfite semi-chemical (NSSC) pulps are also produced in some plants. The unbleached pulps are mainly used for liner- board (used as the smooth-surface facing in corrugated board), wrapping paper, grocery bags, and shipping sacks. Semi-chemical pulps are used mostly as the corrugating medium in corrugated board. 20. The paper mill may be close to or at a distance from the pulp mill. An integrated paper mill is one that is located near a pulp mill, and the pulp is transferred as a slurry directly to the paper-making process. The non-inta- grated mill is usually located at some distance from the pulp mill and receives the pulp in a dry or semi-dry form. The paper stock is prepared by resuspend- ing the dry or semi-dry pulp in water to a consistency of 4 to 6 percent. Stock Preparation 21. The stock is mechanically treated in the refiners to "brush" or cut the individual fibers. This step produces the properties needed to give the required strength to the paper. In cases where good formation is desired, - 351 - such as for fine papers, the stock is also pumped through a jordan, which further cuts the fibers to the necessary length with a minimum of brushing. The amount of cutting and brushing varies with the type of pulp used and the requirements of the and paper product. 22. Chemical additives may be used for various purposes, either before or after stock preparation. For example, resin is used for sizing, which prevents blotting of ink. Clay, calcium carbonate, and.titanius oxide are some of the substances added as fillers where opacity and brightness of the papers are important. A wide variety of other additives such as wat strength resins, dyestuffs, and starches may be used, depending on end-use requirements. Paper Production 23. The final paper or board product is formed on either a Fourdrinier, a cylinder machine, or a twin-wire machine. The Fourdrinier has a flat sheet- forming surface while the cylinder machine utilizes a cylindrical-shaped mold. The Fourdrinier is most widely used at the present time. 24. . In the Fourdriniar operation the dilute pulp flows onto a wire screen, on which the water drains off and the sheet is formed. A suction pick-up roll transfaers the sheet from the wire to presses, which enhances the density and smoothness and removes additional water. It then passes through a series of heated hollow metal cylinders for final drying. 25. In the cylinder operation, revolving wire-mash cylinders rotate in one or more vats of dilute pulp, picking up fibers and depositing them on a moving belt. The pressing and drying procedures are the same as for the Four- drinier operation. The cylinder machine has the capability of producing heavier anlti-layered sheets, and therefore its principal use is in the manufacture of paperboard. 26. In the twin-wire operation the paper stock passes between two wire webs. Water drains simultaneously from each side of the stock, resulting in formation of the sheet. WASTE SOURCES AND CEARACTERISTICS 27. Pulp and paper production affects the environment in several ways, since gaseous, liquid, and solid wastes are produced from various parts of the operations. The greatest environmental impact comes from the bleaching and pulping of chemical pulp. Mechanical pulping operations usually have less impact on the environment. The environmental impacts can be greatly reduced by recycling and reusing most of the process waters and many of the chemicals back into the process. Air Emissions 28. The principal emissions of concern at kraft pulp mills are sulfur dioxide, total reduced sulfur (TRS) compounds and particulate matter. Hydrogen - 352 - sulfide, methyl mercaptans, dimethyl sulfide, and dimethyl disulfide as a group contitute the TRS compounds. The most noticeable characteristics of the TRS group is its highly odorous nature. 29. The TRS group originates mainly in the sulfate cooking process - generally in the digester systems, the brown stock washers, the multiple effect evaporators, the black liquor oxidation systems, the recovery furnace, the smelt-dissolving.tank, the lime kiln, and the condensate stripper systems. Sulfur dioxide originates from the sulfite process as well as from the neutral sulfite and bisulfite processes. Some sulfur dioxide is formed in the recovery boiler of the sulfate process, as well as from burning coal or fuel oil in the power plant. Principal sources are the recovery furnace, lime kiln, smelt dissolving tanks, and the power plant. Principal sources of the particulate matter are the recovery furnaces, the smelt dissolving tank, and the lime kiln. Fly ash particles consist mainly of carbonates and sulfates. 30. Chlorine emissions can occur, but are mostly of the "diffuse" type. This means that they are not located at any particular point source, but orig- inate as fumes from tank vents, wash filters, severs, and other similar sources. The gases are mainly chlorine or chlorine dioxide. Generally concentrations are not significant, but provisions should be made for detecting and handling lethal concentrations, should they develop. Hydrogen sulfide can collect in the stock chests. Good ventilation should be provided; work operations at that location should be carried out by at least two persons together in case of emergency. Liauid Effluents 31. Water is a principal raw material in the manufacture of pulp and paper, and is used extensively in each of the subprocesses. As it flows through the various process steps it is in contact with other raw materials and absorbs many of the substances. 32. The parameters of principal importance for describing the degree of contamination in liquid effluents from pulp and paper mill operations include 5-day biochemical oxygen demand (BD5); total suspended solids (TSS); color (not including groundwood, deinked, and non-integrated sub-categories); amonia nitrogen (for amonia base sulfite and amnia base dissolving subcategories only). In European practice chemical oxygen demand (COD) is also frequently used as a parameter. Typical flows, BOD5, and TSS for untreated wastes (the parameters of most importance in the Bank's activities) are shown in Table 1. 