APTD-1509 NATIONAL INVENTORY OK soi |{< i:s AND EMISSIONS: MANGANESE - 1968 I .S. ENVIRONMENTAL PROTECTION AGENCY Office of Air and Water Programs Office of Air Quality Planning and Standards Research Triangle Park, North Carolina 27711 ------- APTD-1509 NATIONAL INVENTORY OF SOURCES AND EMISSIONS: MANGANESE - 1968 by W. E. Davis § Associates 9726 Sagamore Road Leawood, Kansas Contract No. CPA-70-128 EPA Project Officer: C. V. Spangler Prepared for ENVIRONMENTAL PROTECTION AGENCY Office of Air and Water Programs Office of Air Quality Planning and Standards Research Triangle Park, N.C. 27711 August 1971 ------- The APTD (Air Pollution Technical Data) series of reports is issued by the Office of Air Quality Planning and Standards, Office of Air and Water Programs, Environmental Protection Agency, to report technical data of interest to a limited number of readers. Copies of APTD reports are available free of charge to Federal employees, current contractors and grantees, and non-profit organizations - as supplies permit - from the Air Pollution Technical Information Center, Environmental Protection Agency, Research Triangle Park, North Carolina 27711 or may be obtained, for a nominal cost, from the National Technical Information Service, 5285 Port Royal Road, Springfield, Virginia 22151. This report was furnished to the Environmental Protection Agency in fulfillment of Contract No. CPA-70-128. The contents of this report are reproduced herein as received from the contractor. The opinions, findings and conclusions expressed are those of the author and not necessarily those of the Environmental Protection Agency. The report contains some information such as estimates of emission factors and emission inventories which by no means are representative of a high degree of accuracy. References to this report should acknowledge the fact that these values are estimates only. Publication No. APTD-1509 11 ------- PREFACE This report was prepared by W. E. Davis & Associates pursu- ant to Contract No. CPA 70-128 with the Environmental Pro- tection Agency, Office of Air Programs. The inventory of atmospheric emissions has been prepared to provide reliable information regarding the nature, magnitude, and extent of the emissions of manganese in the United States for the year 1968. Background information concerning the basic characteristics of the manganese industry has been assembled and included. Process descriptions are given, but they are brief, and are limited to the areas that are closely related to existing or po- tential atmospheric losses of the pollutant. Due to the limitation of time and funds allotted for the study, the plan was to personally contact about fifteen percent of the companies in each major emission source group to obtain the required information. It was known that published data con- cerning emissions of the pollutant was virtually nonexistent, and contacts with industry ascertained that atmospheric emis- sions were not a matter of record. ill ------- The manganese emissions and emission factors presented are based on the summation of information obtained from manufactur- ing companies that represent approximately eighty percent of the total production, and reprocessing companies that handle about thirty percent of the manganese used in consumer products. Air pollution control equipment is in use at many of the manganese reprocessing facilities, but its use at processing plants is limited. Manganese emissions and emission factors are considered to be reasonably accurate. IV ------- ACKNOWLEDGEMENTS This was an industry oriented study and the authors express their appreciation to the many companies and individuals in the manganese industry for their contributions. We wish to express our gratitude for the assistance of the various societies and associations, and to the many branches of the Federal and State Governments. Our express thanks to Mr. C. V. Spangler, Project Officer, Office of Air Programs, for his helpful guidance. ------- CONTENTS SUMMARY 1 Emissions by Source. 2 Emission Factors 3 SOURCES OF MANGANESE 4 MATERIAL FLOW Material Flow Chart 6 Mining 7 Imports and Exports 8 Manganese Stocks 8 Processing 9 Reprocessing 10 Carbon Steel 10 Other Steel 11 Cast Iron 11 Welding Rods 12 Nonferrous Alloys 12 Batteries 13 Chemicals 14 EMISSIONS Mining 15 Processing 17 Manganese Metal 17 Manganese Alloys 20 Reprocessing 26 Carbon Steel 26 Other Steel 35 Cast Iron 37 Welding Rods 38 Nonferrous Alloys , . . . . 40 Batteries 42 Chemicals and Other Uses 44 vn ------- Consumptive Uses 48 Coal 48 Oil 51 Incineration and Other Disposal 55 Sewage and Sludge 55 APPENDIX A Companies Dealing in Manganese and Manganese Compounds 56 TABLES Table I Uses of Manganese Ore 9 Table II Properties of Particulate Matter from a Ferromanganese Blast Furnace 22 Table III Spectrographic Analyses of Particulate Discharge from an Open-Hearth Furnace 30 Table IV Particle Size Distribution of Fume from a Basic Oxygen Furnace 32 Table V Composition of Fume and Dust from Basic Oxygen Furnaces 32 Table VI Electric Arc Steel Furnace Fume Particle Size / 34 Table VII Typical Emissions from an Electric Arc Furnace 36 Table VIII Typical Analysis of Welding Rod Coatings .... 39 Table IX Average Manganese Content in Ash of Coal ... 49 Table X Manganese Content of Domestic Crude Oils ... 52 Vlll ------- -1- SUMMARY The flow of manganese in the United States has been traced and charted for the year 1968. The consumption was 1, 150,000 tons while domestic production was only 48, 000 tons. Imports principally from Brazil, Gabon, Republic of South Africa, Congo, Guyana, India, Angola, and Australia totaled 1, 053, 000 tons. Emissions to the atmosphere during the year were 18,992 tons. About 47 percent of the emissions resulted from the production of ferroalloys and about 37 percent from the production of iron and steel. The combustion of coal was also a significant source of manganese emissions. Emission estimates for mining, production of manganese metal, and reprocessing operations are based on data obtained by per- sonal contact with processing and reprocessing companies. ------- -2- Source Category Mining Processing EMISSIONS BY SOURCE 1968 Source Group Reprocessing Consumptive Uses Manganese Metal Manganese Alloys Carbon Steel Cast Iron Welding Rods Nonferrous Alloys Batteries Chemicals Coal Oil Incineration and Other Disposal Sewage and Sludge Short Tons 325 8,946 4,340 2,770 24 60 90 300 1,950 7 9,271 7, 584 1,957 175 175 TOTAL 18,992 ------- -3- EMISSION FACTORS Mining 0. 2 Ib/ton of manganese mined Processing Manganese Metal Ferromanganese Blast Furnace Electric Furnace Silicomanganese Electric Furnace 25. 0 Ib/ton of manganese processed 4. 1 Ib/ton of ferromanganese produced 23. 9 Ib/ton of ferromanganese produced 69.4 Ib/ton of Silicomanganese produced Reprocessing Carbon Steel Blast Furnace Open-Hearth Furnace Basic Oxygen Furnace Electric Furnace Cast Iron Welding Rods Nonferrous Alloys Batteries Chemicals 22.5 lb/1,000 51 lb/1,000 44 lb/1,000 78 lb/1,000 330 lb/1,000 16 Ib/ton of 12 Ib/ton of 10 Ib/ton of 10 Ib/ton of tons of pig iron produced tons of steel produced tons of steel produced tons of steel produced tons of cast iron manganese processed manganese processed manganese processed manganese processed Consumptive Uses Coal 7. 