Prepublicatian issue for EPA libraries
and State Solid Waste Management Agencies
ASSESSMENT OF INDUSTRIAL HAZARDOUS WASTE PRACTICES,
INORGANIC CHEMICALS INDUSTRY
This final report (SW-IO^c) on work performed under
solid waste management contract no. 68-01-2246
was prepared for the
Office of Solid Waste Management Programs
and is reproduced as received from the contractor
•
Copies of this report will be available from the
National Technical Information Service
U.S. Department of Commerce
Springfield, Virginia 22151
U.S. ENVIRONMENTAL PROTECTION AGENCY
1975
-------
NOTICE
This report has been reviewed by the Hazardous Waste Management Division,
Office of Solid Waste Management Programs, EPA, and approved for publication.
Approval does not signify that the contents necessarily reflect the views and policies
of the Environmental Protection Agency, nor does mention of trade names or com-
mercial products constitute endoresement or recommendation for use.
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TABLE OF CONTENTS
Section Page
1.0 INTRODUCTION . 1-1
1.1 Program Methodology 1-2
2.0 SUMMARY . . . . 2-1
2.1 Executive Analysis 2-1
2.2 General Summary 2-2
3.0 DISCUSSION OF THE INORGANIC CHEMICALS
INDUSTRY 3-1
3.1 Introduction 3-1
3.2 Economic Structure and Products of the Alkalies
and Chlorine Industry, SIC 2812 3-1
3.3 Economic Structure and Products of the Industrial
Gases Industry, SIC 2813 3-2
3.4 Economic Structure and Products of the Inorganic
Pigments Industry 3-5
3.5 Economic Structure and Products of the Industrial
Inorganic Chemicals, N.E.C., Industry,
SIC 2819 3-5
3.6 Individual Chemical Processes and Waste Streams . . 3-7
3.7 Future Inorganic Chemical Industry Developments. . 3-13
4.0 INDUSTRY CHARACTERIZATION 4-1
4.1 Categorization 4-1
4.2 Characterization of SIC 2812, Alkalies and
Chlorine Industry 4-2
4.3 Characterization of SIC 2813, Industrial Gases
Industry 4-8
4.4 Characterization of SIC 2816, Inorganic Pigments
Industry 4-14
4.5 Characterization of SIC 2819, Inorganic Chemicals,
N.E.C., Industry 4-20
• • •
in
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TABLE OF CONTENTS - continued
Section
Page
5.0 WASTE CHARACTERIZATION 5-1
5.1 Introduction. . 5-1
5.2 Alkalies and Chlorine (SIC 2812) 5-4
5.3 Industrial Gases (SIC 2813) 5-23
5.4 Inorganic Pigments (SIC 2816) 5-33
5.5 Other Industrial Inorganic Chemicals (SIC 2819) 5-78
6.0 TREATMENT AND DISPOSAL TECHNOLOGY 6-1
6.1 Treatment and Disposal in Alkalies and Chlorine
Manufacture (SIC 2812) 6-3
6.2 Treatment and Disposal in Inorganic Pigments
Manufacture (SIC 2816) 6-4
6.3 Treatment and Disposal in the Manufacture of
Miscellaneous Inorganic Chemicals (SIC 2819) . . . 6-5
6.4 Treatment and Disposal Technology Levels as
Applied to Hazardous Wastes Generated by the
Manufacture of Specific Chemicals 6-7
6.5 General Description of Present Treatment
Technologies 6-21
6.6 On-Site Vs. Off-Site Disposal 6-30
6.7 Safeguards Used in Disposal 6-36
6.8 Private Contractors and Service Organizations . . . 6-38
6.9 Contractor Treatment/Disposal Costs 6-38
7.0 COST ANALYSIS 7-1
7.1 Cost References and Rationale 7-1
7.2 Definition of Technology Levels 7-6
7.3 Costs for Treatment and Disposal of Land Destined
Hazardous Wastes 7-6
8.0 REFERENCES 8-1
9.0 GLOSSARY 9-1
10.0 ACKNOWLEDGEMENTS 10-1
APPENDIX A A-l
APPENDIX B B-l
APPENDIX C C-l
IV
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LIST OF ILLUSTRATIONS
Figure Page
2-1 Current Hazardous Wastes to Land Disposal, Alkalies
and Chlorine (SIC 2812) 2-5
l!-2 Current Hazardous Wastes to Land Disposal, Inorganic
Pigments (SIC 2816) 2-6
2-3 Current Hazardous Wastes to Land Disposal, Inorganic
Chemicals (SIC 2819) (Exclusive of SIC 28199) 2-7
2-4 Current Hazardous Wastes to Land Disposal, Inorganic
Chemicals, N.E.C., (SIC 28199) 2-8
5-' Diaphragm CelI Chlor-Alkali Process 5-6
5-/: Chlor-Alkali Manufacture, Mercury Cell Process 5-9
5-3 Down's Cell Production of Sodium and Chlorine 5-12
5-4 Sodium Carbonate Manufacture by The Sol vay Process. . . 5-14
5-5 Sodium Bicarbonate 5-16
5-6 Acetylene Manufacture 5-24
5-7 Carbon Dioxide Manufacture 5-27
5-8 Helium Manufacture 5-28
5-9 Oxygen, Nitrogen and Rare Gases Manufacture 5-30
5-10 Hydrogen and CarbonMonoxide Manufacture 5-31
5-11 Nitrous Oxide Manufacture 5-32
5-12 Titanium Dioxide Manufacture by the Sulfate Process . . . 5-35
5-13 Titanium Dioxide Manufacture by the Chloride
Process Using 95% Ore or 65% Ore 5-39
5-14 Lead Sulfate Manufacture 5-45
-------
LIST OF ILLUSTRATIONS - continued
Figure Page
5-15 Lead Carbonate Manufacture 5-47
5-16 Zinc Oxide Manufacture by the Thermal Oxidation
Process 5-49
5-17 Antimony Oxide Manufacture 5-50
5-18 Chrome Yellow Manufacture 5-54
5-19 Molybdate Orange Manufacture 5-56
5-20 Zinc Yellow Manufacture 5-57
5-21 Chrome Green Manufacture 5-58
5-22 Anhydrous Chromic Oxide Pigment Manufacture 5-59
5-23 Hydrated Chromic Oxide Manufacture 5-60
5-24 Iron Blues Manufacture 5-62
5-25 Barium Sulfate Manufacture 5-63
5-26 Cadmium Pigments Manufacture 5-64
5-27 Lead Monoxide Manufacture 5-66
5-28 Cobaltic Oxide Manufacture 5-67
5-29 Iron Oxide Pigments Manufacture 5-68
5-30 Carbon Black Manufacture 5-70
5-31 Mercuric Sulfide Manufacture 5-71
5-32 Ultramarine Blue Manufacture 5-72
5-33 Sulfuric Acid Manufacture by Contact Process 5-80
5-34 Sulfuric Acid Manufacture by the Chamber Process .... 5-81
VI
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LIST OF ILLUSTRATIONS - continued
Figure Page
5-35 Hydrochloric Acid Manufacture 5-82
5-36 Hydrochloric Acid Manufacture by the Salt-Sulfuric
Acid Process 5-83
5-37 Hydrochloric Acid Manufacture by the Hargreaves
Process 5-84
5-il8 Boric Acid Manufacture 5-86
5-39 Chromic Acid Manufacture 5-87
5-40 Hydrogen Cyanide Manufacture by the Andrussow
Process 5-88
5-41 Hydrochluoric Acid Manufacture 5-90
5-42 Chlorosulfonic Acid Manufacture 5-91
5-43 Alumina Manufacture from Bauxite 5-95
5-44 Aluminum Chloride Manufacture . . 5-96
5-45 Aluminum Fluoride Manufacture 5-97
5-46 Aluminum Sulfate Manufacture 5-99
5-47 Potassium Manufacture 5-102
5-48 Potassium Sulfate Manufacture 5-104
5-49 Potassium Iodide Manufacture 5-105
5-50 Potassium Chloride Manufacture from Sylvite Ore ..... 5-106
5-51 Borax Manufacture From Ore 5-108
5-52 Sodium Fluoride Manufacture from Hydrofluoric Acid . . . 5-110
5-53 Sodium Fluoride Manufacture from Caustic Soda and
Sodium Silicofluoride . . . 5-111
vii
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LIST OF ILLUSTRATIONS - continued
Figure Page
5-54 Manufacture of Sodium Hydrosulfide and Sodium
Sulfide 5-112
5-55 Sodium Hydrosulfite Manufacture by Zinc Process 5-113
5-56 Sodium Hydrosulfite Manufacture 5-114
5-57 Sodium Silicofluoride Manufacture 5-116
5-58 Sodium Silicofluoride Manufacture from an Impure
Phosphoric Acid Stream 5-117
5-59 Sodium Orthophosphates Manufacture 5-119
5-60 Sodium Tripolyphosphate Manufacture 5-120
5-61 Sodium Borohydride Manufacture 5-121
5-62 Sodium Sulfite Manufacture 5-122
5-63 Sodium Silicate Manufacture 5-124
5-64 Sodium Thiosu I fate Manufacture 5-125
5-65 Chlorates Manufacture 5-126
5-66 Potassium Chlorate Manufacture Alternate Process .... 5-127
5-67 Sodium Perchlorate Manufacture 5-129
5-68 Potassium Perchlorate Manufacture 5-130
5-69 Potassium Nitrate Manufacture 5-131
5-70 Sodium Bisulfite Manufacture 5-132
5-71 Sodium Bromide Manufacture 5-134
5-72 Sodium Cyanide Manufacture 5-135
VIII
-------
LIST OF ILLUSTRATIONS - continued
Figure Page
5-73 Manufacture of Supported Metal Catalyst Materials.... 5-138
5-74 Manufacture of Supported Metal Oxide Catalyst
Materials 5-139
5-75 Activated Carbon Manufacture . . . 5-141
5-76 Ammonium Hydroxide Manufacture 5-142
5-77 Ammonium Chloride Manufacture from Solvay Process
Wastes 5-143
5-78 Manufacture of Arsenic Oxides 5-144
5-79 . Barium Carbonate Manufacture 5-146
5-80 Beryllium Hydroxide Manufacture 5-147
5-81 Beryllium Oxide Manufacture 5-148
5-82 Boron Trichloride Manufacture 5-150
5-83 Bromine Manufacture 5-151
5-84 Iodine Manufacture 5-152
5-85 Open Furnace Calcium Carbide Manufacture 5-154
5-86 Calcium Carbonate Manufacture from Calcium Chloride. . 5-155
5-87 Calcium Carbonate Manufacture from Slaked Lime .... 5-156
i
5-88 Calcium Oxide (Lime) Manufacture 5-157
5-89 Calcium Hydroxide Manufacture 5-158
5-90 Calcium Chloride Manufacture 5-159
5-91 Manufacture of Food Grade Calcium Phosphate 5-161
IX
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LIST OF ILLUSTRATIONS - continued
Figure
5-92
5-93
5-94
5-95
5-96
5-97
5-98
5-99
5-100
5-101
5-102
5-103
5-104
5-105
5-106
5-107
5-108
Manufacture of Animal-Feed Grade Calcium Phosphate . .
Cadmium Sulfide Manufacture
Sodium Dichromate and Chromate Manufacture
Potassium Dichromate Manufacture
Manufacture of Cobalt Compounds (Nitrate, Acetate,
Sulfats, Chloride)
Copper Sulfate Manufacture
Cuprous Oxide Manufacture
Fluorine Manufacture
Hydrogen Peroxide Manufacture by the Electrolytic
Process
Manufacture of Hydrogen Peroxide by Riedl-Pfleiderer
Process
Ferric Chloride Manufacture Solution Grade
Ferrous Sulfate Manufacture from Titania Sulfate Process
Wastes
Lead Nitrate
Lithium Carbonate Manufacture
Lithium Hydroxide Manufacture
Magnesium Sulfate Manufacture
Manganese Sulfate Manufacture
Page
5-162
5-163
5-165
5-167
5-168
5-169
5-171
5-172
5-173
5-174
5-176
5-177
5-179
5-180
5-181
5-183
5-184
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LIST OF ILLUSTRATIONS - continued
Figure Page
5-109 Yellow Mercuric Oxide Manufacture 5-186
5-110 Red Mercuric Oxide Manufacture 5-187
5-111 Bichloride of Mercury Manufacture 5-188
5-112 Nickel Sulfate Manufacture 5-190
5-113 Phosphorus Manufacture 5-191
5-114 Phosphorus Pentoxide Manufacture 5-193
5-115 Phosphorus Pentasulfide Manufacture 5-194
5-116 Phosphorus Trichloride Manufacture 5-196
5-117 Phosphorus Oxychloride Manufacture 5-197
5-118 Potassium Permanganate Manufacture 5-198
5-119 Silver Nitrate Manufacture 5-200
5-120 Strontium Carbonate Manufacture 5-201
5-121 Sulfur Dioxide Manufacture 5-202
5-122 Sulfur Dichloride Manufacture 5-203
5-123 ThionylChloride Manufacture 5-205
5-124 Thai Hum Carbonate Manufacture 5-207
5-125 Stannous Chloride Manufacture 5-208
5-126 Stannic Oxide Manufacture Dry Process 5-209
5-127 Zinc Sulfate Manufacture 5-210
XI
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LIST OF ILLUSTRATIONS - continued
Figure Page
5-128 Zinc Chloride Manufacture 5-212
6-1 Solubility of Copper, Nickel, Chromium and Zinc as
a Function of Solution pH 6-23
6-2 Transportation Costs for Northeastern U.S. Local
Hauling 6-40
6-3 1972 Rail Carload Costs Scales - Basic Data Obtained
From ICC 6-41
6-4 Costs for Liquid and Sludge Contract Treatment/Disposal. . 6-44
7-1 Disposal Costs for Mercury-Containing Sludges -
Chlorine 7-11
APPENDIX
Figure
1 Solubility of Calcium Fluoride in Hydrochloric Acid
Solutions A-42
XII
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LI STOP TABLES
Table No.