33. In the various chemical pulping procedures lignin and lignin deriva- tives enter into solutions from the wood during the cooking process. The spent cooking liquors containing these highly colored compounds are removed from the pulp in a washing sequence following the cooking process. The wash water is highly colored. In spite or recovery procedates many mills continue to discharge wastes having a high degree of color. 넌 354 34. Pulp and papermaking liquid wastes normally contain minor concentra- tions of aumonia, nitrogez4 and nitrogen compounds are often added to provide necessary biological treatment efficiencies in the plant waste treatment s7stem. In the same way, zinc compounds also normally occur in sub-lathal concentrations and henca are of minor concern in pulp YnI11 waste dischn gas. Zinc concentrations in excess of 5 mg/L in waters used for public supply can cause =desirable tastes which persist through conventional water treatment systems. Solid Wastes 35. The characteristics of solid wastes from pulp and paper milI operations wiU very considerably from ane, mill to another@ For the average mill the dis- t%-ibution of total solid wastes will be as follows: Wastmatar- sludges 45 percent Ash 25 percent Backv wood waste 15 percent Paper, trash 10 percent Miscellaneous 5 percent Approximately 75 percent of the solid wastes will be organic in mature. Total solid waste generation for a typical kraft mill producing 200 tons of pulp per day, and typical paper z-111 producing 100 tons/day, are presented in Table 2. Table 2 Solid*Wastas Generated in Typical Pulo and Paper Mill Operations a/ Blaachea Newsprint Waste Principal Kraft Pulp. Source, Constituents Mill Pner Mill Log pond, wood Stones, mud, 500 'ream bark Boiler ash Ash, sand 1200 Knots, screen Wood slivers, 300 rejects pulping Chem. Racausticizing Lima, metals, rejects carbon 1300 Wastewater Fiber, sand, 1400 1200 sludges fine clays Paper, trash Varied 100 30 a/ From Reference No. 4 b Producing 200 tons/da-7 c/ Producing 100 tons/day - 355 - EFFLUENT LIITATIONS 36. Limitationa for air emissions discharged from pulp and paper mill operations ara sh~w in Table 3. Table 3 - Gastous Emission Limitations - Pulp and Paper Mills SourC al Particulate Sulfu T-a Matter Dioxide %c/kg ADP-N (Ament) Bacovery Furnace System 0.075 LAmæ Ei 0.0125 Smalt Tank 0.0125 Bron Stock Washer 0.005 BLack Liquor Oxid. 0.005 *Condensate Stripper 0.005 Digester System_ 0.005 Mult. Eff. Evaporator 0.005 AU Sources 100 l 100_d/ al TRS m Total Raduced Sulfur Compounds, measured as H2S bi/ ADP Air Driad ?up r/ Annual Arith. Mean, max. 24-hours = 1000 pg/Nm3 d/ Annual Geom. Mian, Max. 24-hours a 500 p/Nn3 37. Liquid effluent guidelines for bleached kraft, groundwood sulfite, soda, de±nk and non-intagrated paper m4il, unblaached kraft and semichemical pulp mills arm presented in Table 4. In all cases, the limitations ara based cn the best practicable control technology considered to be widely available. - 356 - Table 4 - Liquid Effluent Limitations - Pulp and Paper Mills (See Appendix A for descriptions of Waste Sources) Waste SourceA/ BODO I TSS ZINC Kg/XT produced/Day- Bleached Kraft Pulp Mills Dissolving Pulp 13.0 15.6 Zfarket Pulp 7.1 10.3 Finepaper Pulp 4.7 7.4 - BCT-- Pulp 6.4 10.3 - Sulfite Pulp Mills Papergrade Pulp 15.2 21.2 - Dissolving Pulp 22.7 26.2 - Soda Pulp Mills 5.8 8.3 - Groundwood Pulp Mills Chemi-mech. Pulp 3.5 5.9 0.13 Therm-Mech. Pulp 2.6 4.4 0.10 Fine.7aper Pulp 3.8 6.4 0.14 HN- Pulp 4.2 7.0 0.15 Deink Paper Mills 7.0 12.6 - Non-Integrated Paper Mills Fine Paper 4.2 4.2 Tissue Paper a/4.7 4.7 Tissue Paper (FWP)- 4.7 4.7 - Unbleached Kraft Pulp Mills 2.8 6.0 - NSSC - Amonia Pulps -- 4.0 5.0 - NSSC - Sadium Pulps 4.4 5.5 - Unbleached Kraft - NSSC Pulps 4.0 6.2 a/ In all cases pH = 6.0 to 9.0 b/ Maximum of average daily values in any 30-day period. Mansmum daily value not to exceed 2 times 30-day average. q/ BCT a Pulp used to manufacture paperboard, coarse papers, and tissue papers. - 357 d/ CM Pulp used to manufacture, coarse, molded fiber and newsprint papers. / FnP - From vasta paper. f/ NSSC * Neutral sulfite semi-chemical process. CONTROL AND TREAMENT OF WASTES 38. Although there are variations in equipment and technology between individual mills manufacturing the sam types of products, such differences do not significantly change the characteristics of the wastes produced in each situation. Currently available control technology will not usually re- quire major changes in production processes. Changes in piping, modification of existing equipment, and other relatively minor changes will generally permit application of existing control technology. Gaseous Wastes 39. Except in an occasional situation (such as unfavorable topography or adverse climatological conditions) sulfur dioxide is not a problem for kraft mills. Adequate control is possible by proper operations, especially of the liquor recovery furnace. Appropriate selection of auiliary fuels will also be a major factor in resolving discharges of the pollutant. Where discharge concentrations are too high fuel degulfurization, flue gas removal, process modification, or some combination of these may be required. 40. The TES gases (can cause unpleasant odors from kraft mill operations. These gases (also referred to as non-condensible) originate in various parts of the mill, especially from the digestor evaporators and the foul condensate stripping. These are commonly collected in headers, scrubbed with an alkali solution to remove a portion of the sulfur, and then burned. Incineration most frequently takes place in the lime kiln, where the TRS is converted to sulfur dioxide which, in turn, is largely recovered by adsorption on the lime dust and in the liquid in the kiln exhaust scrubber. 