7 lb/ 1, 000 tons of coal burned ------- -4- SOURCES OF MANGANESE Manganese is a hard and very brittle metal that melts at 1, 260 C. Its atomic weight is 54.93 and its specific gravity is 7.4. It is a relatively abundant element present in varying quantities in about ninety-five percent of the earth's crust. Ore deposits of commer- cial importance are found throughout the world. The most import- ant manganese-producing countries are Australia, Brazil, China, Gabon, Ghana, India, the Republic of South Africa, and the U.S.S.R.. The most common manganese minerals are pyrolusite, psilomela.ne, braunite, hausmannite, rhodonite, and rhodochrosite. They range in color from red to brown and black, containing from forty to seventy percent manganese. In the United States ores containing manganese are found in Arizona, Arkansas, Colorado, Maine, Montana, Minnesota, New Mexico, and South Dakota. Most of the ore mined in these states is manganiferous ore (5 to 35 percent Mn content). The United States is largely self- sufficient with respect to its use of manganiferous ore, but is almost entirely dependent on other countries for manganese ore (35 percent or more Mn content). ------- -5- Manganese is also commonly found associated with iron ores, usually in concentrations too low to make its commercial re- covery economically feasible. ------- SOURCES MANGANESE MATERIAL FLOW CHART - 1968 Short Tons - Mn Content USES 48,000 DOMESTIC PRODUCTION 1,053.000 IMPORTS 15.000 ^ EXPORTS 73.000 ^ GOVERNMENT STOCK ^ Q nnn INDUSTRY STOCK 1. 160. 000 , 850.000 FERRO- MANGANESE 120,000 SILICO- MANGANESE 10,000 SPIEGELEISEN 18. POO BATTERIES 60. 000 > CHEMICALS 26.000 ELECTROLYTIC METAL 66. 000 jr MISCELLANEOUS 149.000 1.001.000 ^ 744.000 ^ CARBON STEEL" 150,000 ALL OTHER STEEL 16.000 CAST IRON r\ WELDING RODS" > ^UNSUMER 10.000 NONFERROUS ALLOYS 18.000 J BATTERIES 60. 000 ^i CHEMICALS ' PROCESS LOSSES Figure I ------- -7- MATERIAL FLOW MINING Manganese produced in the United States during 1968 was approxi- mately 4 percent of the manganese consumed. Manganese ore (35 percent or more Mn) was produced and shipped from Montana and New Mexico. Manganiferous ore (5 to 35 percent Mn) was produced and shipped from Colorado, Minnesota, Montana, and New Mexico. MANGANESE PRODUCTION IN UNITED STATES l_l 1968 Manganese Content Short Tons Manganese Ore 6,000 Manganiferous Ore 42, 000 Total 48, 000 ]- Personal Communication;. U. S. Department of Interior; Bureau of Mines: August, 1970. ------- -8- IMPORTS AND EXPORTS During 1968 imports of manganese ore were principally from Brazil, the Congo, Gabon, Ghana, India, and the Republic of South Africa. The imports of manganese ore totaled 1,83J,210 short tons (gross weight), silicomanganese imports for consump- tion were 25, 142 short tons (gross weight), and ferroma.nga.nese imports were 207,677 short tons (gross weight) /. The man- ganese content of the imports was 1, 053, 000 short tons /. Exports of all forms of manganese during 1968 were 15, 000 short tons (Mn content) / including ferromanganese, manga- nese and manganese alloys, waste and scrap, ore, and concen- trates containing more than 10 percent manganese. MANGANESE STOCKS During 1968 industry stocks of manganese in all. forms in- creased 9, 000 short, tons (.Mn content), while government. stocks decreased 73,000 short tons (Mn content.) /. 1- Minerals Yearbook; Bureau of Mines; 1968. 2- Personal communication; U. S. Department of Interior; Bureau of Mines; August, 1970. ------- -9- PROCESSING The chief use of manganese ore (35 percent or more Mn) in the United States is in the production of manganese metal, ferro- manganese, silicomanganese, and spiegeleisen. These prod- ucts are used principally in the iron and steel industry. Other important uses of smaller quantities of the ore include its use in the manufacture of chemicals, batteries, welding rods and nonferrous alloys. During 1968, manganese ore was used in the manner shown in Table I. TABLE I USES OF MANGANESE ORE 1J 1968 Short, Tons Use Mn Content Manganese Metal (electrolytic) 26, 000 Ferromanganese 850, 000 Silicomanganese 120,000 Spiegeleisen 10,000 Chemical Manufacture 60, 000 Battery Manufacture 18,000 Miscellaneous 66, 000 1- Personal communication; U. S. Department of Interior; Bureau of Mines; August, 1970. ------- -10- REPROCESSING In the United States the principal use of manga.nese is in the pro- duction of carbon and alloy steels. Metallurgical.ly, it is used chief.ly as ferromanganese and to a lesser extent in the forms of silicomanganese, spiegeleisen and manganese metal. For battery manufacture, it is used in the form of manganese dioxide. In the chemical industry, manganese is used as an oxidizing agent in the manufacture of hydroquinone and for-the production of various chemicals including manganous oxide, manganous chloride, potassium permanganate, and manganese su.lfate. The consumption of manganese in the United States during 1968 has been reported at 1, 101, 000 short tons V. CARBON STEEL Manganese is used in steelmaking, chiefly, to counteract, the effects of sulfur; however, it also has other advantages. It has some deoxidizing power and, when added in certain proportions, it can. act to harden and reduce the plasticity of steel. Steels that contain too much sulfur tend to crack during rolling operations; a condition, known as "hot shortness". Excess sulfur 1- Personal communication; U. S. Department of Interior: Bureau of Mines; October, 1970. ------- -11- also tends to create surface imperfections during fabrication. The use of manganese in steelmaking effectively prevents these difficulties. Most of the unwanted sulfur combines with the man- ganese and is carried into the slag. In the United States the use of manganese in carbon steel during 1968 was 744, 000 short tons _/. OTHER STEEL In addition to its functions in the production of carbon steel, manganese is used as an alloying agent in special steels to produce harder and tougher metals for special applications. In plain carbon steel the manganese content is less than one percent, but in one group of extremely hard and tough alloy stee.ls the man- ganese content is from 10 to 14 percent. During 1968, the use of manganese in other steels was 150, 000 short tons /. CAST IRON The principal use of manganese-in^the~produclion of cast iron is 1- Personal communication; U. ~S.. Department of Interior; Bureau of Mines; October, 1970. 2- Personal communication; U. S. Department of .Interior; Bureau of Mines: August, 1970. ------- -12- t;o nullify the effects of sulfur. During 1968 the use of manganese in cast iron totaled 16, 000 short tons /. WELDING RODS Manganese, in the dioxide form, has important uses in the man- ufacture of welding rods and welding rod coatings. Its principal use is as an oxidizing agent. The MnC^ content of typical weld- ing rod coatings is in the order of 1J percent. During 1968 about 3, 000 short tons of manganese were used in the manufacture of welding rods /. NONFERROUS ALLOYS Manganese is important in many miscellaneous metallurgical applications. It is used in the production of aluminum and mag- nesium and it is alloyed with copper to make manganese bronze. It impa.rts stiffness and ha. rdness to aluminum and magnesium; manganese also increases the corrosion resistance of magnesium. The alloy, manganese bronze, is a. complex b:r.ass. It: has hot 1- Personal communication; U. S. Department of Interior; Bureau of Mines; October, 1970. 2- Personal communication; U. S. Department of Interior; Bureau of Mines: August, 1970. ------- -13- working properties, high strength, and abrasion resistance. It is used extensively for ship propellers, boat shafting and other similar applications. In the United States, the use of manganese in nonferrous alloys during 1968 was 10, 000 short tons _/. BATTERIES Synthetic ore is a term used chiefly to identify manganese di- oxide that is produced chemically or electrolytically for use in dry cell batteries. The Bureau of Mines define synthetic ore as a material that is the equivalent of, or better than, natural. ore, which can be put to the same uses, a.nd is produced by means other than ordinary concentrations, calcining, sintering, or nodulizing. In batteries, manganese dioxide acts as a depola.rizmg agent. Hydrogen released from the electrolyte of the cell tends to form around the carbon electrode and slow down the cell a.ction. Oxy- gen provided by the manganese dioxide corrects this condition by its reaction with the hydrogen. 