United States Office of Air Quality EPA-450/4-84-007g Environmental Protection Planning And Standards Agency Research Triangle Park, NC 27711 July 1984 AIR EPA LOCATING AND ESTIMATING AIR EMISSIONS FROM SOURCES OF CHROMIUM L &E EPA-450/4-84-007G July 1984 Locating and Estimating Air Emissions From Sources of Chromium U.S ENVIRONMENTAL PROTECTION AGENCY Office of Air and Radiation Office of Air Quality Planning and Standards Research Triangle Park, North Carolina, NC 27711 This report has been reviewed by the Office of Air Quality Planning and Standards, U.S. Environmental Protection Agency, and has been approved for publication as recieved from Radian Corporation. Approval does not signify that the contents necessarily reflect the views and policies of the Agency, neither does mention of trade names or commercial products constitute endorsement or recommendation for use. TABLE OF CONTENTS Page List of Tables .......................................................... v List of Figures ...................................................... viii 1. Purpose of Document ......................................... 1 2. Overview of Document Contents ............................... 3 3. Background ........................................... 5 Nature of Pollutant ................................... 5 Overview of Production and Use ........................ 9 Chromium production ............................. 9 Chromium uses .................................. 19 References for Section 3 ............................. 27 4. Chromium Emission Sources .................................. 29 Direct Sources of Chromium ........................... 30 Chromite ore refining .......................... 30 Ferrochromium production ....................... 33 Refractory manufacture ......................... 52 Chromium chemicals manufacture ................. 64 Chromium plating ............................... 77 Steel production ............................... 91 Electric arc furnaces and argon-oxygen decarburization vessels ................. 91 Basic oxygen process furnaces ............ 124 Open hearth furnaces ..................... 135 Leather tanning ..................................... 140 Indirect Sources of Chromium .............................. 147 Coal and oil combustion ............................. 147 Cement production ................................... 160 Municipal refuse and sewage sludge incineration ...................................... 165 iii TABLE OF CONTENTS (Continued) Page Cooling towers ...................................... 174 Asbestos mining and milling ......................... 181 Coke ovens ......................................... 189 References for Section 4 .................................. 196 5. Source Test Procedures .................................... 209 Literature Review of Sampling Methods ............... 209 Literature Review of Analytical Methods ............. 210 Extraction procedures ......................... 210 Analysis procedures ........................... 213 References for Section 5 .................................. 221 iv LIST OF TABLES Table Page 1 Physical Properties of Chromium ............................ 6 2 Oxidation States of Chromium in Various Chromium Compounds and the Major Physical Properties of These Compounds .......................................... 7 3 Composition of Typical Ferrochromium Alloys and Chromium Metal ...................................... 13 4 List of Commercially Produced Secondary Chromium Chemicals and their General Uses ........................ 18 5 Major Chromium Uses and Key Chromium Chemicals Involved .... 25 6 Chromium Emission Factors for Chromite Ore Refining ........ 33 7 Chromium Emission Factors from Processing of Raw Materials at Ferrochrome Plants ..................... 48 8 Chromium Emission Factors from Finishing Operations and Product Handling at Ferrochrome Plants .............. 50 9 Chromium Emission Factors for Electric Arc Furnaces Used to Produce Ferrochromes ............................ 51 10 Location of Plants Producing Chromium Ferroalloys as of 1980 .......................................... 53 11 General Chromium Emission Factors for the Refractory Industry ..................................... 63 12 Controlled Chromium Emission Factors for the Refractory Industry .................................... 65 13 Locations of Plants Producing Chromium Refractory Materials .......................................... 66 14 Chromium Emission Factors for Sodium Dichromate Manufacturing .......................................... 75 15 Chromium Emission Factors for Chromic Acid Production ...... 76 16 Locations of Sodium Chromate and Sodium Dichromate Manufacturing Plants .................................... 