41. Particulates originatz in various elements of the mill operation, such as the recovery furnace, power boilers, lime kiln, exhaust, and others. Control and removal is best achieved by the use of scrubbers, electrostatic precipitation and other similar means. Liquid Wastes 42. Liquid wastes can be reduced in both volume and concentrations by a combination of in-plant control measures and end-of-the-pipe treatment. 43. In-plant measures include effective pulp washing, chemical and fiber recovery, treatment and reuse of selected waste streams, collection of spills, and prevention of accidental discharges. Continuous monitoring of mill sewers should be conducted, including the outfall, in order to receive rapid warning - 358 - of accidental spills. Storage basins, prior to treatment, will serve to absorb shock discharges and provide a more constant loading on the treatment facilities. Waste loadings from wet barking can be materially reduced by recycling the bark- ing water. These and other similar operating and housekeeping measures are very effective. 44. Eternal effluent treatment includes neutralization, primary treatment to remove the settleable solids, and biological (or secondary) treatment to re- duce the effluent BD5. 45. Large pieces of assorted materials, such as knots and rocks, are dis- charged into the sewers from process operations. Large items such as tools and hard hats may also occasionally be discharged to the sewers by accident. Screens are required at strategic locations withIn the mill to remove these materials. Screens may utilize mechanical or manual cleaning, depending upon the loadings eapected. 46. Bleached kraft pulp mill effluents are highly acidic, while effluents from mechanical pulp mills and most paper mills are mildly acidic. Where the pH in the effluent requires only a small adjustment then a liquid alkali such as caustic soda, or an acid, such as hydrochloric, can be used for neutralization. Where wastes are highly acidic some form of lime is used for this purpose. 47. Settleable solids are removed in a clarifier, usually a circular tank in which the particles are allowed to settle to the bottom. In some cases slow stirring is used to cause an agglomeration of particles. Conditioning chemicals are sometimes added to enhance flocculation. At some mills settling basins, either following or in place of clarifiers, are used. These function entirely by gravity, and have a detention time of up to 8 hours. The sludges collected at the bottom of these units is withdrawn at regular intervals and handled by various disposal methods. 48. Biological treatment is now required for effluents from new mills in many industrialized countries. Such treatment facilities are also being in- stalled at many older mills . This type of treatment accomplishes several purposes: it reduces the acute tozicity of the effluent and usually renders it non-toxic to fish; it reduces the potential of the wastes to cause taste, foaming, odors, and tainting of fish flesh; and generally creates an effluent suitable for dis- charge to most surface waters. 49. Where sufficient land is available for the purpose, aerated lagoons are most often used to provide extended detention of pulp and paper mill effluents. This system will consist of one or more lagoons equipped with aerating devices and providing a detention period of several days. As a rough guide, one cubic meter of lagoon capacity will be required for each 30 grams of BOD5 in the in- fluent. As an average, the system will provide a 90% reduction in BOD , with a total detention period of about 10 days. The activated sludge process a; also effective but because of the higher capital and operating costs, its use is ually limited to situations where sufficient land is not available. The activated sludge process also requiroes a high degree of operator attention and skills. Other methods, such as oxidation ditches and trickling filters, have also been effective. - 359 - Solid Wastes 50. The largest volume of solid wastes is generated by the wastewater treatment process. Land disposal, by lagooning or dumping, has been used ex- tensively in the past. This method is being used less and less because of odors from decomposition of the materials, potential pollution of both surface and ground watars, and the elimination of affected lands from future use. However, with the application of proper sanitary landfill measures this method should create few or no environmental problems. 51. Devatering and incineration of sludges are now receiving wider usage. Vaccum filtration produces a filter cake containing 20 to 30 percent solids. Chemical conditioning with ferric chloride, alum, or polyelectrolytes will greatly aid poorly filterable sludges. Although costs are high, three types of incinera- tion are being practiced: burning in a specially designed incinerator, burning in the bark boiler, and burning in a power boiler utilizing fossil fuels. 52. Many of the solid wastes can be utilized for useful purposes. Because they are organic in nature they can be used as a fuel, for agricultural, or other purposes. Fibrous sludges and barks are suitable for manufacturing wallboard and roofing papers. It has been demonstrated that crop yields have significantly im- proved when fibrous sludges have been applied as a mulch. Ash from bark burning boilers is rich in plant nutrients, particularly potash. It can be used as a soil conditioner, particularly for acid soils. There are several other ways in which solid wastes can serve a useful purpose. It is often advantageous to en- list the cooperation of various goverment agencies, local industries, and others in developing by-product recovery and utilization measures. BIBLIOGRAPHY 1. United Nations Environmental Program. "Effluent and Emission Control in the Pulp and Paper Industry". 