1- Personal communication; U. S. Department of Interior; Bureau of Mines; October, 19?0. ------- -14- During 1968 manganese used in batteries totaled 18,000 short tons ./. CHEMICALS Manganese dioxide ores are important in the manufacture of manganese chemicals, ma.ny of which are used as oxidizing agents. Manganese sulfate is used in fertilizers, fertilizer additives, as a constituent of animaJ and poultry feeds, as a paint drier, as a coloring a.gent for ceramics and textiles, and as a ba.se for other chemicals. Manganous chloride is used in dyeing textiles, and as a ve.hic.le for alloying manganese with ma.gnesium. Manganous oxide is also used in a.nima] and poul- try feeds, fertilizers, and welding applications. Manganese used in the manufacture of chemicals du.rin.g 1968 totaled 60,000 short tons ./. 1- Persona] communication; U. S. Department of Interior; Bureau of Mines: August, 1970. ------- -15- EMISSIONS MINING Because of the marked differences in the manner in which man- ganese deposits occur, a wide variety of mining methods are used. In the United States, in recent years, high grade manganese ore has come from underground mines. On the other hand, manganif- erous ores are usually mined in the same manner as iron ores from the same district and, in the United States, this has meant open pit mines. Before 1950, very few of the world's manganese ore producers had milling plants other than simple crushing, screening and washing installations. This wa.s also the situation in the United States, ex- cept in the State of Montana where concentrating equipment was used for battery grade ores. Due to the recent high rate of indus- trial growth more producers have installed various k.inds of con-- ceint,rating equipment, many times including sintering a.nd nodu.hz- ing equipment to agglomerate fines and remove deleterious impurities. While this study was in progress, mining companies were con.i.a.cted concerning the quantity of ore mined, its manganese content, and the manganese emissions occuring during mining and concentration. It was found that records of manganese emissions to the atmosphere are not maintained. Mosi of those contacted indicated losses >,o the ------- -16- atmosphere are slight, occuring principally during ore handling or crushing and due to wind loss from tailings. Based on information obtained and observations made during visits to mining locations, the manganese emissions to the at- mosphere from sources of mining are estimated at 0. 2 pounds per ton of manganese mined. Manganese emissions to the atmos- phere during 1968 were 4.8 tons. ------- -17- PROCESSING In the United States the principal use of manganese ore (35 percent or more Mn) is in the production of manganese alloys and pure manga.nese metal. MANGANESE METAL The process currently used to produce pure manganese metal is an electrolytic process consisting of four principal steps: roasting of the ore, leaching, purification of the leach liquor, and electro- deposition Of the manganese. During roasting the primary object: is to convert all manganese to the oxide form and at the same time leave as much iron as possible as Fe^O.; however, most ores treated by this process are relatively low in iron and roasting is at a high temperature to achieve maximum recovery of manga- nese without regard to iron content. When the iron content is low it can be controlled by pH adjustment of the lea.ching acid. After grinding a.nd roa.sting, the ore is leached with anoJyte from the electrolytic cell. The concentration of the leach is adjusted by addition of ammonium sulphate to maintain a concentra.tion of about 140 grams/litre, and sulphuric acid to give a pH of about 2. 5. After solution, the leach liquor is neutralized to pH 6. 5 by adding ammonia, milk of lime, or calcined ore. On neutrali- zation of the leach liquor, iron and aluminum hydroxides are ------- -18- precipitated. Overall ex.trac.t.ion of manganese f:rom the ore is about 98 percent. The neutral leach liquor contains small quantities of numerous elements, such as arsenic, cobalt, copper, iron, lead, molybde- num, and zinc which must be removed prior to electrolysis. The removal is accomplished by first treating the liquor with hydrogen sulphide or ammonium sulphide, then fi.l.?:e.ring to remove the sulphides. At this point most of the impurities have been removed except colloidal sulphur a.nd small quantities of arsenic and molyb- denum. These are removed by the addition of iron in the form of copperas. The iron is oxidized at room temperature at a pH of 6. 5 to 7. 0 and ferric hydroxide is precipitated; the arsenic, molybdenum, and colloids are absorbed. At. this stage the solu- tion has been purified a.nd is ready for feeding to the el.ec.trolyr.ic cell. The cell, consists of an anode compartment and a. cathode com- partment separated by a diaphragm. The purified solution first enters the cathode compartment, then flows through a. canvas diaphragm into the a.node compartment and is discharged to a storage tank for reuse. The manganese is deposited at the cathode of the cell. ------- -19- The principal manganese emissions to the atmosphere that occur are due to handling, grinding, and roasting of the ore. The data obtained regarding two electrolytic plants indicate overall emissions average 25 pounds per ton of manganese pro- cessed. In the year 1968 the atmospheric emissions of manga- nese resulting from the production, of manganese metal totaled .325 tons. ------- -20- MANGANESE ALLOYS About 85 percent of the manganese ore consumed in the United States during 1968 was used to produce manganese alloys, the greater part of which was in the form of high, medium and low carbon ferromanganese. These and other alloys, including silicomanganese and spiegeleisen, are used principally by the steel industry. Air pollution controls have not been satisfactory in the ferroalloy industry; thus a more intensive effort will be required in order to provide adequate control of process emissions. There a.re numerous technical problems that must be solved and the addition of proper fume collection equipment is not the only requirement for a satisfactory long-range solution. There a.re many dust and fume producing operations. The dust (larger than 2 micron size) that results from raw material handline, as we 1.1. a.s that from crushing and sizing of the product, can be handled by conventional techniques; the major pollution problem is associated with, the ferroalloy furnaces and the collection of fume that is less than 2 microns in size. About 65 percent of the ferromanganese is made in blast furnaces and the remaining 35 percent in electric furnaces. The blast furnaces used in making ferromanganese are the same type as those used in making pig iron; quite often the same furnace is ------- -21- used to produce both products. Ferromanganese is often pro- duced by operating a pig iron furnace on manganese alloy pro- duction long enough to obtain a supply of the alloy, after which the blast furnace is returned to its normal operation of producing pig iron. The effluent from a ferromanganese blast furnace is reported to be a greater air pollution problem than that from an iron blast furnace _/. It is said to be the most, prolific pollution producer of any of the metallurgical processes _/. One investigator has reported that emissions from ferromanganese blast furnaces, if uncontrolled, are nearly ] 50 tons of dust per 1, 000 tons of metal. produced _/. Another invest-.i gator has reported the properties of ferromanganese blast furna.ce fume as shown i.r. Tab.le II. Electric furnaces used for making manganese ferroalloys are the same type as those used in making other ferroalloys a.nd, again, the furnace used is not always devoted, exclusively to making one particula.r product. Jr. fact, there is often some inter change- ability in scheduling production of the various ferroalloys. 