2-1
2-2
3-1
3-2
3-3
3-4
4-1
4-2
4-3
4-4
4-5
4-6
4-7
4-8
4-9
4-10
Summary of Land Destined Hazardous Wastes From
Inorganic Chemical Industry (SIC 281) (Dry Basis)
Summary of Typical Plant Costs for Treatment/Disposal
of Hazardous Waste Streams for Environmental
Quantity and Value of Products: 1972, SIC 2812
Quantity and Value of Products: 1972, SIC 2813
Quantity and Value of Products: 1972, SIC 2816
Quantity and Value of Products: 1972, SIC 2819
SIC 2812 Alkalies and Chlorine, Distribution of
SIC 2812 Alkalies and Chlorine, Distribution of
SIC 2812 Alkalies and Chlorine, Distribution of
Plant Ages
SIC 2812 Alkalies and Chlorine, Distribution of
SIC 2812 Alkalies and Chlorine, Distribution of
SIC 2813 Industrial Gases, Distribution of
SIC 2813 Industrial Gases, Distribution of Plant Sizes. . .
SIC 2813 Industrial Gases, Distribution of Plant Ages . . .
SIC 2813 Industrial Gases, Distribution of Processes. . . .
SIC 2813 Industrial Gases, Distribution of Production . . .
Page
2-4
2-4
3-3
3-4
3-6
3-8
4-3
4-4
4-5
4-6
4-7
4-9
4-10
4-11
4-12
4-13
XIII
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LI STOP TABLES-continued
Table No. Page
4-11 SIC 2816 Inorganic Pigments, Distribution of
Establishments 4-15
4-12 SIC 2816 Inorganic Pigments, Distribution of
Plant Sizes 4-16
4-13 SIC 2816 Inorganic Pigments, Distribution of
Plant Ages 4-17
4-14 SIC 2816 Inorganic Pigments, Distribution of
Processes 4-18
4-15 SIC 2816 Inorganic Pigments, Distribution of
Production 4-19
4-16 SIC 2819 Industrial Inorganic Chemicals N.E.C.,
Distribution of Establishments * 4-21
4-17 SIC 2819 Industrial Inorganic Chemicals N.E.C.,
Distribution of Plant Sizes 4-22
4-18 SIC 2819 Industrial Inorganic Chemicals N.E.C.,
Distribution of Plant Ages 4-23
4-19 SIC 2819 Industrial Inorganic Chemicals N.E.C.,
Distribution of Processes 4-24
4-20 SIC 2819 Industrial Inorganic Chemicals N.E.C.,
Distribution of Production 4-25
5-1 Hazardous Wastes Currently Destined for Land
Disposal FromAlkalies and Chlorine, (metric
tons per year, dry basis) 5-18
5-2 Hazardous Wastes Expected to be Destined for Land
Disposal From SIC 2812, Alkalies and Chlorine
(metric tons per year, dry basis) 5-21
5-3 Hazardous Wastes Expected to be Destined for Land
Disposal From SIC 2812, Alkalies and Chlorine
(metric tons per year, dry basis) 5-22
xiv
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LI STOP TABLES-continued
Table No. Page
5-4 Hazardous Wastes Destined for Land Disposal Generated
by Industry Subcategory 28161, Titanium Pigments
(metric tons per year, dry basis) 5-42
5-5 Hazardous Wastes Destined for Land Disposal Generated
by Industry Subcategory 28162, Other White Pigments,
Currently and Projected for the Years 1977 and 1983
(metric tons per year, dry basis) 5-52
ii-6 Hazardous Wastes Destined for Land Disposal Generated
by Industry Subcategory 28163, Chrome Colors and Other
Pigments (metric tons per year, dry basis) 5-74
5-7 Hazardous Wastes Destined for Land Disposal Expected
to be Generated in 1977 by Industry Subcategory 28163,
Chrome Colors and Other Pigments (metric tons per
year, dry basis) 5-76
5-8 Hazardous Wastes Destined for Land Disposal Expected
to be Generated in 1983 by Industry Subcategory 28163,
Chrome Colors and Other Pigments (metric tons per
year, dry basis) . 5-77
5-9 Hazardous Wastes Destined for Land Disposal from the
SIC 28194 Inorganic Acids Industries (metric tons per
year, dry basis) 5-92
5-10 Hazardous Wastes Destined for Land Disposal from the
SIC 28196 Aluminum Compounds Industries (metric tons
per year, dry basis) 5-101
5-11 Hazardous Wastes Destined for Land Disposal from the
SIC 28197 Potassium and Sodium Compounds Manufacture
(metric tons per year, dry basis) 5-136
5-12 Hazardous Wastes Currently Destined for Land Disposal
From SIC 28199 Other Industrial Inorganic Chemicals
N.E.C. (metric tons per year, dry basis) 5-213
xv
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LI STOP TABLES- continued
Table No. Page
5-13 Hazardous Wastes Expected to be Destined for Land
Disposal in 1977 From SIC 28199 Other Industrial
Inorganic Chemicals, N.E.C. (metric tons per year,
dry basis) 5-215
5-14 Hazardous Wastes Expected to be Destined for Land
Disposal in 1983 From Six 28199 Other Industrial
Inorganic Chemicals, N. E.C. (metric tons per year,
dry basis) 5-216
6-0 Summery of Current Land Disposal of Hazardous Wastes . . 6-2
6-1 Chlor-Alkali-DiaphragmCell Process 6-8
6-2 Chlor-Alkali-Mercury Cell Process 6-9
6-3 Down's Cell Process 6-10
6-4 Titanium Dioxide-Chloride Process 6-11
6-5 Chrome Pigments and Iron Blue Manufacture 6-12
6-6 Hydrofluoric Acid 6-13
6-7 Boric Acid 6-14
6-8 Aluminum Fluoride 6-15
6-9 Sodium Silicofluoride 6-16
6-10 Chromates Manufacture - Ore Processing 6-17
6-11 Nickel Sulfate 6-18
6-12 Phosphorus Manufacture 6-19
6-13 Phosphorus Trichloride and Phosphorus Pentasulfide .... 6-20
6-14 1973 U.S. Motor Rate Transportation Rates Est. From
1971 I.C.C. Information (reference 10) 6-42
XVI
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LI STOP TABLES-continued
Table No. Page
6-15 Bulk Liquid and Sludge Disposal Costs Landfill Areas . . . 6-46
6-16 Drum Disposal Costs - Landfill Areas 6-47
6-17 Segregated Burial or Secured Landfill Costs , . 6-48
6-18 Costs for Ocean Disposal 6-49
7-1 Costs for Treatment/Disposal, Diaphragm Cell Process,
Alkalies and Chlorine (SIC 2812) 7-8
7-2 Costs for Treatment/Disposal, Mercury Cell Process,
Alkalies and Chlorine (SIC 2812) 7-10
7-3 Costs for Treatment/Disposal, Down's Cell Process,
Alkalies and Chlorine (SIC 2812) 7-13
7-4 Costs for Treatment/Disposal, Chloride Process,
Titanium Dioxide Pigment (SIC 2816) 7-15
7-5 Costs for Treatment/Disposal, Chloride Process,
Titanium Dioxide Pigment (SIC 2816) . 7-16
7-6 Costs for Treatment/Disposal, Chrome Pigments and
Iron Blues (SIC 2816) 7-18
7-7 Costs for Treatment/Disposal, Hydrofluoric Acid
Manufacture (SIC 2819) 7-20
7-8 Costs for Treatment/Disposal, Aluminum Fluoride
Manufacture (SIC 2819) 7-22
7-9 Costs for Treatment/Disposal, Sodium Silicofluoride
Manufacture (SIC 2819) 7-24
7-10 Costs for Treatment/Disposal, Chromates Manufacture
(SIC 2819) 7-25
XVII
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LI STOP TABLES- continued
Table No. Page
7-11 Costs for Treatment/Disposal, Nickel Sulfate
Manufacture (SIC 2819) 7-27
7-12 Costs for Treatment/Disposal, Phosphorus
Manufacture (SIC 2819) 7-30
7-13 Costs for Treatment/Disposal, Phosphorus Pentasulfide
Manufacture (SIC 2819) 7-31
7-14 Costs for Treatment/Disposal, Phosphorus Trichloride
Manufacture (SIC 2819) 7-32
XVIII
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INDUSTRYCROSS REFERENCING INDEX
INDUSTRY SEGMENT Page
Chlorine (SIC 28121)
Economic Structure and Products . 3-1
Future Industry Developments 3-13
Industry Characterization 4-2
Waste Characterization 5-4
Treatment and Disposal Technology 6-3
Cost Analysis 7-7
Synthetic Sodium Carbonate (SIC 28122)
Economic Structure and Products . . . ; 3-1
Future Industry Developments 3-13
Industry Characterization 4-2
Waste Characterization 5-13
Sodium Hydroxide (SIC 28123)
liconomic Structure and Products 3-1
Future Industry Developments 3-13
Industry Characterization 4-2
Waste Characterization . 5-15
Cost Analysis 7-7
Other Alkalies (SIC 28124)
Economic Structure and Products 3-1
Fufure Industry Developments 3-13
Industry Characterization 4-2
Wciste Characterization 5-15
XIX
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INDUSTRY CROSS REFERENCING INDEX - continued
INDUSTRY SEGMENT Page
Acetylene (SIC 28132)
Economic Structure and Products 3-2
Future Industry Developments 3-13
Industry Characterization 4-8
Waste Characterization 5-23
Carbon Dioxide (SIC 28133)
Economic Structure and Products 3-2
Future Industry Developments 3-13
Industry Characterization 4-8
Waste Characterization 5-26
Other Elemental Gases and Industrial Gases (SIC 28134)
Economic Structure and Products 3-2
Future Industry Developments 3-13
Industry Characterization 4-8
Waste Characterization 5-26
Titanium Pigments (SIC 28161)
Economic Structure and Products 3-5
Future Industry Developments 3-13
Industry Characterization 4-14
Waste Characterization 5-33
Treatment and Disposal Technology 6-4
Cost Analysis 7-14
xx
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INDUSTRY CROSS REFERENCING INDEX - continued
INDUSTRY SEGMENT Page
Other White Opaque Pigments (SIC 28162)
Economic Structure and Products 3-5
Future Industry Developments 3-13
Industry Characterization 4-14
Waste Characterization 5-44
Treatment and Disposal Technology 6-4
Chrome Colors and Other Inorganic Pigments (SIC 28163)
Economic Structure and Products 3-5
Future Industry Developments 3-13
Industry Characterization 4-14
Waste Characterization 5-53
Treatment and Disposal Technology 6-5
Cost Analysis 7-14
Sulfuric Acid (SIC 28193)
Economic Structure and Products 3-5
Future Industry Developments 3-13
Industry Characterization 4-20
Waste Characterization , . . . . 5-78
Other Inorganic Acids (SIC 28194)
Economic Structure and Products 3-5
Fufure Industry Developments 3-13
Industry Characterization 4-20
Woste Characterization 5-79
Treatment and Disposal Technology 6-5
Coat Analysis 7-19
XXI
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INDUSTRY CROSS REFERENCING INDEX - continued
INDUSTRY SEGMENT Page
Aluminum Oxide (SIC 28195)
Economic Structure and Products . 3-5
Future Industry Developments 3-13
Industry Characterization 4-20
Waste Characterization 5-93
Other Aluminum Compounds (SIC 28196)
Economic Structure and Products 3-5
Future Industry Developments 3-13
Industry Characterization 4-20
Waste Characterization 5-94
Treatment and Disposal Technology 6-5
Cost Analysis 7-21
Potassium and Sodium Compounds (SIC 28197)
Economic Structure and Products 3-5
Future Industry Developments 3-13
Industry Characterization 4-20
Waste Characterization 5-100
Treatment and Disposal Technology 6-6
Cost Analysis 7-21
Chemical Catalytic Preparations (SIC 28198)
Economic Structure and Products 3-5
Future Industry Developments 3-13
Industry Characterization 4-20
Waste Characterization 5-137
XXII
-------
INDUSTRY CROSS REFERENCING INDEX- continued
INDUSTRY SEGMENT
Inorganic Chemicals/ Not Elsewhere Classified (SIC 28199)
Economic Structure and Products 3-5
Future Industry Developments . 3-13
Industry Characterization 4-20
Waste Characterization 5-140
Treatment and Disposal Technology 6-6
Cost Analysis 7-23
XXI11
-------
COMMODITY CROSS REFERENCING INDEX
COMMODITY Pages
Acetylene 5-23, 5-24, 5-25
Activated Carbon 5-140,5-141
Air Distillation Products 5-26
Aluminum Chloride 5-96, 5-94
Aluminum Fluoride 5-94, 5-97, 6-5, 7-21
Aluminum Hydroxide 5-93
Aluminum Oxide 5-93, 5-95
Aluminum Sulfate 5-98, 5-99
Ammonium Chloride 5-140,5-143
Ammonium Hydroxide 5-140, 5-142
Ammonium Carbonate 5-15
Antimony Oxide 5-48, 5-50
Arsenic Oxides 5-140,5-144
Barium Compounds 5-145,5-146
Barium Sulfate 5-61, 5-63
Beryllium Compounds 5-145, 5-147, 5-148
Bichloride of Mercury 5-188
Borax 5-107, 5-108
Boric Acid 5-85, 5-86, 7-21
Boron Halides 5-149, 5-150
Bromine 5-149, 5-151
Cadmium Oxide 5-160
Cadmium Pigments 5-61, 5-64
Cadmium Salts 5-160
Cadmium Sulfide 5-160, 5-163
Calcium Carbide 5-153,5-154
Calcium Carbonate 5-153, 5-155, 5-156
Calcium Chloride 5-153,5-159
Calcium Compounds 5-153
Calcium Hydroxide 5-158
Calcium Oxide 5-153, 5-157
Calcium Phosphate 5-69, 5-70
Carbon Black Pigments 5-69, 5-70
Carbon Dioxide 5-26, 5-27
Carbon Monoxide 5-29, 5-31
XXIV
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COMMODITY CROSS REFERENCING INDEX - continued
COMMODITY
Catalysts
Chlorates
Chlorine
Chlorosulfonic Acid
Chromates
Chrome Yellows and
Oranges
Chrome Green
Chrome Oxide Green
Chromic Acid
Chromic Salts
Cobalt Compounds
Cobalt Pigments
Colored Lead Pigments
and Red Lead
Copper Compounds
Ferric Chloride
Ferrous Sulfate
Fluorine
Helium
Hydrogen
Hydrochloric Acid
Hydrofluoric Acid
Hydrogen Cyanide
Hydrogen Peroxide
Hypophosphites
Iodine
Iron Blues
Iron Compounds
Iron Oxide Pigments
Lead Carbonate, Lead
Basic Carbonate
Lead Compounds (other
than pigments)
Pages
5-137, 5-138, 5-139
5-123, 5-126
5-4, 5-6, 5-9, 5-12, 6-2, 7-7
5-89, 5-91
5-164, 6-6, 6-25, 7-23
5-53, 5-54, 6-2, 6-5, 7-14
5-55, 5-58
5-55, 5-59, 5-60
5-85, 5-87, 5-164
5-166
5-166, 5-168
5-65, 5-67
5-65, 5-66
5-166, 5-169, 5-171, 6-23
5-175, 5-176
5-175, 5-177
5-170, 5-172
5-16, 5-28
5-29, 5-31
5-79, 5-82, 5-83, 5-84
5-89, 5-90, 7-19
5-85, 5-88, 6-22
5-170, 5-173, 5-174
5-175
5-149, 5-152
5-61, 5-62, 7-14
5-175
5-65, 5-68
5-46, 5-47
5-178, 5-179
XXV
-------
COMMODITY CROSS REFERENCING INDEX - continued
COMMODITY
Lead Su I fates
Lithium Compounds
Lithopone
Magnesium Compounds
Manganese Compounds
Mercuric Sulfide
Mercury Compounds
Mercury (redistilled)
Molybdate Orange
Nickel Carbonate
Nickel Compounds
Nickel Hydroxide
Nickel Sulfate
Nitrogen
Nitrous Oxide
Oxygen
Perchlorates
Phosphorus
Phosphorus Oxides, Sulfides
and Chlorides
Potassium Carbonate
Potassium Chloride
Potassium Dichromate
Potassium Hydroxide
Potassium Iodide
Potassium Metal
Potassium Nitrate
Potassium Permanganate
Potassium Sulfate
Pages
5-44, 5-45
5-178, 5-180, 5-181
5-48
5-178, 5-183
5-182, 5-184
5-69, 5-71
5-185
5-182
5-53, 5-56
5-189
5-189, 6-23
5-189
5-190, 6-6, 7-26
5-30
5-29, 5-32
5-30
5-123, 5-127, 5-129, 5-130
5-189, 5-191, 6-6, 7-28
5-192, 5-193, 5-194, 5-196,
5-197, 6-6, 6-7, 7-29
5-15
5-103, 5-106
5-167
5-15
5-103, 5-105
5-100, 5-102
5-128, 5-131
5-195, 5-198
5-103, 5-104
XXVI
-------
COMMODITY CROSS REFERENCING INDEX - continued
COMMODITY
Radioactive Chemicals
Red Mercuric Oxide
Selenium
Silver Compounds
Sodium Bicarbonate
Sodium Bisulfite
Sodium Borohydride
Sodium Bromide