2 Parts. Paris (1979) 2. U.S. Environmental Protection Agency. "Development Document for Advanced Notice of Proposed or Promulgated Rule Making for Effluent Limitations Guidelines and New Source Performance Standards for the Bleached Kraft, Groundwood, Sulfita, Soda, Deink, and Non-Integrated Paper Mills Segements of the Pulp, Paper, and Paperboard Mills Point Source Catagory". Doc. EPA 440/1-75/047, Group I, Phase II. Washington (August 1975). 3. U.S. Environmental Protection Agency. "Standards Support and Environmental Impact Statement - Vol. I: Prosposed Standards of Performance for Kraft Pulp Mills". Doc. EPA 450/2-76-014-a. Washington (September 1976). 4. U.S. Environmatnal Protection Agency. "Standards Support and Environmental Impact Statament - Vol. II: Promulgated Standards of Performance for Kraft Pulp Mills". Doc. EPA 450/2-76-014-6. Washington (December 1977). - 360 - 5. Beak Consultants Limited "Environmental Considerations for the Pulp and Paper Industzy". File K4386 (Draft). Vancouver, B.C. (September 1979). 6. U.S. Environmental Protection Agency. "Development Document for Effluent Limitations Guidelines and New Source Performance Standards for the Un- bleached Kraft and Semichemical Pulp Segment of the Pulp, Paper, and Paper Board Mills Point Source Category". Doc. EPA-440/1-74-025-a. Washington (May 1974)*. 7. APHA, AWA, WPCF "Standard Methods for the Ezamination of Water and Waste- water". 14th Edition. American Public Health Association. New York (1975). 8. U.S. Environmental Protection Agency. "Guidelines for Lowest Achievable Emission Rates from 18 Major Stationary Sources of Particulate, Nitrogen Oxides, Sulfur Dioxide, or Volatile Organic Compounds". Doc. EPA 450/3-79- 024. Washington (April 1979). 9. U.S. Environmental Protection Agency. "Water Quality Criteria". Doc. EPA 23-73-033. Washington (March 1973). 10. Powers, Philip W. "Row to Dispose of Toxic Substances and Industrial Wastes". Noyes Data Corporation. Park Ridge, N.J. and London (1976). 11. Wasser, Abwasser, Abasserreinigung in der Papierindustrie, em. Prof. Dr. -Ing. W. Brecht und Dr.-Ing. H. L. Dalpke, Guatter-Staib Verlag, Postfach 180, D-7950 Biberach/RiB 1, West Germany. (December 1980). - 361 - APPENDIZ A PRINCIPAL GRADES OF FULP AND PAPER PRODUCTION FROM WOOD CELLULOSE FIBERS (*) 1. BLEACE KRAFT: DISSOLVING PULP means the production of a highly bleached pulp by a process utilizing a highly alkaline sodium hydroxide and sodium sulfide cooking liquor. Included in the manufacturing process is a "pre-cook" operation termed prehydrolysis. The highly bleached and purified dissolving pulp is used principally for the manufacture of rayon and other products requiring the virtual absence of lignin and a very high alpha cellulose content. 2. BLEACHED KRAFT: MAREET PULP means the production of bleached pulp by a "full-cook" process utilizing a highly alkaline sodium hydroxide and sodium sulfide cooking liquor. Included in this subcategory are mills producing papergrade market pulp as the only product. 3. BLEACHED KRAFT: FINE PAPERS means the production of bleached pulp by a "full-cook" process utilizing a highly alkaline sodium hydroxide and sodium sulfide cooking liquor. This pulp is used to manufacture fine papers. 4. BRLVAD KRAFT: B.C.T. PAPERS means the production .of bleached pulp, by a "full-cook" process utilizing a highly alkaline sodium hydroxide and sodium sulfide cooking liquor. This pulp is used to manufacture a variety of papers with clays and fillers contents less than eight percent. Included in this subcategory are mills producing paperboard (B), coarse (C) papers, and tissue (T) papers. 5. PAPERGRADE SULFITE means the production of pulp, usually bleached, by a "full-cook" process using an acidic cooking liquor of bisulfites of calcium, magnesium, ammonia, or sodium containing an excess of free sulphur dioxide. This pulp is used to manufacture a variety of paper products such as tissues and fine papers. 6. DISSOLVING SULFITE means the production of highly bleached and purified pulp by a "full-cook" process using very strong solutions of bi- sulfites of calcium, magnesium, amonia, or sodium containing an excess of free sulphur dioxide. This pulp is used principally for the manufacture of rayo and other products requiring the virtual absence of lignin and a very high alpha cellulose content. 7. SODA means the production of bleached pulp by a "full-cook" process utilizing a highly alkaline sodium hydroxide cooking liquor. This pulp is used principally to manufacture a wide variety of papers such as printing and writing papers. (*) Adapted from References (1) and (5) of Bibliography. - 362 - 8. GROUNDWOOD: CMI-MCHANICAL means the production of pulp, with or without brightening, utilizing a chemical cooking liquor to partially cook the wood followed by mechanical defibration by refining at atmospheric pressure. This pulp is used to produce a variety of products including fine papers, newsprint, and molded fiber products. 9. GROUNDUWOD: THEMO-MECHANICAL means the production of pulp, with or without brightening, by a brief cook utilizing steam, with or without the addition of cooking chemicals such as sodium sulfite, followed by mechanical defibration by refiners which are under pressure. This pulp is used in a variety of products such as newsprint and tissue products. 10. GROUNDWOOD: FINE PAPERS means the production of pulp, with or without brightening, utilizing only mechanical defibration by either stone grinders or refiners. 11. GROUNDWOOD: C.M.N. PAPERS means the production of pulp, with or without brightening, utilizing only mechanical defibration by either stone grinders or refiners. This pulp is used to manufacture coarse (C) papers, molded (M) fiber products, and newsprint (N). 