1- Thring, N. W. and Sarjant, R. J. ; "Dust Problems of the Iron and Steel Industry"; Iron and Coal Traders Rev. ; Vol. 174: Mar. 29, 1957. 2- Wurts, T. C. ; "Industrial Sources of Air Pollution - Metallurgical"; PHS Publ. 654; 1959. ------- -22- TABLE II PROPERTIES OF PART1CULATE MATTER FROM A FERROMANGANESE BLAST FURNACE J/ Component Content % Manganese Iron Total alkali (as Na2O and Silicon dioxide Aluminum oxide Calcium oxide (CaO) Ma.gnesium oxide (MgO) Total, sulfur (as SO4) Carbon Pa.rticle Size (a.verage) Appa.rent Density 15 to 25 0. 3 to 0.5 8 to 15 9 to 19 3 to 11 8 to 15 4 to 6 5 to 7 .1. to 2 0. 3 micron ]2 J.b/cu. ft. 1- Bishop, C. A. et al; "Cleaning Ferromanganese B.la.st Furna.ce Gas"; Iron Steel Engine ei; 28; -Aug. 1951. ------- -23- When using the conventional submerged arc electric furnace to produce manganese alloys, large quan.titi.es of carbon monoxide a.re generated as a result of carbon, redxiction of metallic oxides. This gas, along with other primary gas due to moisture in the charge, reducing agent volatile matter, and various products of thermal decomposition, rises from the top of the furna.ce carrying furr.e and entrained micron-size particles of the charge. In an open furnace all of the carbon monoxide burns with induced air at the top of the charge, resulting in a, large volume of high. tempera.ture gas. In a closed furnace most of the carbon monox- ide is removed without combustion with air. Due to the steady state operation of the submerged arc furnace, gas generation is continuous. Additional fume is generated at the furnace ta.ph.oles, principally the result of air flow induced by heat transfer from the molten metal or sl.a.g. After the taphole, there are other sources of fume tha.t occur in. handling the metal. Because most furnaces are tapped intermittently, these fumes occur o.nly part of the operating time. As mentioned above, the fume size is generally below 2 microns; fume chemical analysis from the typical open-type furnace pro- ducing ferromanganese shows the manganese oxide content to be ------- -24- about: 33 percent. In addition to the numerous intermittent and continuous gas flows described, other factors also contribute to the problem of air pollution control. Manganese ores contain volatile mat- ter and moisture that disturb the smooth operation of the fur- nace. Sudden release of gas results in substantial charge ejection from the furnace. Normal gas flow from the typical closed furnace producing ferromanganese is approximately 160 to 170 scfm per mega- watt and peak flows may be 40 percent higher. From an open furnace with, a low hood the gas flow rate may be in the order of 3,.000 to 5, 000 scfm per megawatt. Atmospheric emissions resulting from the production of ferro- manganese in blast furnaces a.verage 4. 1 pounds of manganese per ton based on 95 percent control, 20 percent manganese in the particulate (Table II), and 410 pounds of particulate per ton of ferromanganese (uncontrolled) _/. During 1968 the manga- nese emissions totaled 1, 113 tons. Emissions to the atmosphere from electric furnaces producing 1- Office of Air Programs; Emissions report in progress; 1971. ------- -25- ferromanganese a.verage 23. 9 pounds of manganese per ton of ferromanganese produced including a 10 pound per- ton loss dur- ing handling, mixing, and other non-melting operations _/. .In the United States the manganese emissions from electric fur- na.ces during 1968 totaled 3, 669 tons. Atmospheric emissions due to the production of silicomanganese in electric furnaces averaged. 69.4 pounds of manganese per ton including a 10 pound per ton loss during handling, mixing, and other non-melting operations ./. During 1968 manganese emis- sions resulting from the production of silicomanga.n.ese totaled 4, 164 tons. ] Office of Air Programs; Reactive metals report in progress; J9?l. ------- -26- REPROCESS1NG More than ninety percent of the manganese used in the United States during 1968 was consumed by the steel industry in the production of carbon steel, stainless steel, and special steel alloys, The remainder was used in ma.king cast iron, nonfer- rous alloys, batteries, chemicals, and numerous other products. CARBON STEEL From the standpoint of air pollution, steel mills are very im- portant sources of manganese emissions. The basic steps in the production of steel include the partial removal of impurities when iron ore is reduced to pig iron in the blast furnace. Fur- ther purification takes place when pig iron and scrap are con- verted to steel in an open-hearth, a ba.sic oxygen, or an elec- tiic furnace. Other associated opera.tions include ore crushing, materials handling, sintering, palletizing a.nd scarfing. Blast Furnace - Commencing with i;he production of pig iron, ma.nganese is part of each principal ingredient charged into the blast furnace. It is in the iron and ma..ngajuferous ore, in the scrap, and in the slag recycled from the steel converter. More manganese enters the iron blast furnace through the sma.ll con- tent of manganese in some iron ores than through the deliberate ------- -27- addition of manganese. The pig iron emerging from the blast furnace contains about 70 percent of the manganese from the charge, and the other 30 percent is in the slag and ga.ses that are byproducts of the reaction. As the gas leaves the blast furnace, it contains large quantities of particulates a.veraging about 150 pounds per ton of pig iron /; however, it is subsequently cleaned and used as fuel. The gas cleaning is accomplished in two or. three sta.ges and the annual overall efficiency is a.n estimated 97 percent. During 1968, 140 million tons of net oies and agglomerates were consumed in producing 89 million tons of pig iron /. The estimated manganese content of the particula.te was 0. 5 percent. Emissions to the atmosphere totaled ], 000 tons, based on. 22.5 pounds of manganese per 1, 000 tons of pig iron. Open-Hearth Furna.ce - The nex:t step in steelmak.mg is to pro- duce steel using pig iron, home scrap, and purchased scrap. Three types of furnaces are commonly used; the open-hearth, the basic oxygen, and the electric furnace. Rega.rdless of the 1- "Air Pollutant Emission Fa.cr.or s "; Environmental Protection Agency; Preliminary Document; Apr. 1971. 2- Minerals Yearbook; Bureau, of Mi.ties; 1968. ------- -28- kind of furnace, the primary object of the operation is to reduce the impurities present in the charge to the limits specified for the melt. In the open-hearth furnace, steel is produced from a mixture of scrap (about 45 percent) and pig iron (about 55 percent) using oil, coke-oven gas, natural gas, tar, or producer gas to provide the required heat. The melting begins when the first scrap is charged and continues as solid material is added. After all the scrap has melted, molten pig iron is delivered and poured into the furnace. This step is followed by the ore and lime boil. Next the working period is employed to: (1) lower the phos- phorus and sulfur content; (2) eliminate carbon as rapidly as possible; and, (3) increase the heat for final deoxidation. It is during this process that the greatest loss of manganese oc- curs. About 80 to 90 percent emerges in the fume and slag. It oxidizes readily and tends to pass into the slag, rather than remaining with the product. The overall operating cycle of the open-hearth furnace is about 10 hours; fumes are discharged continuously at varying rates. In spite of the varying actions, average emission factors have been established for operation both with and without oxygen ------- -29- lancing. With oxygen lancing, the factor for uncontrolled emissions is 21 pounds of particulate per ton of steel. With- out lancing, the factor is 8 pounds per ton. The degree of emission control is estimated at 40 percent, and the average emission factor (controlled) for all open-hearth furnace opera- tions is 10. 