Sodium Cyanide
Sodium Dichromate
Sodium Fluoride
Sodium Hydrosulfite
Sodium Hydroxide
Sodium Metal
Sodium Phosphates
Sodium Silicate
Sodium Silicofluoride
Sodium Sulfide and
Hydrosulfide
Sodium Sulfite
Sodium Thiosulfate
Strontium Compounds
Sulfur Chlorides
Sulfur Dioxide
Sulfur Oxychlorides
Sulfuric Acid
Sulfuryl Chloride
Synthetic Soda Ash
Thallium Compounds
Thiocyanates
Tin Compounds
Titanium Dioxide Pigments
Tellurium
Pages
5-195
5-187
5-195
5-199, 5-200
5-15, 5-16
5-128, 5-132
5-118, 5-121
5-133, 5-134
5-133, 5-135
5-164, 5-165
5-109, 5-110, 5-111
5-109, 5-113, 5-114
5-15
5-115
5-118, 5-119, 5-120
5-123, 5-124
5-115, 5-116, 5-117, 6-6, 7-21
5-109, 5-112
5-118, 5-122
5-123, 5-125
5-199, 5-201
5-199, 5-203
5-199, 5-202
5-199
5-78, 5-80, 5-81
5-204, 5-205
5-13, 5-14
5-204, 5-207
5-206
5-206, 5-208, 5-209
5-33, 5-35, 5-39, 5-40, 6-2, 6-4, 7-14
5-195
XXVII
-------
COMMODITY CROSS REFERENCING INDEX - continued
COMMODITY Pages
Ultramarine Pigment 5-69, 5-72
Yellow Mercuric Oxide 5-186
Zinc Compounds 5-106,5-210,5-212,6-23
Zinc Oxide 5-46, 5-49
Zinc Sulfide 5-48
Zinc Yellow 5-55, 5-57
XXVI11
-------
ls.0 INTRODUCTION
This report is the result of a study commissioned by the
U.S. Environmental Protection Agency to assess "Industrial
Hazardous Waste Practices—Inorganic Chemicals Industry."
Concurrently, the EPA pursued similar studies of other
industry categories. This program was intended to provide
the EPA with as much detailed and pertinent information on
the generation, management, treatment, disposal, and costs
related to wastes considered to be ^potentially hazardous."
Such information will be used in developing guidelines or
standards for the management of hazardous wastes.
Throughout this report^ wherever the terms "'hazardous
wastes'" or "potentially -hazardous wastes81 are used it should
be kept in mind that no final judgments are intended as to
such classification. It is recognised and understood that
additional information will be required as to the actual
fate of such materials in a given 8»disposal" or "management"
environment, before a final definition of "hazardous waste"
evolves and is used. As an example, for certain of the
waste streams identified in this report the EPA is currently
supporting other studies designed to investigate leaching
characteristics in various soil and moisture conditions.
Versar Inc., General Technologies Division, began this
program for the Environmental Protection Agency (EPA),
Office of Solid Waste Management Programs (OSWMPJ on 16
January, 1971. It covers standard Industrial Classification
(SIC) 281, the inorganic chemicals industry.
The basic objectives of this study are;
(a) Identify those hazardous wastes which are or will be
generated by the inorganic chemicals industry;
(b) Describe current practices for treatment and disposal of
hazardous wastes;
(c) Determine the control technologies which might be
applied to reduce hazards presented by these wastes upon
disposal; and
(d) Estimate the cost of control technology implementation.
This report contains the essential elements of the technical
information in four major sections:
1-1
-------
Section 4^0 - Industrial Characterization
Characterizes the industry with regard to the
number, location, size, and production of
manufacturing establishments;
Section 5..0 - Waste Characterization
Identifies and quantifies those hazardous wastes
which are or will be generated by the inorganic
chemical industry;
Section 6..0 - Treatment and Disgosal Technology
Describes current practices for treatment and
disposal of hazardous wastes and determines the
control technologies which might be applied to
reduce potential hazards presented by these wastes
upon disposal; and
Section 7^0 - Cost Analysis
Estimates the cost and control technology imple-
mentation.
\.^
The individual elements of each of these phases are
presented in detail in their respective sections of this
report.
1 . 1 Program Methodology
.LJU! fi£t§ Acquisition
The data needed for this study was obtained by four
different methods. The first was by reviewing published
information and data in the technical literature, trade
journals, government reports and technical surveys conducted
by the industry associations. Some of these references are
cited throughout this report.
The second method involved the utilization of data collected
during our previous work on effluent limitations guidelines
studies on the inorganic chemicals industry for the Effluent
Guidelines Division, EPA.
A third method involved trade association participation.
The Chlorine Institute in New York City and the
Manufacturing Chemists Association in Washington, D. C. were
contacted for assistance.
1-2
-------
The fourth method of data acquisition was by personal
contacts and visits to the various plants and corporate
offices of chemical manufacturers. A better and more
thorough understanding of the generation of wastes destined
for land disposal from chemicals production was obtained
through personal interviews.
The results of the overall methodology were fruitful in that
information was obtained froms
-visits or other personal contacts with 63 manufacturing
facilities
-visits to H landfill sites
-visits to 14 waste disposal contractors
-visits to 8 government facilities
-visits to 2 trade associations.
The manufacturers contacted are responsible for over
80 percent of the tonnage of products manufactured in SIC
281 and the 63 manufacturing facilities visited were
concentrated among those having potential for producing
hazardous wastes destined for land. In all instances the
opinions of the manufacturers as to hazardous waste
materials generated in their operations were solicited.
The federal government facilities contacted include those
belonging to the Atomic Energy Commission, the Department of
Commerce, the Department of the Interior, the Environmental
Protection Agency, the Interstate commerce Commission, and
the Tennessee Valley Authority.
ls.li.2 Data An.aly.sis
The major tasks involved in the data analysis were:
(a) to review the collected data for consistency,
sufficiency, and probable accuracy;
(b) to assemble the more reliable data elements into a data
base sufficient to allow meaningful projections to be
made;
(c) to utilize the data base and subsequent waste factors to
allow tabulation of wastes on a state by state, federal
region and national basis.
Because of the excellent cooperation of the Chlorine
Institute and its member companies, the data base, hazardous
waste aggregations and treatment and disposal costs
estimates for the Alkalies and Chlorine Industry, SIC 2812,
are probably the most accurate of the four industries
studied. These are estimated to have an accuracy of
+20 percent.
-------
It was determined that there are no land-destined hazardous
wastes emanating from the Industrial Gases Industry,
SIC 2813, and therefore the industry characterization data
base reported for this industry would have the same standard
error of estimate as the 1972 Census of Manufacturers which
should be well within +10 percent*
The accuracy of data reported for the remaining two
industries; Inorganic Pigments, SIC 2816 and Industrial
Inorganic Chemicals, N.E.C., SIC 2819 is estimated to
average about +40 to 50 percent. In the cases where hard
plant data was obtained, the accuracy is estimated to be as
good as +10 to 20 percent. However, where engineering
estimates had to be made because of either lack of
cooperation or data being withheld to avoid disclosure of
confidential information; the accuracy could be considerably
less.
lilil Criteria For Determination of Hazardous Wastes
"Hazardous wastes" means any waste or combination of wastes
which pose a substantial present or potential hazard to
human health or living organisms because such wastes are
nondegradable or persistent in nature or because they can be
biologically magnified, or because they can be lethal, or
because they may otherwise cause or tend to cause
detrimental cumulative effects.*")
Hazardous wastes include materials which are:
(a) toxic or poisonous (producing injury or illness through
ingestion, inhalation or absorption through any skin
surface) ;
(b) corrosive (destructive to living tissue) ;
(c) irritants (induce local inflammatory reaction in living
tissue);
(d) strong sensitizers (cause hypersensitivity on living
tissue through an allergic or photo-dynamic process);
(e) flammable;
(f) explosive (generate pressure through decomposition, heat
or other means);
(g) infectious (represent a potential source of the trans-
mission of diseases to human, domestic animals or
wildlife);
(i) radioactive.
Most industrial solid waste streams which contain hazardous
constituents also contain significant percentages of
non-hazardous constituents. The properties of the severely
hazardous constituents and their correspondingly strict
disposal requirements overshadow and essentially render
1-4
-------
insignificant the properties and needed disposal
restrictions of other constituents in that same waste
stream. Other industrial solid waste streams contain no
severely hazardous constituents; that is, they contain no
environmentally persistent constituents which would have
severe impact on the normal functioning of the biota when
present in small concentrations. When industrial solid
waste streams have no severely hazardous constituents,
generally their environmentally acceptable disposal may be
handled by following the recommendations for inert and
moderately hazardous materials.
The criteria for determining whether a given waste stream
constituent should be considered totally innocuous,
moderately hazardous or severely hazardous has been based
upon precedents set by previous contracting studies and
lists of hazardous materials promulgated by EPA. See
references 44, 46, 60, 69 and Appendix A references 6, 7,
10, 11, 12, 14, 16, 17, and 19. Initially all waste stream
constituents were considered to be potential hazards and
then all obviously innocuous items were deleted (e.g.,
water, sand, brick dust, etc.). The remaining substances
were studied in greater depth to determine whether they were
toxic, were carcinogens, posed genetic hazards, or were
contact, flammability, or explosion hazards when present in
the environment in high or low concentrations and whether or
not they were environmentally persistent. Those items that
were persistent and hazardous or potentially hazardous due
to an interaction with the environment at low concentration
levels were termed severely hazardous and thus waste streams
containing them in appreciable quantities were considered
"hazardous" for the present study.
The severely hazardous category includes all substances
which are persistent in the environment greater than
3 months and have an acute toxicity of <5 to 500 mg/kg,
and/or are known carcinogens.
The moderately hazardous category includes all substances
with an acute toxicity of 500 to 5000 mg/kg. Where waste
streams contain moderately hazardous materials in high
concentrations and with considerable potential for hazard
after land disposal, they have been considered as
"hazardous" for the purposes of this study. In several
instances, calcium fluoride-containing waste streams have
been so designated.
1-5
-------
taTabulatin
In the tabular data that follow in Sections 2, 4 and 5,
there are data elements that have been obtained by a
process of estimation involving uncertainties of the
order of 10 per cent or higher. The figures developed
by such estimation cannot be justifiably expressed in
terms of more than two significant figures or more
accuracy is implied than is given. These values are
then always rounded off to two significant figures.
This also includes the tabular totals of these figures.
The tables where this predominantly occurs are:
Summary of Land Destined Hazardous Wastes (Section 2)
Distribution of Production (Section 4)
Hazardous Wastes for Land Disposal (Section 5)
Projection of Hazardous Wastes to 1977 and
1983 (Section 5)
1-6
-------
2.0 SUMMARY
2.1 Executive Analysis
The industry facilities manufacturing commodities classified
under Standard Industrial Classification 281, Industrial
Inorganic Chemicals, were found to be currently disposing on
land 2 x 10* metric tons of hazardous wastes per year (dry
basis) from a total annual industrial waste load of
4 x 107 metric tons (also dry basis). There are four major
subcategories of these commodity producers: the alkalies and
chlorine JSIC 2812^ manufacturers that produce such
commodities as chlorine, sodium hydroxide, potassium
hydroxide, and synthetic soda ash; the industrial gases JSIC
28111 manufacturers that produce such commodities as oxygen,
nitrogen, hydrogen and carbon dioxide; the inorganic
pigments _(SIC 2816^ manufacturers that produce such
commodities as titanium dioxide, chrome pigments and iron
blues; and the manufacturers of the industrial inorganic
chemicals not elsewhere classified IS 1C 2819JL that produce a
diversity of commodities such as sulfuric acid, hydrofluoric
acid, alum, sodium sulfide, and phosphorus.
The most prominent hazardous wastes for land disposal
presently are associated with the manufacture of alkalies
and chlorine JSIC 2812^. This industry segment has
relatively large amounts of the potentially toxic waste
materials, mercury, lead and asbestos, which are very
persistent. However, the amounts of these wastes generated
will decrease significantly in the future as the industry
gradually relies less and less on the "mercury cell11
process, substitutes the alternative "diaphragm cell"
process, and adds improvements in its process equipment.