12. DEINK means the production of secondary pulp, sometimes brightened or bleached from recycled waste papers in which an alkaline treatment may be utilized to remove contaminants such as ink and coating pigments. The pulp is used, frequently in combination with chemical pulp, to manufacture a wide variety of papers such as printing, tissue, and newsprint. 13. NON-nMTEGRATMD FINE PAPER means the manufacture of fine papers from wood pulp or deinked pulp prepared at another site. Fine papers are relatively high in price, and include grades such as printing, writing, and technical. 14. NON-InTEGRATED TISSUE PAPER means the manufacture of tissue papers from wood pulp or deinked pulp prepared at another site. Tissue papers include grades such as facial and toilet papers, paper diapers, and paper towels. 15. NON-NTEGRATED TISSUE PAPERS (FROM WASTE PAPER) means the manu- facture of tissue papers from recycled waste papers. Tissue papers include grades such as facial and toilet papers, paper diapers, and paper towels. 16. UNBLEACEED MAST means the production of pulp without bleaching by a "full-cook" process, utilizing a highly alkaline sodium hydroxide and sodium sulfide cooking liquor. This pulp is used principally to manufacture linerboard, the smooth facing of "corrugated boxes," but is also utilized for other products such as grocery bags and cement sacks. - 363 17. SODIM BASE NEUTRAL SULfITE SEMI-CEMCAL means the production of pulp without bleaching utilizing a neutral sulfite cooking liquor having a sodium base. Mechanical fiberizing follows the cooking stage, and the principal product made from this pulp is the corrugating medium or inner layer in the corrugated box "sandwich." 18. AMONIA BASE NEUTRAL SULFITE SEMI-CEMICAL means the production of pulp without bleaching, using a neutral sulfite cooking liquor having an aimonia base. Mechanical fiberizing follows the cooking stage, and the pulp is used to manufacture essentially the same products as is sodium base NSSC. 19. UNBLEACEED IRAPT-NSSC (CROSS RECOVE) means the production of unbleached kraft and sodium base NSSC pulps in the same mill wherein the spent NSSC liquor is recovered within the inbleached kraft recovery process. The products made are the same as outlined above for the unbleached kraft and NSSC subcategories, respectively. - 364 - THE WORLD BANK OCTOBER 1980 OFFICE OF ENVIRO1M1TAL AFFAIPS RODNTICIDES GUIDELINES FOR USE 1. Several World Bank projects include transporting, storing and pro- cassing food grain. Minimizing losses due to pests, mainly rodents, is a major consideration. 2. Rodenticides are being used whose toxicity to mammals, including man, varies widely. This guideline describes the main rodenticides being used and gives the important characteristics of each product. Choice of Rodenticide 3. The basis of choice for pesticide use should also be applied here. Biodegradability and toxicity are the two most important criteria. 4. The rodenticides have been separated into three different classes. In Class I the products whose use require only normal precautions. In Class II the products whose use should be discouraged or severely controlled. In Class III the products whose use should be banned. Class I Normal Precautions 5. This class includes the anticoagulants, and the following rodenticides: Red Squill, Norbormide and Zinc Phosphide. 6. The anticoagulants are the safest of all rodenticides. Unfortunately the rapid spread of resistance to them among rats and mice has made necessary the use of other types. The anticoagulants should be the first choice in areas where rodents are not yet resistant to them. 7. Red Squill, known also as Dethdiet (powder) or Rodine (liquid extract), is the powdered bulb of Urginea Maritima, a perenial growing in the Mediterra- nean area. It is extremely irritating to the skin and causes vomiting in most mamals (but not rats). Despite reported cases of cattle, sheep and chicken poisoning, the possible hazards to man are quite remote. Red Squill being a natural product, its potency is not uniform. 8. Norbormide has a good efficacy against rats with a low toxicity to - 365 - other maals. The other name is Raticata. 9. Zinc Phosphide (Zn3P2). This gray powder with high melting point is widely used. Stable when dry, but decomposes slowly in moist air. Reacts violently with acids to form inflammable phosphine gas (PR3) giving off the characteristic garlic-Like odor. While highly toxic to domestic fowl, this product has a good safety record. Class II - Severe Control 10. These products should only be applied by trained operators under the conditions specified by the manufacturer. This class includes the following products:- sodium fluoroacetate, fluoroacatamide and strychnine. 11. Sodium fluoroacatate (CH2FCOONa). Odorless, tasteless and fast acting, this chemical is extremely toxic to warm-blooded animals. It acts chiefly on the heart with secondary affect on the central nervous system. The possession, transport and sale of this compound are strictly regulated in the US. Its use should be restricted to areas (i.e. locked warehouses and sewers) to which access by unauthorized persons or by animals can be prevented complete- ly. The acute oral LD50 (rat) is 0.22 mg/kg. One trade name is 1080. 12. Fluoroacetamide (FE2C - CO - NE2). It is a highly toxic material and all precautions that apply to sodium luoroacetate should also apply to it. Its acute oral LD50 (rat) is 15 mg/kg. Trade names are: 1081 Fussol Fluorakil 100 13. Strychnine. This alkaloia is extracted from the seeds of nux vomica. Mainly used as strychnine sulfate in poison baits for jackrabbits, coyotes and wolves. It is only moderately successful in rodent control but can be quite hazardous to human beings and domestic animals. The LD50 for man is 30 - 60 mg/kg. Class III - Banned Usage 14. The products in this class should be banned because they are too dangerous for man and/or the environment. They include arsenic trioxide, phosphorous, thallium sulfate, naphtylurea (ANT) and gophacide. 