2 pounds of particulate per ton of steel produced /. The mean particle size of the dust is generally considered to be 0. 5 micron _/ and a typical chemical analysis is shown in Table III. During 1968 the steel produced in open-hearth furnaces was 65 million short tons _/, and the manganese content of the particulate matter emitted was about 0. 5 percent. Manganese emissions to the atmosphere totaled 1, 660 tons based on 51 pounds per 1,000 tons of steel produced. Basic Oxygen Farnace - The basic oxygen furnace is a re- fractory-lined, cylindrical vessel that is mounted on trunions so that it can be rotated and placed in a horizontal or vertical 1- "Emissions, Effluents and Control Practices"; Environ- mental Protection Agency; Study in progress (unpublished); 1970. 2- Aberlow, E. B. ; "Modification to the Fontana Open-Hearth Precipitators"; JAPCA; 7_; May, 1957. 3- Minerals Yearbook; Bureau of Mines; 1968. ------- -30- TABLE III SPECTROGRAPHIC ANALYSIS OF PARTICULATE DISCHARGE FROM AN OPEN-HEARTH FURNACE 1/ , Approximate Amount Element ^ _ Percent Fe Zn Na K Al Ca Cr Ni Pb Si Sn Cu Mn Mg Li Ba Sr Ag Mo Ti V Remaining amount 10 to 15 1 to 2 1 to 2 5 5 2 2 5 5 1 0. 5 0. 5 0. 1 Trace Trace Trace 0.05 Trace Trace 0.05 These data are qualitative only and require supplementary quantitative analysis for actual amounts. 1- Air Pollution Engineering Manual; Public Health Service Publication No. 999-AP-40; p. 243; 1968. ------- -31- position as required during operation. When charged and in the vertical position, a stream of oxygen is supplied from overhead downward into the converter. The oxygen impinges on the liquid metal surface causing violent agitation and inti- mate mixing with the pig iron. During the operating cycle of about one hour, large quantities of gas and particulate are dis- charged from the furnace. The emission factor for the basic oxygen furnace has been es- timated at 46 pounds of particulate per ton of steel _/ and the degree of emission control at 97 percent. The mean particle size of the dust is 0. 7 micron (Table IV). During 1968 the steel produced in basic oxygen furnaces was 48 million short tons _/ and the estimated manganese content of the particulate emissions was 3.2 percent (Mn,O. 4.4 per- cent ao shown in Table V). Manganese emissions to the atmos- phere totaled 1, 060 tons during the yea.r, based on 44 pounds per 1, 000 tons of steel produced. 1- "Air Pollutant Emission Factors"; Environmental Protection Agency; Preliminary Document: Apr. 1971. 2- Minerals Yearbook; Bureau of Mines; 1968. ------- -32- TABLE IV PARTICLE SIZE DISTRIBUTION OF FUME FROM A BASIC OXYGEN FURNACE ]/ Microns Percent 0-0.5 20.0 0.5 - 1.0 65.0 1.0 - 15.0 15.0 TABLE V COMPOSITION OF FUME AND DUST FROM BASIC OXYGEN FURNACES 1 / Material Percent Fe2O3 90.0 Mn3O4 4.4 FeO 1. 5 SiO-, 1.3 CaO2 0.4 P205 0. 3 A12O3 0. 2 1- Gaw, R. G. ; "Symposium on Basic Oxygen Furnaces, Gas Cleaning"; Iron Steel Engr. ; 37; Oct. I960. ------- -33- Electric Furnace - Electric arc furnaces are well suited to the production of alloy steels and are used extensively for that purpose. They are refractory-lined, cylindrical vessels with large carbon electrodes passing through the furnace roof. Emissions generated during steelmaking consist of fume and dust emitted from the furnace during charging and refining. While charging the furnace, the top is open to receive the cold metal and the exposure of the1 cold charge to the high tempera- ture inside the furnace results in the generation of large quan- tities of fume. In general, the rate of fume release increases throughout the operation. Particulate emissions from electric arc furnaces have been estimated at 11 pounds per ton of steel with oxygen lancing, and 7 pounds per ton without _/. The particle size is shown in Table VI. The degree of control is estimated at 78 per- cent, and the average emission factor (controlled) at 2. 5 pounds per ton of steel produced. During 1968 the steel produced in electric arc furnaces was 16 million short tons /. The manganese content of the 1- Air Pollutant Emission Factors; Environmental Protection Agency; Preliminary Document; Apr. 1971. 2- Minerals Yearbook; Bureau of Mines; 1968. ------- -34- TABLE VI ELECTRIC ARC STEEL FURNACE FUME PARTICLE SIZE ..,. Percent Microns B 0-5 71. 9 67.9 5-10 8.3 6.8 10 - 20 6.0 9.8 20 and larger 13.8 15.5 A - Los Angeles County Air Pollution Control District, unpublished data, Los Angeles, California, 1950-51. B - Erickson, E. O. ; "Dust Control of Electric Foundries in Los Angeles Area"; Electric Furnace Steel Process; American Institute of Mining and Metallurgical Engi- neers; 11; 1953. ------- -35- particulate emissions is estimated at 3. 1 percent (4 percent MnO as shown in Table VII). Manganese emissions to the atmosphere totaled 620 tons, based on 78 pounds per 1, 000 tons of steel produced. OTHER STEEL Even though there is more manganese in certain alloy steels than in carbon steel, the production steps are essentially the same. The principal difference is that more of the alloying elements are added near the end of the cycle. Stainless steels are usually produced in an electric arc or high-frequency induction furnace. The largest tonnages are processed in an electric arc furnace of the Heroult type. This furnace is refractory-lined and the steel may be poured by tilting the entire furnace. After the working period the slag' is removed and a finishing slag is placed on the bath prior to the addition of manganese and other alloying elements. Manganese steels are made by any of the conventional steel- making processes with the exception that an acid-lined furnace may not be used. Only a base iron charge is melted in the acid-lined furnace. The ferromanganese or other manganese alloy is melted separately in a basic-Lined furnace and added ------- -36- TABLE VII TYPICAL EMISSIONS FROM AN ELECTRIC ARC FURNACE l/ Component Weight % Zinc Oxide (ZnO) 37 Iron Oxides 25 Lime (CaO) 6 Manganese Oxide (MnO) 4 Alumina (A12O ) 3 Sulfur Trioxide (SOJ 3 Silica (SiO2) 2 Magnesium Oxide (MgO) 2 Copper Oxide (CuO) 0. 2 Phosphorus Pentoxide (P^Cv) 0. 2 1- Coulter, R. S. ; "Smoke, Dust, Fumes Closely Controlled in Electrode Furnaces"; Iron Age; 173; Jan. 14, 1954. ------- -37- to the base iron in the ladle. Hadfield's method consists of adding molten ferromanganese to carbon-free blown iron. This is the most widely used method for producing manganese steel castings. Manganese emissions resulting from the production of alloy steels have been included with the emissions estimated for carbon steel. CAST IRON The principal use of manganese in cast iron is to nullify the effects of sulfur. In spite of recent advancements in the tech- nology of melting with electric arc and induction furnaces, the cupola is still the most widely used method for producing cast iron. The charge into the cupola furnace includes coke, scrap, and pig iron, each-containing some manganese. As air is in- troduced, the coke burns and causes the metallic charge in the furnace to melt. Part of the manganese oxidizes and part com- bines with sulfur to form manganese sulfide which is discharged in the slag. The rate of particulate emissions from gray iron cupolas has been reported as 4 to 26 pounds per ton of process weight not including emissions from handling, charging, or other non- melting operations. ------- -38- Based on information obtained from industry the pa.rticulate emission factor is estimated at 22 pounds per ton of process weight, including melting and non-melting operations. The manganese content of the particulate is 2 percent / and the degree of emission control approximately 25 percent. During 1968 the pig iron and scrap used by iron foundries totaled 16,788,000 short tons _/. Manganese emissions to the atmosphere due to the production of cast iron were 2, 770 tons. WELDING RODS Some welding rods and welding rod coatings contain manganese. In the coatings there is approximately 10 percent manganese dioxide as shown in Table VIII, and in aluminum welding rods there is as much as 1. 