This industry segment has the second largest tonnage of
potentially hazardous constituents destined for land of the
whole SIC 281 group of industrial inorganic chemical
industries. The mercury cell process for the manufacture of
chlorine is utilized in 28 plants and produces the major
amounts of hazardous wastes from this segment. These wastes
are from water treatment systems.
The second-ranking industry segment in terms of prominence
of land-disposed hazardous waste problems is the inorganic
pigments segment (SIC 2816) which generates somewhat smaller
amounts of hazardous ingredients but larger tonnages of
total waste destined for land than Sic 2812. However, these
wastes contain several heavy metal elements as the principal
hazardous ingredients, which are potentially toxic and very
persistent in the environment. The most significant amounts
for land disposal arise from 9 plants that manufacture
2-1
-------
chrome pigments and 6 plants that manufacture titanium
dioxide by the £ljl2£idle
The SIC_28.19 industry segment of industrial inorganic
chemicals not elsewhere classified generates the largest
tonnages of wastes containing potentially hazardous
constituents but is not considered to be as critical a
problem as the foregoing two industry segments. This
category includes 923 plants and diverse end products and
manufacturing processes. The number of potentially
"problem" processes and plants which generate potentially
hazardous wastes is much smaller than this. As an example,
the manufacture of hydrofluoric acid accounts for 30 percent
of the tonnage of potentially hazardous constituents
(primarily fluoride) and about 65 percent of the tonnage of
total wastes containing hazardous constituents for this
industry segment. Hydrofluoric acid is manufactured at
14 plants. The manufacture of phosphorus is also of
concern; this results in a smaller amount of waste
containing hazardous constituents (20 percent of the total
for this SIC code) , but accounts for HO percent of the
potentially hazardous constituents. Phosphorus is
manuf act ured at 10 plants. The manufacture of aluminum
fluoride at 3 plants and the manufacture of sodium
silicofluoride at 8 plants result in smaller amounts of
hazardous constituents and wastes. Although the tonnages of
wastes generated by this industry segment (SIC 2819) are
large, the hazard presented by the wastes (primarily calcium
fluoride) may not be so critical as those from SIC 2812 and
SIC 2816. The latent danger in calcium fluoride residue is
in acidification and the potential for release of
hydrofluoric acid therefrom.
The industrial gases segment ^SIC 2813). is not a generator
of significant amounts of hazardous wastes destined for
land. It is important to note that not all commodities
which could be considered industrial gases on a technical
basis are included in this statistical classification.
Several are included in SIC 2819 (e.g., sulfur dioxide and
fluorine) and SIC 2812 (chlorine).
2A2 General Summary
The industrial hazardous waste practices were assessed for
the inorganic chemicals industry in four phases of effort.
I - Industrial Characterization
The industrial inorganic chemicals industry, SIC 281, is
subdivided into four major industry categories which were
covered in this study:
2-2
-------
SIC 2812, Alkalies and Chlorine Industry
SIC 2813, Industrial Gases Industry
SIC 2816, Inorganic Pigments Industry
SIC 2819, Industrial Inorganic Chemicals, Not
Elsewhere Classified
The presentation of the data was facilitated by further sub-
dividing each of the major industry categories into their
respective 5-digit SIC subcategories. There are seventeen
such subcategories in SIC 281 and they are fully
characterized with respect to number and distribution of
establishments, size on the basis of daily production
capacity, age, processes used and yearly production tonnage
in Section U of this report. A total of 1607 plants
producing 112.U million metric tons of products per year
were accounted for in this study.
Phase II - Waste Characterization
The land destined hazardous wastes from the inorganic
chemicals industry originates either directly from the
manufacturing processes or from air or water effluent
treatment. The amount of water in these land-destined waste
streams will vary usually between 30 and 80 percent
depending on whether the waste is a filter cake or a sludge
going to a settling pond. Slurries pumped to deep wells or
other land disposal have a greater water content.
Therefore, all the waste streams and their hazardous
constituents are reported on a dry basis for consistency and
are summarized in Table 2-1 which lists currently generated
amounts along with projected amounts expected in 1977 and
1983.
Figures 2-1 through 2-4 summarize the current state-by-state
distribution of total hazardous waste streams (dry basis) to
land disposal from the industries that generate these
land-destined wastes. These figures are meant to give the
reader a quick picture of the relative amounts of
land-destined hazardous wastes emanating from the industrial
inorganic chemicals industry and the disposal locations
within the u. S. These figures do not indicate the relative
degrees of toxicity, flammability, etc., or concentrations
of hazardous ingredients, which vary widely.
The waste streams are identified in detail in Section 5 of
this report.
2-3
-------
Table 2-1. Summary of Land Destined Hazardous Wastes From
Inorganic Chemical Industry (SIC 281)
Major
Industry
Category
SIC 2812,
Alkalies & Chlorine
SIC 2813,
Industrial Gases
SIC 2816,
Inorganic Pigments
SIC 2819,
Industrial Inorganic
Chemicals, Not
Elsewhere
Classified
SIC 281 ,
Inorganic Chemicals
Industry
Hazardous
Constituents
asbestos, chlorinated
hydrocarbons, lead,
mercury
none
antimony, arsenic,
cadmium, chromium,
cyanide, lead,
mercury, zinc
arsenic, chromium,
fluoride, nickel,
phosphorus, zinc
see above
Metric tons per year to land disposal
Haz. Constituents (dry)
current
7,000
0
4,700
52,000
64,000
r 1977
7,500
0
5,800
53,000
66,000
1983
4,200
0
6,900
66,000
77,000
Total Haz. Waste Stream (dry/wet)
current
57,000/
110,000
0
160,0007
350,000
1,800,0007*
2,900,000
2,000,0007
3,400,000
1977
56,0007
109,000
0
230,0007
510,000
2,000,0007
3,300,000
2,300,0007
3,900,000
1983
45,0007
89,000
0
320,0007
710,000
2,400,0007
4,000,000
2,800,0007
4,800,000
Table 2-2. Summary of Typical Plant Costs for Treatment/Disposal of Hazardous
Waste Streams for Environmental Adequacy (Level III)
Industry Subcotegory
SIC 28121 Chlorine
SIC 28161 Titanium Dioxide Pigment
SIC 28163 Chrome Colon
SIC 28194 Inorganic Acids
SIC 28196 Aluminum Compounds
SIC 28197 K and No Compounds
SIC 28199 Others N.E.C.
Product/Process
Diaphragm Cell
Mercury Cell
Down's Cell
Chloride Process
Chrome Pigments and Iron Blue*
Hydrofluoric Acid
Aluminum Fluoride
Sodium Si llcofluoride
Sodium Dichromate
Nickel Sulfate
Phosphorus
Phosphorus Pentasulfide
Phosphorus Trichloride
Treatment/Disposal Cost
(j/metric ton of product)
0.3
2. -3.
0.1
1.-4.
7. -8.
11. -15.
0.6
0.6
7.
4.
6. -11.
0.07
0.4
Product Selling Price
1973, (S/merric ton)
83
605-615
770-1,363 (1971)
616-679
295 (1971)
175
380
750(1971)
419
299
292
Percentage of Treatment
Cost to Product Cost
0.4
2.4-3.6
0.1
0.2-0.7
0.6-1.0
1.7-2.3
0.2
0.3
1.8
0.5
1.4-2.6
0.02
0.1
*Does not include 9QOVOOQ metrtc tons of arsenic sal fide wastes from the
manufacuture of Sodium Tetraborate Decahydrate. (For details see pages 5-107
- 5-109)
2-4
-------
10
I
ALASKA-0
HAWAII -0
LEGEND: (AMOUNT, DRY BASIS)
[ | 0-100 METRIC TONS PER YEAR
IOO-I.OOO METRIC TONS PER YEAR
if| 1,000-10,000 METRIC TONS PER YEAR
HAZARDOUS
CONSTITUENTS
ASBESTOS
'" CALCIUM-SODIUM ALLOY
CHLORINATED HYDROCARBONS
LEAD
MERCURY
FIGURE 2-1
CURRENT HAZARDOUS WASTES TO LAND DISPOSAL
ALKALIES AND CHLORINE (SIC 2812)
-------
N>
a\
ALASKA-0
HAWAtl-0
LEGEND'^ (AMOUNT, DRY BASIS)
NONE
100-1,000 METRIC TONS PER YEAR
fSppj I,OOO-IO,OOO METRIC TONS PER YEAR
IO,OOO-IOO,OOO METRIC TONS PER YEAR
FIGURE 2-2
B - MWSTES BARGED TO SEA CURRENT HAZARDOUS WASTES
D - WASTES DISCHARGED TO LAND DISPOSAL
INORGANIC PIGMENTS (SIC 2816)
HAZARDOUS
CONSTITUENTS
ANTIMONY
ARSENIC
CADMIUM
CHROMIUM
CYANIDE
LEAD
MERCURY
ZINC
-------
ro
-4
ALASKA-0
1-0
LEGEND: (AMOUNT, DRY BASIS)
O-lOO METRIC TONS PER YEAR
IOO-IJOOO METRIC TONS PER YEAR
l,000-K)tOOO METRIC TONS PER YEAR
OVER IQflOO METRIC TONS PER YEAR
FIGURE 2-3
CURRENT HAZARDOUS WASTES TO LAND DISPOSAL
INORGANIC CHEMICALS (SIC 2819)
(EXCLUSIVE OF SIC 28199)
HAZARDOUS
CONSTITUENTS
ARSENIC
FLUORIDE
-------
oo
ALASKA-0
HAWAII-0
LEGEND: (AMOUNT, DRY BASIS)
[ | 0-100 METRIC TONS PER YEAR
100-1,000 METRIC TONS PER YEAR
1,000-10,000 METRIC TONS PER YEAR
10,000-100flOO METRIC TONS PER YEAR
FIGURE 2-4
CURRENT HAZARDOUS WASTES TO LAND DISPOSAL
INORGANIC CHEMICALS, N.E.C. (SIC 28199)
HAZARDOUS
CONSTITUENTS
ARSENIC
CHROMIUM
FLUORIDE
NICKEL
PHOSPHORUS
ZINC
-------
Phase III - Tr.eatmen£ and Disposal Technology
Land-destined hazardous wastes from this industry are
usually in the form of slurries or wet solids. The
technology used in their treatment and disposal depends, for
the most part, on:
- the volume of hazardous waste involved
- the chemical composition of the waste
• the local disposal regulations
- the geographical location and
- the availability of disposal land.
Only about 12,000 metric tons per year (or 0.6 percent of
the total) of hazardous wastes currently go into secured
landfill. On-site storage and disposal (including deep
welling) currently accounts for over 75X of the total waste
generated by the industry. It is estimated that this
percentage will not drop significantly in the foreseeable
future. Specifics regarding treatment and disposal
technology for hazardous wastes are discussed in Section 6
of this report.
Phase IV - Costs of Treatment and Disposal Technology
Table 2-2 summarizes the typical plant, costs for
treatment/disposal of hazardous waste streams from the
industrial inorganic chemicals industry for environmental
adequacy (Level III Technology). It is apparent that the
treatment/disposal costs expressed as a percentage of the
product selling price are relatively low throughout this
industry.
2-9
-------
3.0 DISCUJ5SION OF THE INORGANIC CHEMICALS INDUSTRY
3.2.1 Introduction
The products of the industry covered in this report are
listed under four categories in the 1972 Standard Industrial
Classification (SIC) Manual. These are SIC 2812, Alkalies
and Chlorine; SIC 2813, Industrial Gases; SIC 2816,
Inorganic Pigments and SIC 2819, Industrial Inorganic
Chemicals, N.E.C. The production and other overall
statistics of the industry broken down into the four SIC
codes are published by the Bureau of the Census, U. S.
Department of Commerce, in the Census of Manufacturers,
Industry Series. Much of the information presented in this
overall industry characterization is from the Preliminary
Reports, 1972 Census of Manufacturers, which are the most
recent ones available. <*> <*J
3.2 Economic Structure and Products of the Alkalies and
Chlorine Industry^. SIC 2812
The Alkalies and Chlorine Industry includes establishments
primarily engaged in manufacturing alkalies and chlorine.
The following summarizes the Bureau of Census information on
SIC 2812.<*>
In 1972, the value of products shipped and miscellaneous
receipts of establishments classified in the Alkalies and
Chlorine Industry amounted to $803 million, an increase of
12 percent compared with 1967. Value added by manufacture
at $U37 million in 1972 was 4 percent above value added in
1967. Average employment in the industry showed a decrease
of 31 percent from 1967 to a total of 13 thousand employees
in 1972.
Of the $803 million total value of shipments and other
receipts of establishments classified in the Alkalies and
Chlorine Industry, $262 million were products primary to
other industries and $18 million were receipts for
miscellaneous activities. The industry shipments of primary
products represented 67 percent of the total manufactured
products shipments, primary and secondary. This percent,
called the "specialization ratio" for the industry, was 67
percent in 1967, also.
The total value of alkalies and chlorine shipped by all
producers in 1972 was $801 million of which $523 million, or
65 percent, was shipped by plants classified in Industry
2812, Alkalies and Chlorine, while the remainder was shipped
by plants classified in other industries. This percentage,
called the "coverage ratio," was 75 percent in 1967.
3-1
-------
The types of products, quantities produced and value of
shipments for this industry in 1972 are shown in Table 3.1.
3.3 Economic Strugture and Products of the Industrial Gases
Ifldustrjk. SIC 28.13
The Industrial Gases Industry includes establishments pri-
marily engaged in manufacturing gases for sale in
compressed, liquid, and solid forms. The following
summarizes the Bureau of Census information on SIC 2813.<•>
Establishments primarily engaged in manufacturing fluorine
and sulfur dioxide are classified in industry 2819; house-
hold ammonia in industry 2842, other ammonia in industry
2873; and chlorine in industry 2812. Distributors of
industrial gases and establishments primarily engaged in
shipping liquid oxygen are classified in trade.
In 1972, the value of products shipped and miscellaneous
receipts of establishments classified in the Industrial
Gases Industry amounted to $673 million, an increase of
14 percent compared with 1967. Value added by manufacture
at $463 million in 1972 was 15 percent above value added in
1967. Average employment in the industry showed a decrease
of 9 percent from 1967 to a total of 9.4 thousand employees
in 1972.
Of the $673 million total value of shipments and other
receipts of establishments classified in the Industrial
Gases Industry, $31 million were products primary to other
industries, and $47 million were receipts for miscellaneous
activities. The industry shipments of primary products
represented 95 percent of the total manufactured product
shipments, primary and secondary. This percent, called the
"specialization ratio" for the industry, was 96 percent in
1967.