15. Arsenic trioxide. This chemical has been used for many centuries and is very effective against rodents. It is also dangerous to man as a toxicant and a carcinogen. 16. Phosphorous. White phosphorous is sold in many LDCs in a 1 - 2% pasta formUlation as a cockroach poison and a rodenticide. This has led to poisoning, especially in children eating the formulation. A dose of 15 mg is highly toxic and one of 50 mg is nearly always fatal. - 366 - 17.. Thallium sulfate. It is highly toxic to rodents but also to man and useful animals that can be poisoned if they eat other animals already poisoned by thsiu. It is rapidly absorbed through the skin and the gastrointestinal tract and its elimination from the system is very slow. There have been a growing number of accidental poisonings coming from its use in household pesticidal baits. In the US, only government agencies can use it. 18. Naphytylthiourea (AMTM). A 2% impurity of this product is 2- naphtylamine, itself a known carcinogen. 19. Gophacide. This organic phosphate is highly toxic to rats and other mammaels with ready absorption through the skin as an increased hazard. Taxi- cological studies have also shown that gophacide may have delayed neurotoxic effects. New Anti-Coagulant 20. On December 5, 1979, the US EPA announced that it had approved a new poison that kills rats immune to the lethal effects of WARFARIN or other anti- coagulants. The new toxin made by ICI Americas, Wilmington, Delaware is used in 4 different baits to control rats and mice and-is called "TALON". This pro- duct should be kept away from children. - 367 - TEE WORD RAN JANUARY 1981 OFFICE OF ENVIRONMETAL AFFAIRS CRMIB RUBBER PRODUCTION EFFLUENT GuIDEL S 1. Solid rubber, for the fabrication of various products, is produced both as a natural material extracted from plant life, and synthetically from the chemical reaction of specific materials. This document will confine it- self to natural rubber only, since this is the type usually produced in countries to which Bank projects are directed. 2. Although many variaties of plants are known to contain natural rubber, only a few of these are considered to be of commerical significance. Today, the major portion of the worlds supply of natural rubber comes from a single species of tree - the Hevea brasiliensis. Although native to the Amazon Basin, it is now cultivated in tropical regions throughout the world. 3. The most favorable rubber growing areas are located within a range of 10* to 15* latitude on either side of the equator, where rainfall is heavy and evenly distributed, and the temperatures range from 200 to 32* C. The largest producers of natural rubber, as of 1976, were Malaysia, Indonesia and Thailand. Other significant producers included Sri Lanka, India, Liberia, Nigeria, Brazil, Cameroon, Ivory Coast, Cambodia and Burma. These countries were producing about 95% of the world supply. PRODUCTION PROCESSES 4. Natural rubber is marketed in a variety of forms and grades, of which the chief forms are categorized as latez, crude dry rubber, and crepe. The major share of production is for crude dry rubber. 5. Latex is obtained from the tree by cutting into the latex vessels in the bark, using a procedure called "tapping". A spout is inserted at the end of the cut (which slopes downward), and the latex flows through the spout and into a cup attached to the tree. A small amount of preservative (sodium sulfite) is usually placed in the cup to prevent coagulation. Three to four hours after tapping, the later is collected in buckets and carried to a re- caiving station. 6. At the receiving station the later is strained to remove particles of bark, dirt and other foreign matter and then transfarred to the factory by tank trucks or other means. More preservative is added to assure that the material will arrive at the factory in a well-preserved liquid condition. Sodiun sulfite is generally used to preserve latex destined for dry rubber production. - 368 - 7. In recent years new developments have been made in preparing, pack- ing, and grading natural rubber. The tendency has been towards small compressed, neatly wrapped bales marketed on the basis of technical specifications in only a few grades. 8. The material received at the factory is treated by coagulation in order to separate the rubber. Acetic and formic acids are the reagents most commonly used for this purpose. The latex coagulates into thick curds at this point. The solid forms of rubber are produced by various processes in which the rubber coagulum is reduced to small particles, washed thoroughly and dried as a crumb, either in hot air tunnels. or extrustion driers. 9. In many of the plants the coagulum is mechanically reduced to small particles by a rotary knife cutter or similar chopping or shredding device. The chopped granules are dried in deep bed trays by a forced air draft, at fairly high temperatures. Following drying the granules are compressed into bales and wrapped in plastic for marketing. 10. The Rubber Research Insitute of Malaysia has developed a mechano- chemical granulation process for the production of crumb rubber. The process uses conventional equipment but combines this with the application of a very small amount of castor oil(0.4 to 0.7 percent) as a crumbing agent. The re- sulting crumb is easily dried in hot air circulating driers. The product is marketed as "Reveacrumb". 11. Crumb rubber is generally marketed in bales weighing about 35 kilo- grams. Crumb rubber is also frequently referred to as "technically specified rubber" and as block rubber. WASTE SOURCES AND .CARACTERISTICS 12. Large quantities of water are used for washing, cleaning, and dilu- tion purposes in rubber processing operations. Some H2S odors may be emitted from stabilization ponds used to treat the effluent, but under normal conditions there are no gaseous emissions of any significance. 