5 percent manganese. During the production of aluminum welding rods the manganese is added as a general purpose alloy for applications requiring moderate strength and good workability. An aluminum-rich alloy ingot containing the manganese is added to a charge of 1- Private communication with industrual source. 2- Minerals Yearbook; Bureau of Mines; 1968. ------- -39- TABLE VIII TYPICAL ANALYSIS OF WELDING ROD COATINGS Material SiO2 TiO2 MnO-, Fe2°3 MgO CaO co2 Moisture, organic volatile matter Other TOTAL Percent 20.5 41.5 10.9 8.8 5.9 2.5 1.4 6.9 1.6 100. 0 ------- -40- virgin aluminum and alloy scrap in a reverberatory furnace fired to a temperature of about 1,400 F. During the melting process the metal flows from the main furnace hearth to the holding hearth through a trough outside the furnace enclosure. The metal is then tapped and poured into ingots and cooled. Next, the ingots are heated and rolled in the blooming mill prior to milling in the rod mill. The product is finished by forging, swaging, or drawbenching. Based on information obtained from three industrial sources, manganese emissions to the atmosphere are estimated at 16 pounds per ton of manganese processed. During 1968 the man- ganese emissions resulting from the manufacture of welding rods totaled 24 tons. NONFERROUS ALLOYS In aluminum alloy production, manganese is dissolved in the molten aluminum to provide superior hardness, tensile strength, and corrosion resistance. Such alloys contain man- ganese at a level of less than 25 percent; one master alloy uses 4 or 5 percent. Magnesium producers use manganese chloride as a flux to im- part qualities of stiffness, hardness, and corrosion resistance. ------- -41- Also, magnesium can be melted and alloyed in steel pots when manganese is used since it inhibits alloying of the magnesium with the steel. When alloyed with copper and zinc, manganese bronze is formed. These bronzes, containing up to 3. 5 percent manga- nese, possess good tensile strength and are well known for their resistance to the corrosive effects of sea water. Manganese-copper-nickel alloys have a high affinity for carbon and rapidly'attack acid refractories. Therefore, melting should be conducted in a basic-lined high-frequency furnace. The basis of the furnace charge consists of ordinary carbon- free metallic manganese, ingot copper, nickel pellets, and returned scrap from previous melts, if available. Satisfac- tory results have been obtained by melting the copper and nickel under an oxidizing slag of manganese ore. Producers of nonferrous alloys contacted during this study stated their atmospheric emissions average about 12 pounds per ton of manganese processed. During 1968 manganese emissions to the atmosphere were 60 tons. ------- -42- BATTERIES An important use of manganese dioxide is as a depolarizing agent in the ordinary dry cell battery. Hydrogen released from the electrolyte of the cell tends to form around the car- bon electrode, slowing the action of the cell. This condition is corrected as the hydrogen combines with the oxygen that is provided by manganese dioxide contained in the cell mix. The main steps in a dry cell battery-making process are dia- gramed in Figure II. Emissions to the atmosphere are principally during the early stages of production. Manganese dioxide, calcined manganese, and other dry ingredients are emptied from vats and containers into a dry mixer. These mixed ingredients then travel in buc- ket elevators to the hopper where they are dumped and enter the wet mixer. Information obtained from manufa.cturers of dry cell batteries shows that their manganese emissions to the atmosphere aver- age 10 pounds per ton of manganese processed. During 1968 the atmospheric emissions were 90 tons. ------- -43- FLOW DIAGRAM BATTERY MANUFACTURING Manganese dioxide, calcined manganese, graphite carbon black, ammonium chloride, and vita film Zinc chloride and ammonium chloride solution Battery cases Zinc and ammonium chloride solution Carbon rod added by machine Wet Mixer Pulverizer Paste Filling Machine Solution Filling Machine Combining Machine Figure II ------- -44- CHEMICALS AND OTHER USES Manganese ore, mainly in dioxide form, is used in the chemical industry as an oxidizing agent in the manufacture of hydroqui- none and for the production of various manganese chemicals, including potassium permanganate, manganese sulfate, manga- nous chloride, and manganous oxide. It is used in the lea.ching of uranium and zinc ores, in fertilizers as a trace element, in animal and poultry feed as a supplement, in pharmaceuticals, frits, glass, ceramics, and to give a variety of coloring effects to face brick. For certain of these applications the ore is used directly; for others, it may be processed into compounds or salts of manganese prior to use in the final product. Hydroquinone is important as a photographic developer. Per- manganates have many uses in a wide variety of applications. They are used in the chemical industry in air pollution control for sulfides and mercaptans, in water treatment, as bacteri- cides and pesticides, and for odor control in barnyards. Potas- sium permanganate is a powerful oxidant. Manganese sulfate is used in a multitude of commercial prod- ucts; one of the largest areas is as a fertilizer or fertilizer additive. It is also important as a constituent of animal and ------- -45- poultry feeds, fungicides, paint driers, coloring agents for the textile and ceramic industries, and is bften used as a base for the production of other manganese chemicals. Approximately 10, 000 tons of manganese are used annually in the production of fertilizers. Manganous oxide is also found in fertilizers and in animal and poultry feeds. In addition it is used in certain welding applica- tions. In dyeing textiles, making welding rod fluxes, and in alloying manganese with magnesium, manufacturers use man- ganous chloride. Another area of interest is the molybdenum-manganese process of joining ceramics to metal, better known as the moly-manganese process. It is one of the most widely employed methods in elec- tronic applications. A thin coating (0. 005 to 0. 002 inch) of a fine suspension of molybdenum and manganese is fired on the ceramic in a reducing atmosphere at temperatures approaching 3, 000 F. Then a coating of nickel and copper is electroplated over the molybdenum and manganese, and is wetted by a brazing alloy. The resulting metal-ceramic bonds ha.ve a better high- temperature strength than those formed by any other method. Tensile strength of 20, 000 pounds per square inch has been re- ported. ------- -46- Fuel additives of organic manganese compounds have been patented and tested. The most successful antiknock compound is methylcyclopentadienyl manganese tricarbonyl, which is mixed with tetraethyl lead to increase the octane rating of gas- oline. A typical mixture is composed of the following ingredi- ents: 57.5 percent tetraethy] lead; 7.0 percent methylcyclo- pentadienyl manganese tricarbonyl; 16. 