The total value of industrial gases shipped by all producers
in 1972 was $649 million of which $595 million, or
92 percent, was shipped by plants classified in industry
2813, Industrial Gases, while the remainder was shipped by
plants classified in other industries. This percentage,
called the "coverage ratio," was 89 percent in 1967.
The types of products, quantities produced and value of
shipments for this industry in 1972 are shown in Table 3.2.
3-2
-------
Table 3-1. Quantity and Value of Products: 1972, SIC 2812
(adapted from Bureau of Census, reference 5)
Product Code
2812- --
t
28121 —
28121 11
28121 15
28122 —
28122 51
28122 31
28122 41
28122 45
28123 —
28123 51&70
28123 61 &71
28123 65475
28122 67&T7
28124 —
28124 21
28124 22
28124 23
28124 90
Product
ALKALIES AND CHLORINE, Total
Chlorine, Compressed or Liquefied, Total '
Gas
Liquid
Sodium Carbonate (Soda Ash), Total
Synthetic (58% Na2O):
Crude bicarbonate equivalent
Finished bicarbonate
Finished dense ash
Finished light ash
Sodium Hydroxide (Caustic Soda):
All processes (100% NoOH)
68-74% Liquid
All other liquid7
Dry (all forms)8
Other Alkalies, Total
Potassium hydroxide (caustic potash) i
(88-92% KOH):
Total liquid
Liquid
Solid
Other alkalies
Unit of
Measure
—
—
1 ,000 metric torn
ditto
__
1,000 metric torn
ditto
ditto
ditto
~
1 ,000 metric tons
ditto
ditto
ditto
~
1 ,000 metric tons
ditto
ditto
—
Production
for all
Purposes
(X)
(X)
8,955
4,461
(X)
3,909
112.7
2,114
1,676
(X)
9,267
732
7,962
431
159.2
142.2
17.0
(X)
Value of
Shipments
(million dollars)
801.4
208.0
24.7
182.5
147.0
(X)
10.6
82.0
52.6
410.5
(X)
30.6
319.9
50,5
(X)
21.4
3.1
6.0
(X) Not Applicable.
3-3
-------
Table 3-2. Quantity and Value of Products: 1972, SIC 2813
(adapted from Bureau of Census, reference 6)
Product Cede
2813- —
28132 -
28133 ~
28133 11
28133 31
28134 -
28134 15
28134 20
28134 40
28134 SO
28134 71
28134 98
28130 00
28130 02
Product
INDUSTRIAL GASES, Total
Acetylene, total
Carbon Dioxide, Total
Liquid and gas
Solid (dry ice)
Elemental Gases and Compressed and Liquefied
Gasei, N.E.C., Total
Argon, high purity (99.87-100%)
Helium
Hydrogen
Nitrogen
Gas
Liquid
Oxygen
Gas
Liquid
Nitrous oxide
Other Industrial gases, n.e.c., including
crude argon, carbon dioxide produced and
transferred for further processing, and
crude and high purity helium produced in
privately owned plants
Industrial gases, n.s.k., as reported In census
of manufactures for companies with 10 em-
ployees or more
Industrial gcues, n.s.k., as reported in census
of manufactures for companies with less than
10 employees
Unit of
. . Measure
..' •• ' "'
Mll.cu.m.
1,000 metric torn
ditto
ditto
__
Mll.cu.m.
ditto
ditto
ditto
ditto
ditto
ditto
ditto
ditto
Mll.cu.m(STP)
„
__
..
i
Production
for all
Purposes
(X)
10,492
1,343.5
1,065.5
278
(X)
3,450
(NA)
53,413
175,540
114,059
59,481
320,343
(NA)
, (NA)
1,159/4
(X)
w
(X)
Value of
Shipments
(million dollars)
648.8
94.5
39.2
23.4
15.8
479.2
33.1
(NA)
30.3
130.3
33.4
96.9
216.8
123.1
93.4
4.5
50.1
25.2
3.5
(X) Not applicable. (NA) Not available, n.e.c. Not elsewhere classified, n.s.k. Not specified by kind
3-4
-------
3.4 Economic Structure and Products of the Inorganic
" Pigments Industry, lie 2816
The Inorganic Pigments Industry includes establishments pri-
marily engaged in manufacturing inorganic pigments.
Important products of this industry include black pigments,
white pigments, and color pigments.
Organic color pigments, except animal black and bone black,
are classified in industry 2865. The following summarizes
the Bureau of Census information on SIC 2816*
In 1972, the value of products shipped and miscellaneous
receipts of establishments classified in the Inorganic
Pigments Industry amounted to $793 million, an increase of
44 percent compared with 1967. Value added by manufacture
at $384 million in 1972 was 22 percent above value added in
1967. Average employment in the industry showed an increase
of 1 percent from 1967 to a total of 12.7 thousand employees
in 1972.
Of the $793 million total value of shipments and other
receipts of establishments classified in the Inorganic
Pigments Industry, $103 million were products primary to
other industries, and $34 million were receipts for
miscellaneous activities. The industry shipments of primary
products represented 86 percent of the total manufactured
product shipments, primary and secondary. This percent,
called the "specialization ratio" for the industry, was
90 percent in 1967.
The total value of inorganic pigments shipped by all
producers in 1972 was $756 million of which $656 million, or
87 percent, was shipped by plants classified in industry
2816, Inorganic Pigments, while the remainder was shipped by
plants classified in other industries. This percentage,
called the "coverage ratio," was 84 percent in 1967.
The types of products, quantities produced and value of
shipments for this industry in 1972 are shown in Table 3.3.
ls.5 Economic Structure and frgdjjcjbs og the Industrial
Inorganic Chemical^ N.E.C.. Industry* sic 2819
The Industrial Inorganic Chemicals, N.E.C., Industry
includes establishments primarily engaged in manufacturing
industrial inorganic chemicals, n.e.c. Important products
of this industry include inorganic salts of sodium
(excluding refined sodium chloride), potassium, aluminum,
calcium, chromium, magnesium, mercury, nickel, silver, tin;
inorganic compounds such as alums, calcium carbide, hydrogen
3-5
-------
Table 3-3. Quantity and Value of Products: 1972, SIC 2816
(adapted from Bureau of Census, reference 7)
Product Code
2816- —
28161 11
28162 -
28162 13
28162 21
28162 25
28162 98
28162 00
28163 --
28163 10
28163 11
28163 13
28163 15
28163 17
28163 18
28163 19
28163 27
28163 31
28163 41
28163 45
28163 51
28163 61
28163 88
28163 91
28163 98
28163 00
28160 00
28160 02
Product
INORGANIC PIGMENTS, Total
Titanium Pigments, Composite and Pure
(100% TIO2), Total
Other White Opaque Pigments
White lead, basic carbonate and sulfate,
excluding white lead in oil
Zinc oxide pigments:
Lead-free zinc oxide
Leaded zinc oxide
All other white opaque pigments, including
antimony oxide, lithopono, and pure
zinc sulflde
Other white opaque pigments, n.s.k.
Chrome Colors and Other Inorganic Pigments
Chrome colors. Total
Chrome green (chrome yellow and
iron blue) (C. P.) .
Chrome oxide green (C.P.)
Chrome yellow and organce (C.P.)
Molybdate chrome orange (C.P.)
Zinc yellow (zinc chromate) (C.P.)
Other chrome colors (C.P.)
White extender pigments, including barytes.
blanc fixe, and whiting
Color pigments other than chrome colors and
lakes and toners:
Iron oxide pigments
Colored lead pigments:
Red lead
Litharge
Iron blues (Prussian blue, milort blue, etc.):
As reported in census of manufactures
Pearl essence
Carbon blacks (bone and lamp), excluding
furnace and channel carbon black and
charcoal
Ceramic colors
All other color pigments, including ultramarine
>lue (excluding organic pigments, lakes, and
toners)
Unit of
Measure
—
1 ,000 metric tons
—
1 ,000 metric tons
ditto
ditto
—
— •
—
—
1 ,000 metric tons
ditto
ditto
ditto
ditto
ditto
ditto
ditto
ditto
ditto
ditto
ditto
ditto
ditto
—
Chrome colors and other inorganic pigments, n.s.k.
Inorganic pigments, n.s.k., for companies with
10 employees or more
norgonic pigments, n.s.k., for companies with
ess than 10 employees
—
for all
Purposes
(X)
639.7
(X)
16.6
212.9
(D)
(X)
(X)
(X)
(X)
(0)
5.6
30.6
11.2
5.2
(S)
(S)
(S)
24.0
162
4.8
(0)
2
(S)
(X)
(X)
(X)
(X)
Value of
Shipments
(million dollars)
755.7
355.3
101 .-S
5.0
79.2
*
14.5
2.9
284.5
59.1
(D)
5.9
24,5
13.7
4.6
(S)
14.2
40.1
11.1
49.3
6.5
(D)
.9
36.5
58.9
7.9
9.0
5.1
Included with product code 28163 98. (X) Not applicable (S) Withheld - poor data.
(D) Withheld to avoid disclosing
figures for individual companies.
3-6
-------
peroxide, sodium silicate, ammonia compounds (except
fertilizers), rare earth metal salts and elemental bromine,
fluorine, iodine? phosphorus, and alkali metals (sodium,
potassium, lithium, etc0J. Establishments primarily engaged
in mining, milling* or otherwise preparing natural
potassium, sodium, or boron compounds (other than common
salt) are classified in industry "8474. Establishments
primarily engaged in manufacturing household bleaches are
classified in industry 2842; phosphoric acid in industry
2874; and nitric acid, anhydrous ammonia and other
nitrogenous fertilizer materials in industry 2873. The
following summarizes the Bureau of Census information on SIC
2819.<«>
In 1972, the value of products shipped and miscellaneous
receipts of establishments classified in industry 2819
amounted to $3,658 million. The 2819 industry reported
value added by manufacture of $10997 million and employment
of 61 thousand in 1972.
Of the $3,658 million total value of shipments and other
receipts of establishments classified in the 2819 industry,
$323 million were products primary to other industries, and
$1,032 million were receipts for miscellaneous activities.
The industry shipments of primary products represented
88 percent of the total manufactured product shipments,
primary and secondary. This percentage is called the
"specialization ratio.01
The total value of industrial inorganic chemicals, n.e.c.,
shipped by all producers in 1972 was $2,946 million of which
$2,303 million or 78 percent, was shipped by plants
classified in industry 2819, Industrial Inorganic Chemicals,
N.E.C., while the remainder was shipped by plants classified
in other industries. This percentage is called the
"coverage ratio."
The types of products, quantities produced and value of
shipments for this industry in 1972 are shown in Table 3.4.
3^.6 Individual Chemical Processes and Waste Streams
The processes by which the various chemicals covered in this
report are manufactured and their associated waste streams
are discussed in detail in Section 5 of this report.
The inorganic chemicals industry is further characterized by
the number of plants, age of plants, size of plants and
location of plants in Section 4 of this report.
3-7
-------
Table 3-4. Quantity and Value of Products: 1972, SIC 2819
(adapted from Bureau of Census, reference 8)
Product Code
2819- —
28193 —
28193 11
28193 15
28193 17
28193 31
28193 51
28193 71
28194 —
28194 11
28194 31
28194 41
28194 45
28194 47
28194 51
28194 61
28194 65
28194 67
28194 98
28195 —
28196 --
28196 11
28196 15
28196 17
28196 25
28196 27
28196 51
28196 55
28196 71
28197 -
28197 13
Product
INDUSTRIAL INORGANIC CHEMICALS,
N.E.C., Total
Sulfuric Acid, Total
Contact acid:
Oleum under 40%
Oleum 40%
Oleum over 40%
Other than oleum grades
Chamber acid
Spent acid used in fortification in contact
units and included in production reported
above, including acid from own production
or received from outside sources
Inorganic Acids, except Nitric and Sulfuric,
Total
Boric (boraic) (100% H3BO3)
Chromic acid (100%CrO;j)
Hydrochloric, including anhydrous
(100% HCI)
From salt
From chlorine
Byproduct and other
Hydrocyanic, including anhydrous
(100%HCN)
Hydrofluoric(100%HF):
Anhydrous
Technical
Mixed (sulfuric and nitric)
Other Inorganic acid acids, n.e.c.
Aluminum Oxide, Except Alumina
(100% AI2O3), Total
Other Aluminum Compounds, Total
Chloride:
Liquid (32° Be1)
Crystal (32° Be1)
Anhydrous (1 00% AICI3)
Hydroxide: trihydrate (100% AI2O3' 3H2O)
Fluoride (technical)
Sulfate:
Commercial (17% Al2O3>
Iron free (17% AI2C3)
Other inorganic aluminum compounds,
Including sodium aluminate, light
aluminum hydroxide, cryolite,
and alums
Potassium and Sodium Compounds (Except
Bleaches, Alkalies, and Alums), Total
Potassium compounds, n.o.c.
Iodide (100% Kl)
Unit of
Measure
„_
1 ,000 metric tons
ditto
ditto
ditto
ditto
ditto
—
»_
1 ,000 metric tons
ditto
ditto
ditto
ditto
ditto
ditto
ditto
ditto
ditto
ditto
ditto
1 ,000 metric tons
—
1 ,000 metric tons
ditto
ditto
ditto
ditto
ditto
ditto
—
....
1,000 metric tons
Production
for all
Purposes
(X)
28,388.8
1,706.9
484.9
218.2
25,849.3
129.5
1,118.1
(X)
110.2
24.6
2,088.3
103.2
93.3
1,891.8
123.2
218.7
16.1
185.5
(X)
5,624.2
(X)
(D)
(D)
30.3
480.1
126
1,139.5
64.6
(X)
(X)
.99
Value of
Shipments
(million dollars)
2,946.5
248.1
31.4
(D)
(D)
205.6
0.4
(X)
153.0
11.1
15.8
36.9
4.2
3.7
29.0
*
52.7
7.9
*
28.9
387.9
174.2
(D)
(D)
8.9
47.2
36.1
51.6
3.0
27.3
501.1
4.5
(X) Not applicable. (D) Withhold to avoid disclosing Individual company data. * Included with product code 28163.