13. Liquid effluents consitute the most important source of pollution from natural block (crumb) rubber production. The most important parameters are biochemical oxygen demand (BOD), chemical oxygen demand (COD) total sus- pended solids (TSS), total solids (TS), ammonia nitrogen (NE3 - N), and hydro- gen-ion concentrations (pH). The quality of effluent from a typical plant is given in Table 1. - 369 - ABLE 1 - Characteristics 'of a Typical Waste from Natural Block (Crumb) Rubber Production Parameter Concentration in Effluent 30D(a) 1,140 Mg/L COD 1,620.Mg/L Total Susp Sol. 230 Mg/L Total Solids 995 mg/L N33-9- 55 Mg/L pH 6.3 Flow (b) 54 L/T Produced (a) 3 day - 30' C. (b) Estimambased. on Malaysia experience, covering 86Z block rubber and 14% latex concentrate production. EFFLENT LIMITATIONS 14. Liquid effluents discharged from block rubber plants should conform to the limitations given in Table 2, below. TABLE 2 - Effluent Limitations for Natural Block (Crumb) Rubber Plants Parameter I Limitation BOD (5-day, 20C) 100 Mg/L COD 225 Mg/L Total Susp. Sol. 100 Mg/L NE3-N 15-20 Mg/L pH 6 - 9 - 370 - CONTROL AND TEEATMNT OF WASTES 15. As shown above, wastewater from rubber processing contains organic matter and nitrogenous materials at sufficiently high levels to cause pollu- tion if discharged to receiving waters without prior treatment. Measures to reduce effluent concentrations include a combination of internal measures before treatment, followed by treatment systems. 16. Internal measures prior to treatment could include, but not be limited to: a) Application of good housekeeping practices. b) Use of rubber and/or settling trays to recover lost rubber particles and reduce solid matter in the effluent. c) Proper miming and combining of all effluents to assure maximm dilution prior to treatment. 17. Simple biological treatment, such as aerobic-anaerobic pond systems have been found effective in treating these effluents. Such systems have been found to remove 80 to 95% of the BOD, 80 to 85% of the COD, 80 to 95% of the suspended solids, and 40 to F0% of the ammonia nitrogen. Such a system re- quires a large land space and hence may not be practical for factories situ- ated in urban areas. 18. Land disposal of effluent has also been used successfully, especially where the land is planted with mature rubber or oil palm trees. While this technique has not been extensively used thus far it has been found to have the following advantages: a) Increases the yield of both rubber and oil palm in the range of 11 to 19%. b) Results in cost savings for fertilizers which might otherwise be required. c) Supplies moisture to the land, from the water in the effluent, during periods of low precipitation. d) Eliminates direct discharge of effluents into waterways. 19. Rotating bio-disc systems have also been used successfully for this purpose. Average reductions of 78% in BOD, 67% in COD, 93% in ammonia nitrogen, and 75% in total nitrogen have been achieved by this method. 20. Experimental work is now underway on the use of water hyacinth (Eichhornia crassipes) to remove a major part of the pollutant in block rubber/concentrate effluents. - 371 - 21. Other experimental work-is underway to produce methane from anaerobic treatment of the effluent. BIBLIOGRAPHY 1. "Summary of Proceedings of the Twenty-Fourth Assembly". International Rubber Study Group. Jakarta, 28-31 October 1975.(Printed by Bell, Logan & Carswall, Ltd., Belfast) 2. Polhanus, Loren G. "Rubber-Botany, Production and Utilization". Leonard Hill (Books) Ltd., London and Interscience Publishers, Inc., New York (1962). 3. "Rubber and Energy Crisis". The Economist Intelligence fUait, Ltd., London (1974). 4. "The Vanderbilt Rubber Handbook". G. G. Winspear, ad. R.T. Vanderbilt Co., Inc. New York (1968). 5. "Rubber Technology". M. Morton, ad. Second Edition. Van Hastrand Reinhold Company. Now York (1973). 6. Sittig, Marshall. "Pollution Control in the Plastics and Rubber Industry". Noyes Data Corporation. London and Park Ridge, New Jersey. (1975). 7. Rubber Research Institute of Malaysia. "Annual Report - 1978" pp. 201-203. Kala Lumpur (1979). 8. Rubber Research Insituts of Malaysia "Annual Report - 1975" pp. 158-159. Kuala Lumpur (1976). 9. "Treatment of Effluents from Rubber Processing Factories". International Rubber Conference. Kuala Lumpur (1975). 10. "Land-Disposal of Rubber Factory Effluent: Its Effects on Soil Properties and Performance of Rubber and Oil Palm". Proceedings of the Rubber Research Institute of Malaysia Planters' Conference, 15-17 October 1979. pp 436-457. Kuala Lumpur (1979). 11. "Technology and Standards for Treatment of SMR Block Rubber Effluent". Pro- cedings of the Rubber Research Institute of Malaysia Planters Conference, 17-19 October 1977. pp. 201-214.Kuala Lumpur (1977). - 372 - TE WORLD BAMK OCTOBER 1980 0FICE OF ENV AFFAIRS SECONDAEY ENVIONTAL EFFECTS OF IDUSTRIAL PROJECTS 1. When.the Bank is financing a project in the-heavy industry or in a labor intensive industry, secondary effects on the eaviroumnt will be im- portant and mst be trYan into account. 2. These effects are the consequences of a population inflax in the town or the region and they include water and power distribution, sewage collection and treatment, bousing, schools and roads. 3. In developed countries, the ratio between employment in the new plant and new employment in the region is usually one to seven, or one to eight. Although the conditions are different in LDC's, the sam ratio can be applied. If satellite industries, like mechanical repair shops for in- stance are less likely to be created, the necessity of additional services like banking or schools is apparent. 