7 percent ethylene di- bromide; 17.6 percent ethylene dichloride; and 1.2 percent other additives such as dye and inert materials. Various methods of using manganese to remove air pollutants ha.ve been suggested. Manganese nodules from the ocean floor can be loosely packed in a column through which a gas passes, causing a reaction with the sulfur dioxide in the gas to produce manganese sulfate. One-third of the manga.nese can be re- covered from the sulfated nodules by ]eaching with weak su.l- furic acid. There is no reliable information regarding the average manga- nese emissions that occur during the production, of compounds and the subsequent manufacture of products that contain man- ganese. However, a few rough estimates of atmospheric emis- sions have been obtained from people in industry. In this report ------- -47- manganese emissions to the atmosphere are 10 pounds per ton of manganese processed. During 1968 the manganese in chemicals and other miscellaneous uses was 60, 000 tons, and atmospheric emissions were an esti- mated 300 tons. ------- -48- CONSUMFTIVE USES The largest manganese emissions to the atmosphere during consumptive use are those due to the combustion of coal and oil. Others that occur are usually of such a nature that atmos- pheric emissions are negligible. COAL The manganese content of various samples of coal has been re- ported as shown in Table IX, and the average concentration in domestic coal is about 26.4 ppm. Coal consumed in the United States during 1968 was 508,990, 000 tons (bituminous and anthra- cite) /; therefore, the manganese in coal was about 1.3,400 tons. Since fly ash is about 65 percent of total ash and approxi- mately 75 percent of fly ash is collected, the manganese emis- sions to the atmosphere should be 16 percent of the manganese contained in the coal, or 2, 150 tons. A study has been made regarding emissions from coal fired power plants and the emissions of manganese have been recorded. Six power boilers were tested, each a different type, and each value reported was the average of at least two tests. Two of 1- Minerals Yearbook; Bureau of Mines; 1968. ------- TABLE IX AVERAGE MANGANESE CONTENT IN ASH QF COAL Region Frequency of Mn Content Ash Content Detection - % of Ash - % of Coal - % Eastern Province 100 0. 026 9. 3 Interior Province 100 0.0325 10.5 Western States 100 0.0212 9.8 Average Manganese Content of Coal Mn Content of Coal -% 0. 0024 0. 0034 0.0021 0. 00264 NOTE - The above table based on "Spectrochemical Analyses of Coal Ash for Trace Elements" Table 1; Bureau of Mines RI7281; July, 1969. ------- -50- the boilers were fired with Illinois coal; two burned Pennsyl- vania coal; one used some coal from Ohio and some from West Virginia; one burned part Kentucky and part West Virginia coal. Manganese concentrations in the fly ash samples taken before fly A ash collection ranged from 4. 2 to 17. 0 grains per scf x 10 . A The average was 8.47 grains per scf x 10' . In the samples taken after fly ash collection, the manganese concentration ranged from 0. 26 to 1. 6 grains per scf x 10 and the average was 0. 92 grains per scf x 10"4 _/. Based on 508, 990, 000 tons of coal consumed in the United States during 1968, 90 percent application of control, 160 scf of flue gas per pound of coal and the average concentration in fly ash stated above, the manganese emissions for 1968 due to the combustion of coal are calculated at 1, 950 tons. In this report the figure of 1,950 tons is used as manganese emis sions to the atmosphere due to the combustion of coal. 1- Cuffe, Stanley T. and Gerstle, Richard W. ; "Emissions from Coal Fired Power Plants"; Public Health Service Publication No. 999-AP-35; 1967. ------- -51- OIL In order to estimate manganese emissions to the atmosphere resulting from the combustion of fuel oil, it was necessary to determine the manganese content as well as the quantity of oil received from numerous foreign and domestic sources. Analy- ses of more than 400 samples of crude and residual oils were obtained from the major oil companies and the utilities along the east coast of the United States. The data show that nearly all crude oil contains some manga- nese; the concentrations ranging from nearly zero to more than 2,000 ppm. It also shows that residual oil contains a higher percentage of manganese than the crude. When oil is refined the manganese and other trace metals tend to concen- trate in the heavy fractions; the residual oil, the road oil, and the asphalt. According to the information obtained from oil companies, the residua] fuel oils may be expected to contain 4 to 6 times as much manganese as the crude oils. Unfortunately, most of the analyses available weve of crude oil. They show oil from California, Colorado, and Utah con- tains more manganese than that from Kansas, Oklahoma, and Texas (Table X). Residual fuel oil from the United States con- tains about 158 ppb manganese, while that from the Middle East ------- -52- TABLE X MANGANESE CONTENT OF DOMESTIC CRUDE Oi:LS Source Arkansas California Colorado Kansas Montana New Mexico Oklahoma Texas Utah Wyoming Manganese Content - ppb 120 138 208 13 5 21 30 29 1,445 44 NOTE - The above table is based on private communication with industrial sources. ------- -53- averages about 120 ppb. Analyses of eight residual fuel oils from South America show that manganese is below the limit of detection. During 1968 the demand for residual fuel oil in the United States was 668, 239, 000 barrels. Imports were 409, 928, 000 barrels, and the remainder were principally from domestic production V. Imports were about 92 percent from South America and the West Indies; 8 percent from the Middle East, Canada, and other countries /. MANGANESE IN RESIDUAL OIL, CONSUMED IN THE UNITED STATES - 1968 g Quantity Mn Content Mn Content Barrels ppb Tons United States South America Middle East and Other TOTAL 258, 311, 376,000, 33,928, 668,239, 000 158 000 000 120 000 7 - 1 8 1- "Crude Petroleum, Petroleum Products, and Natural-Gas- Liquids: 1968"; Petroleum Statement, Annual; Mineral Industry Surveys; Bureau of Mines; Washington, D. C. 2- Based on import data from the Office of Air Programs; Durham, N. C. ------- -54- In the past power boilers designed to burn fuel oil were not us- usually equipped with air pollution control apparatus. It was only the coal fired or the combination coal-oil units that included mechanical collectors and/or electrostatic precipitators. When these combination units burn oil, only a small part of the particu- late matter becomes an atmospheric emission. The records show that 669 million barrels of residual oil were consumed in the United States during 1968. The electric utili- ties used 28 percent of the total, or 185 million barrels, and were the only users with any significant degree of air pollution control. A survey was conducted and it was determined that the electric utility percent of control when burning fuel oil was about 32 percent. Based on 10 percent overall control, the manganese emissions to the atmosphere during 1968 due to the combustion of fuel oil totaled 7 tons. ------- -55- INCINERATION AND OTHER DISPOSAL Information concerning sewage and sludge was the only data available during this study regarding atmospheric emissions of manganese that result from incineration or disposal. SEWAGE AND SLUDGE A recent report concerning the burning of sewage and sludge indicates the present burning rate in the United States is about Z, 000 tons per day /. Based on a manganese content of 240 ppm (dry weight) / the atmospheric emissions currently total 175 tons of manganese per year. 1.- Private communication from the Federal Water Pollution Control Authority. 