3-8
-------
Table 3-4. Quantity and Value of Products: 1972, SIC 2819
(adapted from Bureau of Census, reference 8)
Product Code
2819- -
28193 --
28193 11
28193 15
28193 17
28193 31
28193 51
28193 71
J8.194 —
28194 11
28194 31
28194 41
28194 41
28194 47
28194 51
28194 61
20194 65
28194 67
28194 98
28195 --
28196 -
28196 11
28196 15
28196 17
28196 25
28196 27
58196* 51
28196 55
28196 71
28197 --
28197 13
Product
INDUSTRIAL INORGANIC CHEMICALS,
N.E.C., Toial
Sulfuclc Acid, total
Contact acid:
Oleum under 40%
Oleum 40%
Olcun over 40%
Other than oleum grades
Chamber acid
Spent oc!d used in fortification in contact
unit* and Included In production reported
obove. Including odd fiom own production
or received from outside sources
Inorganic Adds, except Nitric ond Sulfuric,
Total
Boric (boroic) (100% H3BO3)
Chromic acid (100%CrC3)
Hydrochloric, Including anhydrous
(100% HCI)
From salt
From chlorine
BvnicHuct uitd olhur
Hydrocyanic, including anhydrous
(100%HCN)
Hydiolluoric (100% HP):
Anhydrous
Technical
Mixed (lulfuric ond nitric)
Other Inorganic acid acids, n.o.c.
Aluminum Oxide, Except Alumina
(100% AI2O3), Total
Other Aluminum Compounds, Total
Chloride:
Liquid (32° Be1]
Crystal (32° Bo1)
Anhydrous (100% AlCIs)
Hydloxitlc: Irihydrote (100% AI2O3' 3H2O)
Fluoride (technicol)
Sulfute:
Commerciol (17%AI2O3)
lronlree(17%AI2O3)
Other Inorganic aluminum compounds,
Including sodium aluminitc, light
aluminum hydroxide, cryolite.
ond alums
Potassium ond Sodium Compounds (Except
Bleaches, AlkaHci, ond Alumv), Tola!
Potassium compounds, n.e.c.
Iodide (100% Kl)
Unit of
Measure
..
1,000 metric tons
ditto
ditto
ditto
ditto
ditto
—
-
1 ,000 metric tons
ditto
ditto
ditto
ditto
ditto
ditto
ditto
ditto
ditto
ditto
ditto
1 ,000 metric tons
. ~
1,000 mctiic tons
ditto
ditto
ditto
ditto
ditto
ditto
.-
„
1 ,000 metric Ions
Production
lor all
Purposes
(X)
28,388.8
1,706.9
484.9
218.2
25,849.3
129.5
1,118.1
(X)
110.2
24.6
2,088.3
103.2
93.3
1,891.8
123.2
218.7
16.1
IBS. 5
(X)
5,624.2
(X)
(0)
(01
30.3
480.1
126
1,139.5
64.6
(X)
(X)
.99
raucor"
Shipment*
(million dollar*)
2,946.5
248.1
31.4
(0)
(0)
205.6
0.4
(X)
153.0
11.1
15.8
36.9
4.7
3.7
29.0
•
52.7
7.9
*
28.9
387.9
174.2
(0)
(D)
8.9
47.2
36.1
51.6
3.0
27.3
501.1
4.5
(X) Not applicable. (D) Will.hcld to ovoid disclosing Individual company data. • Included with product code 7QI6X
3-9
-------
Table 3-4. Quantity and Value of Products:
continued (adapted from Bureau
reference 8)
1972, SIC 2819 -
of Census,
Product Codi-
70197 16
78197 10
20197 17
28197 21
28197 24
28197 27
20197 28
28197 29
20197 30
20197 32
20197 33
20197 34
28197 35
28197 36
20197 37
28197 38
28197 41
_2B197 43
28197 51
28197 61
20197 65
20197 67
78197 81
28197 82
28197 83
28197 C4
28197 85
20197 87
28198 —
28199 —
28199 01
28199 02
20199 04
28199 06
28199 07
28199 09
Z0199 10
28199 11
20199 12
26199 13
20199 14
28199 15
20199 16
20199 41
78199 19
20199 20
20199 10
20199 21
Product
Sulfiile (100% K?SO.|)
Tclrapolcissiiim pyuf|>lu>yhule
(100% KjP207l
Other potassium salts and compounds,
n.e.c.
Sodium (metal) (100% Na)
Sodium compounds, n.e.c.:
Berate (borax)
. Chlorate (100% NoC 103)
Fluoride
Hydrosulfide (sodium sul (hydrate)
(100%NaSH)
Hydrosulfile (100% NajS^^)
Phosphate:
Monobasic (100% NaH2PO4)
Dibasic (100% Na2HPO4)
Tribosic (100% Nc3PC>4)
Tctrobasic (100% Nc.jPjO;)
Meta (100% Nnr03)
Acid pyro (100% Na?H2P2O7)
Tripoly (100% No5P3O|0)
Silicates:
Soluble silicate glass (water glass)
solid and liquid (anhydrous)
Metosilicate (100-\- No2SiO3' 5H2O)
Silicofluoride (100% Nc^SiF^)
Sulfale:
High purity (refined) (100% No2SO4)
low purity (?9% of less Na2SO4)
(100% No2S04)
Glauber's salt (100% Na25O4'10H2O)
Sulfidc:
Crystal
Concentrated (60-62% No?S)
Other, Including liquid and crystal
(60-6% No2S)
Sulfilc (100% No2SC4)
Thiosulfate (hypo) (100% Na2S2O3'5H2O)
Other sodium compounds, n.e.c.
Chemical Catalytic Preparations, Total
Other Inorganic Chemicals, H.E.C., Total
Reagent and high purity grades of. inorganic
chcmicols refined from purchased
technical grades
Antimony compounds, (excluding pigment
grades)
Barium compounds:
Carbonate (precipitated) (100% BoCO3)
Other barium compounds
Bismuth compounds:
Subcarbonotc (100% (8120^03) 'H2O)
Other bismuth compounds
Bromine (100% Br)
Codium compounds
Calcium compounds:
Calcium compounds:
Corbide (commercial)
Carbonate (precipitated) (1 0%CoCOs)
Chloride:
Solid, excluding (lake (73-75% CoCI2)
rioki. (/7-eQ%C«CI?)
Liquid (40-40% CoCl2)
Calcium hypochloritc (high test)
(70% avail. Cl)
Phosphate:
Dibasic:
Aninol feed giudes
Other grades (cxc< pt fertilizer grades
Monobasic
Tribosic
Unit of
Measure
ditto
ditto
—
1,000 metric tons
ditto
ditto
ditto
ditto
ditto
ditto
ditto
ditto
ditto
ditto
ditto
ditto
1 ,000 metric tons
ditto
ditto
ditto
ditto
ditto
ditto
ditto
ditto
ditto
ditto
—
-
--
...
—
1,000 metric tons
1,000 metric tons
—
1,000 metric tons
—
1,000 metric tons
ditto
ditto
ditto
ditto
1,000 metric Ions
ditto
ditto
• -
••"
Production
for all
Pur[»si-s
364.9
44.6
(X)
145.6
498.5
175.8
5.6
22.8
42.4
• 30.5'
18.9
52.5
42.1
72.1
24.7
936.7
599.2
251.1
52.1
726.1
477.5
477.5
130.1
130.1
130.1
202.5
19.6
(X)
(X)
(X)
(X)
63.7
(X)
(Z)
(X)
(X)
(X)
447.5
200.4
589.7
589.7
470.4
(0)
627.5
627.5
(X)
(X)
Voh.c-ol
Shipuu-nls
(million dnlluiO
16.4
5.0
90.1
37.2
10.4
16.7
2.2
2.7
20.9
7.1
4.4
10.5
8.7
16.7
6.7
143.6
45.3
21.3
6.3
17.0
11.1
11.1
4.9
4.9
4.9
9.4
2.7
130.9
167.5
1,303.4
44.4
2.3
8.3
8.9
0.3
2.2
14.1
8.4
24.6
12.1
76.1
26.1
4.9
(D)
61.8
61.8
9.7
9.7
(X) Not applicable. (0) Withhold to ovoid disclosing Individual compnny data, (2) Less than half of Iho unit of measure shown
3-10
-------
Table 3-4. Quantity and Value of Products: 1972, SIC 2819 -
continued (adapted from Bureau of Census,
reference 8)
Product Code
2819V 23
28)99 24
28199 K
28199 27 & 31
28199 32
28199 33
28199 34
28199 35
28199 36
28199 37
28199 39
28)99 40
28199 42
28199 43
28199 44
— "
28199 45
28199 47
28199 48
28199 49
26199 50
28199 52
28199 53
28199 55
28199 90
28199 56
28199 57
28199 58
28199 59
28199 60
28199. 63
28199 61
28199 65
28199 66.
28199 68
28199 69
20199 70
28)99 71
28199 72
20199 73
Product
Other Inorganic calcium compounds
Corbon, activated:
Decolorizing
Water purification
Chromium compounds:
Bichromate! and chromotei:
Sodium bichromate and cliromole
(hydrous)
Other chromium compounds including
potoisium bichromate and chromato
(hydrous) (excluding chrome colon)
Coboll compounds
Copper compounds:
Cupric oxide (100% CuO)
Cuprous oxide (100% CujO)
Copper sulfote (100%CuSO4' SHjO)
Other coppor compounds (including
copper cyanide)
Hydrogen peroxide
Iodine, crude* or rcsublimrd (100% ))
Iron compounds:
Ferric chloride (100% FeCI3)
Ferrous sulfolc (100% FoSO^HjO)
Other iron compounds
Lead Compounds:
Nitrate
Other lead compounds (excluding
pigment grade)
Magnesium compounds:
Sulfate, including Fpsom salts
(100% Mg.S04>
Other magnesium compounds
Monponcse compounds:
Suirole(100%MnSO4"lH4O)
Other manganese compounds, including
potassium and other permanganate! and
manganese dioxide, battery grade
Mercury ond compounds:
Mercury, redistilled (Ib)
Other mcrcuiic compounds, except
mercuric fulminate and medicinal
grades
Molybdenum, platinum, radium, strontium.
tantalum, thallium, ond tungsten
compounds
Nickel compounds:
Sulfoto (100%, NiSO4'6H2O)
Other nickel compounds
Phosphorus ond compounds:
While (yellow) (technical)
Red (technical)
Oxychloridc ()00%POCl3)
Trichloride (chloride) (100% PCIl)
Pcnlosulfidc (100% P?S5)
Rare earth compounds '
Selenium compounds
Silica gel:
Butadiene catalyst grade
Dosi cant grade
Aviation QOS catalyst grade
Silver compounds: '
Cyanide (100% AqCN)
Nilrolc (100% AgNoj)
Other silver compounds
Unit of
Mcosurc
..
1,000 metric tons
ditto
ditto
— -
— •
--
1,000 metric Ions
ditto
ditto
—
1 ,000 metric Ions
1,000 metric tons
1 ,000 metric tons
ditto •
— •
~
— •
•-
—
\ ,000 metric tons
—
1 ,000 metric tons
— •
—
1 ,000 metric tons
—
1,000 metric tons
ditto
ditto
ditto
ditto
«
--
--
—
—
28.35 kg.
ditto
•••
Production
(or oil
Purposes
(X)
79.3
79.3
133.1
(X)
(X)
(X)
1.6
1.7
(D)
(X)
66.5
(S)
69.6
(0)
(X)
(X)
(X)
(X)
(X)
28.7
(X)
313.1
(X)
(X)
9.3
(X)
504.2
31.4
31.4
57.7
55.5
(Xj
(X)
(X)
(X)
(X)
36.8kg
2, 832.2 kg.
(X)
Volue of
Shipments
(million dollnis)
48.5
29.3
29.3
24.5
8.9
8.9
10.8
1.4
2.0
(D)
23.5
31.0
(S)
5.6
-------
Table 3-4. Quantity and Value of Products: 1972, SIC 2819 -
continued (adapted from Bureau of Census,
reference 8)
Product Code
28)99 74
28199 75
28199 77
^
28199 80
28199 81
28199 87
28199 88
28199 91
28199 92
28199 94*95
28199 98
28199 00
28199 02
Piodurl
Sulfur, recovered elemental
Sulfur compounds:
Dioxide (produced lor sold (100% SO?)
Oilier sulfur compounds (Including sulfur
chlorUe)
Tin compounds:
Ouicfe (ttonnic) (lOO'iSnOj)
Oilier tin compounds (including stannic
anj stonnoui chloride)
Zinc compound*:
Sulfote (IOO%7nSar~H2O)
Other zinc compounds excluding piometil
grades
Radioactive iicochrs including liquid lime
faleacries
All other inoigomc cKomicoU, n.c.c.
Industrial inorganic chemicals, ri.s.k., rrpc>rtrtd
In census of rmnufoctuirn, for companies with
10 employees or mote
tn ccrnii: of manuioctuibs, for companies willi
less
\"l
Value o(
Shipments
(million dollar!)
29.8
5.4
10.9
(D)
19.B
-
6.8
13.o
37.9
15.9
5.1
214.7
18.8
Q
(X) Not applicable. (D) V.'iihhcld to ovoid dtidosmg individual company dnto.
3-12
-------
3^7 Future Inorganic Chemicals Industry Developments
As a whole the inorganic chemicals industry is a basic and
an expanding industry. Future changes in the industry will
probably be dictated by economic and environmental
considerations along with availability of raw materials.
Some of the presently known probable occurrences will be:
SIC 2812: Three trends are taking place in the chlor-alkali
industry that will greatly reduce the generation of
hazardous wastes to land disposal: No new construction of
mercury cell chlor-alkali plants, carbon anodes will be
gradually replaced with coated metal anodes which will
reduce the chlorinated hydrocarbon wastes in this industry,
the eventual use of synthetic separators to replace asbestos
separators and therefore the asbestos waste.<•*> ces) (66)
<67> NO new Solvay Process soda ash plants are expected to
be constructed in the near future because of both economic
and environmental considerations.
SIC 28.13: No significant changes are projected for this
industry other than general growth with the national
economy.
SIC 2816; Based on opinions expressed by industry members,
the major trends for the inorganic pigments industries are
as follows. No new sulfate process titania plants are
planned for the near future and the chloride process for
producing titania is expected to bear the projected
expansion in the industry.<*o) The chrome pigments industry
is expected to experience only slow growth over the next
decade.
SIC 2JM9: Industry opinion is that these commodities in
general will experience growth in line with the national
economy. Some process changes may be made or product lines
dropped if certain raw materials do not become more
available. A case in point is metallic zinc. One
manufacturer in the Northwest is known to have closed down
their zinc sulfate production because of inability to obtain
zinc raw material. Otherwise, no major changes are expected
in these industries.
Details and discussions of these trends are given in the
Section 5 presentation for the various commodities.