4. As an example, a steel plant employing a little less than 1000 people was built close to a town of 6000. Five years after start up, the town population had jumped to 42,000, with appalling results for the environ- meant and the,quality of life. 5. Urban Development Planning or Financing is the field of specializet departments in the Bank. They should be consulted on problems likely to arise. The goal of this guideline is only to draw the attention on the potential for trouble and to suggest economical solutions in certain areas, thus preventing the expansion of urban slum. 6. In the forecasts for water and power consumptions, not only the plant requirements but also the town future uses should be taken into consid- eration. A common water intake and pumping station or a common power line whenever possible, will usually prove more economical for both parties. 7. Sewage collection and treatmnt should receive special attention. In the case of the steel plant mentioned above, the town bad no treatmnt whatsoever with direct discharge into a river estuary. The assimilative capacity of the estuary was sufficient at the time but totally inadequate for a town of 42000. The steel plant did not help by discharging untreated industrial sevage into the same river. After a few woaths the river was dead, the beaches close to the estuary became unhealthy and their access bad to be forbidden. Finally,commercial fishing in the bay stopped.for lack of fish. 8. A pretreatment of the industrial effluent followed by treatment in a sewage plant common to both the town and the plant has advantages .for both parties. Usually both the costs for iLdustrial wastes eontrol and for municipal sewage treatment are decremsed when this solution is adopted. - 373 - 9. Dom tc and industrial garbage diUposal has created problms in the stecl plant project. The disposal should be addreassed in the plarning stages and a gultable dump arta identified. 10. FinalUy, adequata housiug, schools, as vall as road and transporta- tion should be provided. ii. F=ancing of these additlonaL expenes i, agad complicate the situation. The industrial projact caot a"a be saddled with costs for irovlng the general Infragtructure of the tow or the region. On the other hand, the town may not havs the necesary rusources to face important expend- ±iures. i9 - 374 - TI WOLD BANK OCTOBER 1980 OFFICE OF ENT AIOMTAL AFFAIRS SLAUGRTERBOUSES PART I - INDUSTRIAL WASTE DISPOSAL 1. Slaughterhouses generally limit their operations to killing of cattle and hogs, and processing of carcasses for consa=r markets or prepa- ration of a variety of products. Sheep, lamb and calves are generally handled in the sme manner. Such a facility may be a simple installation limited to k1iling and marketing of carcasses only, or it may be part of a large meat processing installation. 2. This guideline will be confined to slaughtering operations for large animals only. Separate guidelines have been prepared to cover meat processing and rendering and to cover the poultry industry. INDUSTIAL PROCESS 3. For a simple slaughterhouse operation, the steps generally involved inc:ude holding in stockyards or pens, killing, blood removal, hide removal or hog dehairing, evisceration, triaing, and cutting for market. Simple slaughterhouses are small .to medinm in size, with small installations having a live weight kill (LRK) of under 45 magagrams per dat -while medium installa- tions may range as high as 350 magagrams LWK per day.* 4. A complex slaughterhouse is one which carries out at least three by- product operations such as paunch and viscera handling, blood processing, hide or hair processing and rendering. Most complex slaughterhouses are mediu to large in size, and will normally have a LK above 350 megagrams per day. A process flow diagram is shown in Figure 1. SOURCES AND CHARACTER OF WASTES 5. Liquid wastes, carrying varying amounts of solids,are the major con- cern in this industry. Volumes of solid wastes, produced mainly from screening and housekeeping, will depend upon the degree of separation and by-product re- covery practiced at each individual plant. Other than odor problems, gaseous wastes are not significant. The purely hazardous types of waste components, such as heavy metals and pesticides, are not normally found in the effluents. 6. The most significant pollution parameters are the 5-day biochemical oxygen demand (BOD5) total suspended solids (TSS), oils and greases (0 + G), hydrogen-ion concentration (pH), and fecal coliform orgaanisms. 7. Odors originate from various sources, and generally result from bac- terial activity on organic matter. Putrescible substances result from unloading * 1 Mg I 1 megagram - 1 metric ton 月 376 .......... and ~~cm. 01 "JZ;Tgcm, m~= ~21.rng and storage,9 blood callect:i= and storaza,9. and ~raca pilan of solid trash or &artaga. 8. Tha glaugåter-läg operaticu in the larzact sinxlc llqu:Ld vacta in tha maat Ind=t=yq and bload is the major c=t=:Lbut:Lon. Cattla. for ex låt cantaln ap ta 23 kg o£ blood per, anå=l, acud only 70 parcent, is t7pically re- =verad for furthar p=cass:L=g. Tha- stmumh cantentst when vashad outg co=tituta =otbaz, scurca. Howv~m&* tUs matudål U often Inolatad and aith procasgad ar ha~4 ta landf-11 2 g end tb= docc not cout=ibut to the v»ta effluent. Other pol-at:t= sou=cen stzachtaz-lag opara~ Includa ca=ss wash-Ing. alon& with VUGGra. =d offal procaccing. la som plants hidas are =catad by a=scula dipplzgg prudnaång spant a=*=-fc solutions which- e= pt~at a spcc-(--kl d:Uposal prablem. 9. R~ w~ta ~ etazej for a typ:Lml. slaughterhousc, operation, are presentad In Table. la Table 1. Týmlcal Uv *asta Cha.,actax-lat:Lan - Slauzhtarho«a Opc=atlmg&o Flow BOD TSS O+G al Typa, of (Uters) Per magagram Liva Välght Killed 51=pla. plant 5,330 6.0 5.6 2.1 complaz Planzi: 79383 11 9.6 5.9 0 Ollå and Graauo UPLUM. LMTA=ONS 10. Efflumt 11+m