77 17 Locations of Companies Producing Secondary Chromium Chemicals .......................................... 78 18 Typical Chromium-Plating Conditions Using Conventional Baths ...................................... 87 v LIST OF TABLES (Continued) Table Page 19 Uncontrolled Chromium Emission Factors from One Hard Chromium Plating Facility .......................... 90 20 Fugitive Emissions Capture Technology Combinations (Carbon and Specialty Steel EAF) ....................... 112 21 Fugutive Emissions Capture Technology Combinations (Specialty Steel AOD) .................................. 115 22 Uncontrolled Chromium Emission Factors for Electric Arc Furnaces (EAFS) and Argon-Oxygen Decarburization Vessels (AODS) ......................................... 117 23 Chromium Content of Electric Arc Furnace Dust for Each Step of Furnace Operation at One Facility ......... 118 24 Locations of Electric Arc Furnaces in the United States -- 1981 .................................. 119 25 Location of Steel Plants with EAFs and AOD Vessels -- 1981 .................................... 122 26 Locations of Argon-Oxygen Decarburization (AOD) Vessels in the United States in 1981 ................... 123 27 Locations of Basic Oxygen Process Furnaces (BOPFS) in the Iron and Steel Industry ............................ 137 28 Locations of Steel Plants with Open Hearth Furnaces ....... 141 29 Largest U. S. Leather Tanning Facilities and Locations .... 145 30 Chromium Content of Domestic Coals by Type ................ 148 31 Chromium Content of Domestic Coals by Source .............. 148 32 Chromium Content of Various Crude and Fuel Oils ........... 149 33 Chromium Collection Efficiencies for Electrostatic Precipitators ......................................... 152 34 Chromium Collection Efficiencies for Fabric Filters ....... 152 35 Chromium Collection Efficiencies for Wet Scrubbers ........ 153 36 Chromium Emission Factors for Oil Combustion .............. 155 37 Chromium Emission Factors for Coal Combustion ............. 157 vi LIST OF TABLES (Continued) Table Page 38 Chromium Emissions Factors for Cement Plants .............. 164 39 Design Temperature Profile of a Sewage Sludge Multiple Hearth Furnace .............................. 170 40 Emission Factors for Chromium from Municipal Refuse and Sewage Sludge Incinerators .................. 173 41 Population of Municipal Refuse and Sewage Sludge Incinerators in the United States in 1983 .............. 175 42 Chromium Emission Factors for Fresh Water Utility Cooling Towers ......................................... 180 43 Chromium Emission Factors for Asbestos Mining and Milling ......................................... 188 44 Locations of Asbestos Mines and Mills in 1981 ............. 190 45 Coke Plants in the United States as of January 1980 ....... 193 46 Instrumental Methods for the Determination of Chromium ......................................... 214 vii LIST OF FIGURES Figure Page 1 Simplified flowchart for the production of chromium compounds and metallic chromium from chromite ............ l0 2 Industrial recycling/reuse flow of chromium scrap .......... 15 3 Primary and secondary use distribution of chromium in the United States ..................................... 20 4 Final consumer use distribution of chromium in the United States in 1981 .................................... 21 5 End use tree for sodium dichromate in 1982 ................. 24 6 Flow chart for chromite ore-refining ....................... 31 7 Flow chart of ferrochrome production by the electric arc furnace process ...................................... 35 8 Open electric arc furnace .................................. 37 9 Semisealed electric arc furnace ............................ 39 10 Sealed electric arc furnace ................................ 40 11 Typical flow chart for the production of low-carbon ferrochrome by the exothermic silicon reduction process .......................................... 42 12 Vacuum furnace for the production of low-carbon ferrochrome .......................................... 43 13 Flow chart for production of chromium-containing basic brick by casting and pressing processes ............ 55 14 Flow chart for production of chromic oxide bricks by casting and pressing processes ........................ 56 15 Flow chart of production of unformed refractories .......... 57 16 Flow chart for the production of sodium chromate ........... 69 17 Flow chart for the production of sodium dichromate from chromate liquor ..................................... 70 18 Flow chart for chromic acid production ..................... 73 19 Flow chart for decorative chromium plating on a steel substrate .......................................... 83 20 Flow chart for hard chromium plating ....................... 84 21 Cut-away