3-13
-------
4.0 INDUSTRY CHARACTERIZATION
U.I Categorization of the ^ndustry
The first phase of this assessment of hazardous waste
practices for the Inorganic Chemicals Industry consisted of
a statistical characterization of the industry in terms of
the number and location of manufacturing plants, the
distribution of plant sizes in terms of production capacity,
the distribution of plant ages, the distribution of
processes used and the distribution of actual production for
each industry subcategory. The data are meant to be
representative of 1974. The sources of the data are given
in Section 1.1, Methodology. The data base represents a
variety of time periods and was made base consistent by
extrapolation.
This report covers the products manufactured in the
following four major categories: <*> <7> <8> <™>
SIC 2812 - Alkalies and Chlorine
SIC 2813 - Industrial Gases
SIC 2816 - Inorganic Pigments
SIC 2819 - Industrial Inorganic Chemicals
elsewhere classified)
(not
A further breakdown into five-digit SIC classifications is
sufficiently detailed for a thorough subcategorization of
the industry as follows:
SIC 2812 Alkalies and Chlorine
28121 Chlorine
28122 Sodium Carbonate (Synthetic Soda
Ash S Sodium Bicarbonate)
28123 Sodium Hydroxide
28124 Other Alkalies (includes KOH, K2CO3)
SIC 2813 Industrial Gases
28132 Acetylene
28133 Carbon Dioxide
28134 Elemental Gases 6 other Industrial
Gases (NEC) (includes A, He, H2, N2,
O2, N2O, Ne)
4-1
-------
SIC 2816 Inorganic Pigments
28161 Titanium Pigments
28162 Other White Opaque Pigments (includes
White Lead, ZnO, Sb2O3, Lithopone,
ZnS, PbSOU)
28163 Chrome Colors and Other Inorganic Pig-
ments (NEC) (includes chrome colors,
white extender pigments, iron oxide
pigments, colored Pb pigments, iron
blues, carbon blacks)
Sic 2819 Industrial^Inorganic Chemicals
28193 Sulfuric Acid (includes oleum)
28194 Inorganic Acids, except nitric and
sulfuric (includes boric, chromic,
HC1, HCN, HF, mixed)
28195 Aluminum Oxide
28196 Other Aluminum Compounds
28197 Potassium and Sodium Compounds
(except bleaches, alkalies, and
alums)
28198 Chemical catalytic Preparations
28199 Other Inorganic Chemicals (NEC)
It should be noted that the total number of facilities
making the products in the SIC 281 group that were found in
this search is approximately 1,600, when broken down by this
5-digit SIC code method. This method double accounts for
certain complexes making more than one of the SIC 281
commodities, as well as including plants within complexes
which are not engaged primarily in 281 manufacture; e.g.,
chlorine plants within paper mills. Therefore the number of
facilities in the 4 digit code major categories generally is
less than the total of the plants in the constituent 5-digit
subcategories.
In the industry characterization data tables that follow,
the values given for annual production have been expressed
in a form that gives no more than two significant figures so
that no greater accuracy is implied than is justified by the
estimation processes used to develop the values. Because of
the rounding off to two significant figures, the values
given for the national and regional totals will not
necessarily be identical to the numerical sum of the state
values.
iiJ Characterization of SIC 2812. Alkalies and Chj.orine
Industry
Tables 4-1 through 4-5 characterize this industry with the
following information:
4-2
-------
Table 4-1. SIC 2812 Alkalies and Chlorine,
Distribution of Establishments
Numbor of
Establishments
IV Alabama
X Alaska
IX Arizona
VI Arkansas
XX California
VIII Colorado
I Connecticut
III Delaware
IV Florida
IV Georgia
IX Hawaii
X Idaho
V Illinois
V Indiana
VII Iowa
VII Kansas
IV Kentucky
VI Louisiana
I Maine
III Maryland
I Massachusetts
V Michigan
V Minnesota
IV Mississippi
VII Missouri
VIII Montana
VII Nebraska
IX Nevada
I New Hampshire
II New Jersey
VI New Mexico
II New York
IV North Carolina
VIII North Dakota
V Ohio
VI . Oklahoma
X Oregon
III Pennsylvania
I Rhode Island
IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII Utah
I Vermont
III Virqinia
X Washington
III West Virginia
V Wisconsin
VIII Wyoming
TOTAL
Region I
II
III
IV
V
VI
VII
VIII
IX
X
26121
Chlorine
4
1
1
3
1
1
2
9
1
4
1
1
2
5
2
4
1
3
11
1
1
4
3
\
67
1
7
5
15
11
20
1
2
5
2dl22*
Synthetic
Sodium
Carbonates
2
1
1
2
1
2
9
1
3
3
2
28123
Sodium
Hydroxide
4
1
1
3
1
1
2
9
1
4
1
2
2
2
3
'1
2
9
1
3
2
59
1
4
5
13
10
18
1
2
5
261 i4
Other
Alkalies
2
1
1
1
1
1
3
1
1
1
2
15
4
2
4
3_
2
2612
as a
Whole
4
1
1
3
1
1
2
10
1
4
I
1
3
5
3
4
1
1
3
12
1
1
4
3
Z
2
74
1
8
I
16
11
22
1
2
2
«;
4-3
-------
Table 4-2. SIC 2812 Alkalies and Chlorine,
Distribution of Plant Sizes
Plant Size,
Daily Capacity (metric tons)
IV Alabama
X Alaska
IX Arizona
VI Arkansas
IX California
VIII Colorado
I Connecticut
III Delaware
IV Florida
IV Georgia
IX Hawaii
X Idaho
V Illinois
V Indiana
VII Iowa
VII Kansas
IV Kentucky
VI Louisiana
I Maine
III Maryland
I Massachusetts
V Michican
V Minnesota
IV Mississiooi-
VII Missouri
VIII Montana
VII Nebraska
IX Nevada
I New Hampshire
II New Jersey
VI New Mexico
II New York
IV North Carolina
VIII North Dakota
V Ohio
VI Oklahoma
X Oregon
III Pennsylvania
I Rhode Island
IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII Utah
I Vermont
III Virginia
X Washinoton
III West Virginia
V Wisconsin
VIII Wvoming
TOTAL
Region I
II
III
IV
V
VI
VII
VIII
IX
X
28121
Chlorine
A
0
B
1
1
1
1
1
1
1
]
8
1
a
'2
1
1
c
a
1
?
1
2
7
1
4
1
1
2
fl
1
3
1
3
ft
4
3
1
-------
Figure 4-3. SIC 2812 Alkalies and Chlorine,
Distribution of Plant Ages
Plant Age (years)
IV Alabama
X Alaska
IX Arizona
VI Arkansas
IX California
VIII Colorado
I Connecticut
III Delaware
IV Florida
IV Georgia
Ik Hawaii
X Idaho
V Illinois
V Indiana
Vii "Iowa
VII Kansas
IV Kentucky
VI Louisiana
I Maine
lli Maryland
I Massachusetts
V Michigan
V • Minnesota
IV Mississippi
VII Missouri
VIII Montana
VII Nebraska
IX Nevada
I New Hampshire
II New Jersey
VI New Mexico
II New York
IV North Carolina
VIII North Dakota
V Ohio
VI Oklahoma
X Oregon
III Pennsylvania
I Rhode Island
IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII Utah
I Vermont
III Virginia
X Washington
III West Virginia
V Wisconsin
VIII Wyoming
TOTAL
Region I
II
III
IV
V
VI
VII
VIII
IX
X
281 21
Chlorine
A
2
1
1
3
I
8
1
1
1
5
B
4
1
:
i
i
2
5
'
2
'
2
3
1
2
4
2
11
40
J
z
13
8
V
3
C
2
2
3
4
1
2
1
19
3
2
^
3
6
2
2
28122
Synthetic
Sodium
Carbonate
A
0
B
2
2
2
C
1
2
1
1
2
1
1
y
i
3
3
26123
Sodium
Hydroxide
A
2
1
1
4
1
1
2
B
4
1
3
1
1
2
5
1
2
2
2
5
2
1
2
38
3
2
11
7
10
3
C
2
2
1
1
1
1
4
1
2
1
17
1
2
1
Ji
Q
2
2
28124
Other
Alkalies
A
1
1
2
1
1
B
1
1
1
1
1
1
1
7
2
_2_
3
C
1
1
1
1
2
0
1
3
2
KEY: A = less than 5; B = 5 to 30; C = Over 30
4-5
-------
Table 4-4. SIC 2812 Alkalies and Chlorine,
Distribution of Processes
Process Types,
No. of Facilities
IV Alabama
X Alaska
IX Arizona
VI Arkansas
IX California
VIII Colorado
I Connecticut
III Delaware
IV Florida
IV Georgia
IX Hawaii
X Idaho
V Illinois
V Indiana
VII Iowa
VII Kansas
IV Kentucky
VI Louisiana
I Maine
III Maryland
I Massachusetts
V Michigan
V Minnesota
IV Mississipoi
VII Missouri
VIII Montana
VII Nebraska
IX Nevada
I New Hamoshire
II New Jersey
VI New Mexico
II New York
IV North Carolina
VIII North Dakota
V Ohio
VI Oklahoma
X Oregon
III Pennsylvania
I Rhode Island
IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII Utah
I Vermont
III Virginia
X Washington
III West Virginia
V Wisconsin
VIII Wyoming
TOTAL
Region I
II
III
IV
V
VI
VII
VIII
IX
X
28121
Chlorine
A
4
1
?
1
2
3
]
1
3
1
1
1
2
?
?
?R
I
4
3
10
3
s
2
B
1
1
l
7
4
1
1
2
1
7
1
1
8
1
?
?
37
3
3
t
7
1-1
1
2
3
C
1
1
1
1
1
•5
1
1
1
?
0
7
?
?
t
Synetfieic NJ
Sodium jj
Carbonate *»
F
2
1
1
1
1
1
2
1
7
1
3
3
G
1
1
1
_2~J
1
1
?
i
28123
Sodium
Hydroxide
A
4
1
2
1
7
3
1
1
1
1
]
1
7
?
?
1
?6
1
?
3
in
3
,1
2
B
1
1
1
7
4
1
1
l
2
7
1
1
fl
i
2
7
1
37
2
3
4
7
Ifi
1
7
3
C
1
1
1
28124
Other
Alkalies
A
'4
]
l
1
1
l
1
1
?
?
2
1
1
1
B
1
1
?
1
1
H
1
1
1
4
1
1
1
]
1
1
1
1
3
1
1
1
A = Mercury Cell; B = Diaphragm Cell; C = Down's Cell; D = HCI Process;
E = NOCI Process; F= Solvay Process; G= Bicarbonate Process;
H = Potassium Carbonate Process; I = Ammonium Carbonate Process
4-6
-------
Table 4r5. SIC 2812 Alkalies and Chlorine,
Distribution of Production
Annual Production
103 metric tons
IV Alabama
X Alaska
IX Arizona
VI Arkansas
ISH California
Vlil Colorado
I Connecticut
III Delaware
W Florida
IV Georgia
IX Hawaii
X Idaho
V Illinois
V Indiana
VII Iowa
VII Kansas
IV Kentucky
VI Louisiana
I Maine
III Maryland
I Massachusetts
V Michigan
V . Minnesota
IV Mississippi
VII Missouri
VIII Montana
VII Nebraska
IX Nevada
I New Hampshire
II New Jersey
VI New Mexico
II New York
IV North Carolina
Vlli North Dakota
V . Ohio
VI Oklahoma
X Oregon
III Pennsylvania
I . Rhode Island
IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII Utah •
I . Vermont
III Virginia
X Washington
III West Virginia
V Wisconsin
VIII Wyoming
TOTAL
Region I
II
• ' . Ill
IV
V
vi '
VII
vi ii
IX
X
28121
Chlorine
320
15
130
180
32
73
2(0
2.6(0
65
510
46
48
240
460
7l
7AO
130
330
4 000
73
17
330
590
76
11,000
65
700
740
880
6 Ann
73
73
.460
28122
Synthetic
Sodium
Carbonates
960
750
1.000
790
770
A40
4,400
1.000
1.500
1 900
640
28123
Sodium
Hydroxide
345
17
150
190
59
80
2.700
72
560
. 53
260
140
78
.250
110
290
2rOOO .
18
310
650
88
8.600
72
4QO
820
i "inn .
V960
4 700
80
7)
42 1
28124
Other
Alkalies
100
M
55
23
0
9
0
30
0
6.6
250
9
25
17p
85 .
6 A
2812
as a
Whole
760
32
300
370
f
150
150
44(
6.3«L
140
1.800
46
100
500
1,600
150
1.300
240
0
620
6r300
73
35
600
1.200
160
640
24.000
140
2r100
i.spo
7 400
3'^ 00
13 000
150
70XL
13i)
840
4-7
-------
Table 4-1 gives the distribution and number of establish-
ments producing the products in the four 5-digit SIC sub-
categories. The number of establishments covered in SIC
2812 was 78 with the heaviest concentration in EPA Region VI
(almost 30%) . Louisiana and Texas contain all of the Region
VI SIC 2812 facilities.
Table 4-2 gives the distribution of plant sizes by daily
production capacity in the four industry subcategories.
Seventy-six percent of SIC 28121 plants have daily
capacities in the range of 100-999 tons. SIC 28122 plants
are divided 44 percent in the 100-999 tons per day range and
56 percent in the over 1000 tons per day class. Most (81
percent) SIC 28123 plants are in the 100-999 tons per day
range. The other alkalies subcategory, SIC 28124, is almost
evenly divided into the 10-99 tons per day and 100-999 tons
per day brackets.
Table 4-3 lists the distribution of plant ages in SIC 2812.
Most SIC 28121 and SIC 28123 plants (approximately 60%) fall
in the 5-30 year age range. Over 75% of SIC 28122 plants
are over 30 years old and over 85% of SIC 28124 plants are
almost evenly split in the two age ranges of 5-30 years and
over 30 years. The reason for the relatively old
distribution of ages in 28122 is the lack of new
construction of Solvay plants because of the recent
exploitation of natural sources of soda ash.
Table 4-4 shows the distribution by process types in
SIC 2812,
Table 4-5 lists the distribution of production in this
industry. About 54% of total production in SIC 2812 takes
place in EPA Region VI.