2- Clark, L. J. and Hill, W. L. ; "Occurrence of Manganese, Copper, Zinc, Molybdenum, and Cobalt in Phosphate Fertilizers and Sewa.ge Sludge"; J. Assoc. Official Agr. Chemists; 4]; pp. 63.1-637; 195*T ------- -56- APPENDIX A COMPANIES DEALING IN MANGANESE AND MANGANESE COMPOUNDS ALABAMA Woodward Company LOCATION Woodward CALIFORNIA American Potash and Chemical Corp. Capco Alloy Steel Company Electronic Space Products, Inc. Metal Organics, Inc. Wilson and George Meyer ;& Company Mountain Copper Company, Ltd. Los AngeJ.es Los Angeles Los Angeles San Carlos So. San Francisco Martinez CONNECTICUT Anaconda American Brass Company Waterbury Michael Schiavone & Sons, Inc. New Haven D. C. Hercules, Inc. Wa shington GEORGIA Frank Smith Tennessee Corporation Carre rsville Atlanta ILLINOIS Amsco Division of Abex Corp. Atlantic Chemicals and Metals Co. Carus Chemical Company Ben J. Harris and Company Hickma.n, Williams and Company Kraft Chemical Company Chicago Heights Chicago LaSalle Chicago Heights Chicago Chicago ------- -57- R. Lavin and Sons, Inc. Miller and Company Stresen-Reuter International Wilson Labs Chicago Chicago Bensonville Chicago IOWA Bonewitz Laboratories, Inc. Burlington MARYLAND Ansam Metals Corporation Baltimore Chemetals Division, Diamond Shamrock Chemical Company Baltimore Glidden Metals Group Baltimore Manganese Chemical Corporation Baltimore MICHIGAN Frankel Company, Inc. Haviland Products Company Detroit Grand Rapids MINNESOTA Manganese Chemical Corporation Minneapolis MISSOURI Mallinckrodt Chemical Works St. Louis NEW JERSEY Advance Division, Carlisle'Chemical Works, Inc. A and S Corporation J. T. Baker Chemical Compa.ny Leonard J. Buck, Inc. Eastern Chemical Corporation New Brunswick Verona Phillips burg Jersey City Pequannock ------- -58- General Metallic Oxides Company Hummel Chemical Company, Inc. Import Chemical Company Metallurgical International Inc. Nitine, Inc. Octagon Process, Inc.. Shieldalloy Corporation Taylor-Wharton Company Tenneco Chemicals, Inc. Troy Chemical Corporation Var-Lac-Oid Chemical Company Max Zuckerman and Sons, Inc. Jersey City Newark Jersey City New Shrewsbury Whippany Edgewater Newfield High Bridge Piscataway Newark Elizabeth Owings Mills NEW YORK Airco Alloys and Carbide Division Air Reduction Company, Inc. Allied Chemical Corporation Alloys Unlimited, Inc. American Smelting and Refining Co, Anchor Metal Company, Inc. Anglo-American Metal & Fe.rro Alloy Corporation Associated Metals and Minerals Corp. Atomergic Chemetals Company H. J. Baker Brothers, Inc. Be]mont Smelting & Refining Works, Inc. Berkshire Chemicals, Inc. Charles B. Chrystal Company, Inc. City Chemical Corporation Cometals, Inc. Continental Ore Corporation Debevoise-Anderson Company, In.c. Faesy and Besthoff, Inc. Fallek Products Company, Inc. Galla rd-Schlesinger Chemi ca.l Manufacturing Corporation. M. Golodetz and Company W. R. Grace and Company Herzog Metal Corporation Hooker Chemical Corporation Industrial Chemical and Dye Corp. A. Johnson and Company, Inc. Kingston Chemical Company, Inc. Niagara Falls New York New York Melville New York Brooklyn New York New York Carle Place, L.I. New York Brooklyn New York New York New York New York New York New York New York New York Carle Place, New York New York New York Niagara Falls New York New York New York L.I. ------- -59- Kolon Trading Company, Inc. Mackenzie Chemical Works McKesson Chemical Company Messina, Inc. Metallurg Alloy Corporation Milwaukee Tool and Equipment Co. Wm. H. Muller and Company, Inc. Naftone, Inc. The New Jersey Zinc Company Ore and Ferro Corporation Pancoast International Corporation Charles Pfizer and Company, Inc. Philipp Brothers Primary Industries Corporation Progressive Alloys Corporation The Selney Company, Inc. Semi Alloys, Inc. E. M. Sergeant Pulp and Chemical Company, Inc. Smith Chemical and Color Co. , Inc. Sterwin Chemicals, Inc. C. Tennant Sons and Company The Titan Industrial Corporation Union Carbide Corporation, Ferro- alloys Division Union Carbide Corporation, Mining and Metals Division United Mineral and Chemical Corp. Winth.rop Laboratories Witco Chemical Corporation New York Central Islip New York Bedford Hills New York New York New York New York New York New York New York New York New York New York Brooklyn New York Mount Vernon New York Brooklyn New York New York New York New York New York New Yor k New York New York NORTH CAROLINA Mineral Research and Development Corp. Concord OHIO Barium and Chemicals, Inc. Steubenville Chemetron Corporation Cleveland Chemical. Division Ferro Corporation Bedford Glidden-Du.r.kee Division Cleveland Globe Metallurgical Division, Interlake Steel Corporation Cleveland ------- -60- Haley Smelting, Inc. Hall Chemical Company Harshaw Chemical Company McGean Chemical Company Mooney Chemicals, Inc, Oglebay-Norton Company Ohio Ferro-Alloy Corporation Pickards Mather and Company I. Schumann and Company S. C. M. Corporation Shepherd Chemical Company C. L. Zimmerman Company Parma Wickliffe Cleveland Cleveland Cleveland Cleveland Canton Cleveland Bedford Cleveland Cincinnati Cincinnati PENNSYLVANIA Bethlehem Steel Corporation Bram Metallurgical Chemical Co. Brass and Copper Sales, Inc. C. E. Minerals Ceramic Color and Chemical Manufacturing Company Chase Chemical Corporation Chemalloy Company, Inc. Chromium Mining and Smelting Corp. Colonial Metals Company Damascus Steel Casting Fisher Scientific Company Foote Mineral Company Gano Moore Company, Inc. O. Hommel Company Lavino Division, International Minerals and Chemicals Corp. Mercer Alloys Metallurgical Products Company J. Meyer and Sons, Inc. Prince Manufacturing Company Reading Alloys, Inc. Fra.nk Samuel and Company, Inc. Shenango, Inc. Taylor Wha.rton Company, Division of Harsco Corporation Charles A. Wagner Company, Inc. Welding Wholesale Company Bethlehem Philadelphia Philadelphia King of Prussia New Brighton Pittsburgh Bryn Mawr Pittsburgh Columbia New Brighton Pittsburgh Exton Wynnewood Pittsburgh Philadelphia Greenville Philadelphia. Philadelphia Bowmanstown Robesonia. King of Prussia Pittsburgh Easton Philadelphia Philadelphia ------- -61- TENNESSEE Eastman Chemical. Products, Inc. Kingsport Foote Mineral Company Knoxville (American Meta] Market, Aug. 10, 1970; Thorny s Register, Dec. 1968 Ed. ) ------- BIBLIOGRAPHIC DATA SHEET 1. lU-port No. APTD-1509 3. Recipient's Accession No. 4. Title and Subtitle National Inventory of Sources and Emissions: Manganese - 1968 5- Report Date August 1971 6. 7. Author(s) 8- Performing Organization Kept. No. 9. Performing Organization Name and Address W. E. Davis & Associates 9726 Sagamore Road Leawood, Kansas 10. Project/Task/Work Unit No. 11. Contract/Grant No. CPA 70-128 12. Sponsoring Organization Name and Address ENVIRONMENTAL PROTECTION AGENCY Office of Air Programs Durham, North Carolina 13. Type of Report & Period Covered 14. 15. Supplementary Notes 16. Abstracts The inventory of atmospheric emissions has been prepared to determine the nature, magnitude, and extent of the emissions of manganese in the United States for the year 1968. The flow of manganese in the U. S. for that .year has been traced and charted. The consumption was 1,150,000 tons while domestic production was only 48,000 tons. Imports principally from Brazil, Gabon, Republic of South Africa, Congo, Guyana, India Angola, and Australia totaled 1,053,000 tons. Emissions to the atmosphere during the year were 18,992 tons. About 47% of the emissions resulted from the production of ferroalloys and about 37% from the production of iron and steel. The combustion of coal was also a significant source of manganese emissions. 17. Key Words and Document Analysis. 17a. Descriptors Air pollution Emission Inventories Sources Manganese Consumption Production International trade Industries Reprocessing 17b. Identificrs/Open-Ended Terms Year 1968 United States Utilization Metallurgical furnaces 17c. COSATI Field/Group 13B 18. Availability Statement FORM NTIS-35 (REV. 3-721 Unlimited 19..Security Class (Tliis Report) UNCLASSIFIED 20. Security Class (This Page UNC1.ASS1FIFD 21. No. of Pages 68 22. Price USCOMM-DC I4Q52-P72 ------- INSTRUCTIONS FOR COMPLETING FORM NTIS-35 (10-70) (Bibliographic Data Sheet based on COSATI Guidelines co Format Standards for Scientific and Technical Reports Prepared by or for the Federal Government, PB-180 600). 1. 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