According to the 1972 Census of Manufacturers, the
establishments primarily engaged in SIC 2812 manufacture
average 283 total employees per establishment and
202 production employees per establishment. Eighty-one
percent of the reported establishments have 20 or more
employees.
iiil Characterization of SIC 2.813* Industrial Gases Industry
Tables 4-6 through 4-10 characterize this industry with the
following information:
Table 4-6 gives the distribution and number of
establishments producing the products in the three 5-digit
SIC subcategories. The number of establishments covered in
4-8
-------
Table 4-6. SIC 2813 Industrial Gases,
Distribution of Establishments
Number of
Establishments
IV Alabama
X Alaska
IX Arizona
VI Arkansas
IX California
VIII Colorado
I Connecticut
HI Delaware
W Florida
IV Georgia
IX Hawaii
X Idaho
V Illinois
V Indiana
VII Iowa
VII Kansas
IV Kentucky
VI Louisiana
I Maine
III Maryland
I Massachusetts
V Michigan
V Minnesota
IV Mississippi •
VII Missouri
VIII Montana
VII Nebraska
IX Nevada
I New Hampshire
II New Jersey
VI New Mexico
II New York
IV North Carolina
VIII North Dakota
V Ohio
VI Oklahoma
X Oregon
III Pennsvlvania
I Rhode Island
IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII Utah
I Vermont
III Virginia
X Washington
III West Virginia
V Wisconsin
VIII Wyoming
TOTAL
Region I
II
III
IV
V
VI
VII
VIII
IX
X
28132
Acetylene
3
2
2
1
6
4
1
6
3
2
2
4
4
2
2
2
7
1
2
2
2
3
3
3
2
]
1
2
1
3
2
6
3
2
fl
1
1
6
17
1
3
2
3
2
1
137
4
5
16
26
21
29
8
9
11
8
28133
Carbon
Dioxide
2
1
?
9
1
1
3
2
3
1
6
5
1
10
2
1
2
3
1
2
1
2
9
3
1
4
4
20
2
3
3
2
2
116
2
2
10
Is
13
37
16
5
11
5
28134
Other
Industrical
Gases
11
2
4
1
40
4
3
6
8
6
4
2
16
3
11
3
20
1
•)
5
7
5
2
6
3
2
18
1
9
2
28
7
3
28
1
9
46
3
7
3
13
2
1
365
9
27
56
42
65
75
20
11
50
10
2813
as a
Whole
13
3
5
3
47
5
3
7
13
10
6
7
20
9
9
17
5
31
1
3
7
8
6
5
9
3
4
3
18
3
10
5
40
11
4
33
2
1
17
69
<5
12
7
15
2
3
514
11
28
70
70
85
117
39
17
61
16
4-9
-------
Table 4-7. SIC 2813 Industrial Gases,
Distribution of Plant Sizes
Plant Size
Daily Capacity (metric tons)
IV Alabama
X Alaska
IX Arizona
VI Arkansas
IX California
VIII Colorado
I Connecticut
III Delaware
IV Florida
IV Georgia
IX Hawaii
X Idaho
V Illinois
V Indiana
VII Iowa
VII Kansas
IV Kentucky
VI Louisiana
I Maine
III Maryland
I Massachusetts
V Michigan
V Minnesota
IV Mississiooi
VII Missouri
VIII Montana
VII Nebraska
IX Nevada
I New Hampshire
II New Jersev
VI New Mexico
II New York
IV North Carolina
VIII North Dakota
V Ohio
VI Oklahoma
X Oregon
III Pennsylvania
I Rhode Island
IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII Utah
I Vermont
III Virginia
X Washinaton
III West viroinia
V Wisconsin
VIII Wvoming
TOTAL
Region I
II
III
IV
V
VI
VII
VIII
IX
X
28132
Acetylene
A
2
1
1
1
1
2
3
3
1
]
2
2
2
1
1
7
2
7
1
2
1
1
2
1
46
4
3
9
9
12
2
2
1
|
4
3
*
2
2
]
10
1
'3
1
1
3
1
2
2
2
1
8
1
2
5
2
1
4
?
9
3
2
1
94
5
10
10
10
10
]S
1?
>>
11
6
C
10
1
1
1
30
2
1
3
3
3
2
a
3
2
1
1
13
2
5
3
2
a
1
1
5
4
2
14
3
1
IB
6
27
3
4
1
6
1
1
198
3
9
31
27
34
44
7
6
34
3
D
1
3.
3
3
4
1
1
1
2
3
6
4
1
1
8
5
1
48
.•j
10
T
14
1?
1
3
KEY: A = 0-9 metric tons; B = 10-99 metric tons; C = 100-999 metric tons;
D = 1000 & up
4-10
-------
Table 4-8. SIC 2813 Industrial Gases,
Distribution of Plant Ages
Plant Age (years)
IV Alabama
X Alaska
IX Arizona
VI Arkansas
IX California
VIII Colorado
I Connecticut
III Delaware
IV Florida
IV Georgia
IX Hawaii
X Idaho
V Illinois
V Indiana
VII Iowa
VII Kansas
IV Kentucky
VI Louisiana
I Maine
III Maryland
I Massachusetts
V . Michigan
V Minnesota
IV Mississippi
VII Missouri
VIII Montana
VII Nebraska
IX Nevada
I New Hampshire
II New Jersey
VI New Mexico
II New York
IV North Carolina
VIII North Dakota
V Ohio
VI Oklahoma
X Oregon
III Pennsylvania
I Rhode Island
IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII Utah
I Vermont
III Virginia
X Washington
III West Virginia
V Wisconsin
VIII JVyoming
TOTAL
Region I
II
III
IV
V
VI
VII
VIII
IX
X
28132
Acetylene
A
1
1
2
1
1
1
1
1
1
1
1
2
14
l
3
3
3
1
3
B
2
?
A
4
4
2
2
2
3
2
2
1
4
1
2
,_ 2
2
2
2
3
2
1
1
2
1
2
2
4
3
2
6
1
1
5
13
1
3
2
3
_2_
1
109
4
4
14
18
15
22-
- 7
9
8
8
C
\
1
1
1
2
2
1
1
1
1
2
14
1
1
5
3
4
28133
Carbon
Dioxide
A
1
y
i
i
2
1
3
1
1
2
I
1
1
(,
1
26
1
3
3"
11
• 4
1
3
B
1
1
5
1
1
2
2
2
2
1
3
4
1
6
2
1
2
2
1
2
1
1
6
2
1
3
3
1?
1
3
3
?
2_
84
2
2
9
15
9
23
11
4
7
5
C
1
1
1
1
2
6
1
3
1
1
28134
Other
Industrial
Gases
A
1
1
10
1
1
2
1
1
3
2
4
2
1
1
1
3
3
5
2
5
2
9
1
1
1
71
2
6
10
0
12
15
4
3
12
1
B
8.
X
X
1
22
3
2
5
5
4
2
2
11
6
2
9
3
H
i
2
4
4
4
2
5
2
JL
13
1
5
2
20
5
3
20
1
6
34
2
5
2
'0
2
1
261
7
18
42
31
47
55
16
8
28
?
C
2
\
8
1
1
1
2
2
1
2
1
3
3
1
3
1
33
3
4
5
6
5
10
KEY: A = Under 5; B = 5 to 30; C = Over 30
4-11
-------
Table 4-9. SIC 2813 Industrial Gases,
Distribution of Processes
Process Type,
No. of Facilities
IV Alabama
X Alaska
IX Arizona
VI Arkansas
IX California
VIII Colorado
I Connecticut
III Delaware
IV Florida
IV Georgia
IX Hawaii
X Idaho
V Illinois
V Indiana
VII iowa
VII Kansas
IV Kentucky
VI Louisiana
I Maine
III Maryland
I Massachusetts
V Michigan
V Minnesota
IV Mississippi
VII Missouri
VIII Montana
VII Nebraska
IX Nevada
I New Hampshire
II New Jersey
VI New Mexico
II New York
IV North Carolina
VIII North Dakota
V Ohio
VI Oklahoma
X Oregon
III Pennsylvania
I Rhode Island
IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII Utah
I Vermont
III Virginia
X Washington
III West Viroinia
V Wisconsin
VIII Wyoming
TOTAL
Region I
II
III
IV
V
VI
VII
VIII
IX
X
28132
Acetylene
'from carbide)
3
2
2
1
6
4
1
6
3
2
2
4
4
2
2
2
7
t
2
2
2
3
3
3
2
1
1
2
1
3
2
6
3
2
8
1
1
6
17
1
3
2
3
2
1
137
6
2
5
8
6
5
4
6
4
4
28133
Carbon Dioxide
A
2
7
2
3
2
3
1
6
3
8
2
1
2
3
1
1
2
8
2
1
2
3
12
1
2
3
2
1
87
2
2
6
13
12
22
14
2
?
5
B
2
1
I
1
2
1
6
1
1
IP
1
1
1
3
1
C
1
1
1
1
2
1
1
2
2.
11
3
1
1
4
1
1
28134
Other Industrial Gases
D
7
3
1
24
4
2
2
7
4
2
2
11
5
3
1
2
13
1
2
5
5
4
2
6
3
8
1
8
2
18
5
2
25
1
6
26.
3
6
3
6
2
1
246
8
16
41
31
45
46
10
11
29
9
E
4
2
23
2
1
5
3
3
3
9
3
3
3
9
2
2
1
1
10
3
11
2
8
6
21
1
5
146
3
13
19
13
32
30
3
2
29
2
F
2
J
1
1
1
1
1
7
1
1
1
1
1
2
G
1
2
1
1
1
6
1
1
1
1
2
1
1
5
1
26
2
2
?
1
1
7
6
1
4
KEY: A = NH3 by-product; B = Natural Gas Wells; C = Other; D = Air Separation; E =
CO and H2 process; F = Nitrous Oxide; G = Helium
4-12
-------
Table 4-10. SIC 2813 Industrial Gases,
Distribution of Production
Annual Production
103 metric tons
IV Alabama
X Alaska
IX Arizona
VI Arkansas
IX California
VIII Colorado
I Connecticut
III Delaware
W Florida
IV Georgia
tX ' Hawaii
X Idaho
V Illinois
V Indiana
VII Iowa
VII Kansas
IV Kentucky
VI Louisiana
I Maine
III Maryland
I Massachusetts
V Michigan
V Minnesota
IV Mississippi
VII Missouri
VIII Montana
VII Nebraska
IX Nevada
I New Hampshire
II New Jersey
VI New Mexico
II New York
IV North Carolina
VIII North Dakota
V Ohio
VI Oklahoma
X Oregon
III Pennsylvania
I Rhode Island
IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII Utah
I Vermont
III Virginia
X Washington
III West Virginia
V Wisconsin
VIII Wyoming
TOTAL
Region I
II
III
IV
V
VI
VII
VIII
IX
X
28132
Acetylene
15
2
5
8
1
30
15
1
4
3
a
2
3
7
30
1
2
4
2
4
5
1
2
2
4
3
15
6
11
2
5
4
2
30
nn
5
15
3
15
2
1
400
2
7
42
15°
20
1<40
7
21
3°
to
28133
Carbon
Dioxide
9
5
41
1 6
17
28
85
16
51
44
43
°5
47
28
105
17
28
9
14
17
17
35
28
130
62
5
17
57
inn
17
28
34
28
43
9
1.500
17
52
100
9sn
260
400
iAn
43
16f)
*
28134
Other
Industrial
Gases
500
18
i75
160
1,200
82
11
120
140
44
36
1.900
nan
55
78
280
970
13
220
100
950
190
84
260
37
4
400
1
580
170
1,900
5
25
3.300
160
440
3 am
150
230
55
Ir200
300
5
21.000
120
980
5,100
i onn
6^100
4r900
ion
270
1 TOO
'^30
2813
as a
Whole
520
24
,ft
210
1,300
110
12
338
530
170
96
40
1.900
BRO
13)
130
310
1.100
14
222
120
950
190
120
270
42
15
6
420
22
620
2)0
2,000
78
32
3,300
160
2
530
4.100
ITO
270
92
1.200
340
15
23,000
150
1,000
5.200
7 2HO
6r300
5.500
-------
SIC 2813 was 514 with over 65% of them located in EPA
Regions III, IVr V and VI.
Table 4-7 gives the distribution of plant sizes by daily
production capacity in the three industry subcategories.
Fifty-nine percent of SIC 28132 plants have daily capacities
in the range of 10-99 tons. Sixty-eight percent of
SIC 28133 plants fall into the 100-999 tons per day range
and the majority (54%) of SIC 28134 plants fall into the
same range.
Table 4-8 lists the distribution of plants ages in SIC 2813.
Most of the plants in this industry fall into the 5-30 year
age bracket: 80% in SIC 28132, 12% in SIC 28133 and 71% in
SIC 28134.
Table 4-9 shows the distribution by process types in SIC
2813. Acetylene is made by only one process in SIC 281
facilities. The bulk of carbon dioxide plants (7556) use the
ammonia by-product process. The vast majority of SIC 28134
plants use either air separation or carbon monoxide/hydrogen
processes.
Table 4-10 lists the distribution of production in this
industry. The industry as a whole produces about 23,000,000
metric tons per year of products with the heaviest output
being in EPA Regions III, V and VI.
According to the 1972 Census of Manufacturers, the
establishments primarily engaged in SIC 2813 manufacture
average 19 total employees per establishment and 11
production employees per establishment. Only 27 percent of
the reported establishments have 20 or more employees.
4.4 Characterization of SIC 281.6X Inorganic Pigments
Industry
Tables 4-11 through 4-15 characterize this industry with the
following information:
Table 4-11 gives the distribution and number of establish-
ments producing the products in the three 5-digit SIC
subcategories. The number of establishments covered in SIC
2816 was 92 with the heaviest concentrations (66% of total)
in EPA Regions II, III and V.
Table 4-12 gives the distribution of plant sizes by daily
production capacity in the three industry subcategories.
Seventy-three percent of SIC 28161 plants have daily
capacities in the range of 100-999 tons. Both SIC 28162 and
4-14
-------
Table 4-11. SIC 2816 Inorganic Pigments,
Distribution of Establishments
Number of
Establishments
IV Alabama
X Alaska
IX Arizona
VI Arkansas
IX California
VIII Colorado
I Connecticut
III Delaware
IV Florida
IV Georgia
tX Hawaii
X Idaho
V Illinois
V Indiana
VII Iowa
VII Kansas
IV Kentucky
VI Louisiana
I Maine
III Maryland
I Massachusetts
V Michigan
V Minnesota
IV Mississippi
VII Missouri
VIII Montana
VII Nebraska
IX Nevada
I New Hampshire
II New Jersey
VI New Mexico
II New York
IV North Carolina
VIII North Dakota
V Ohio
VI Oklahoma
X Oregon
III Pennsylvania
I Rhode Island
' IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII Utah
I Vermont
III Virginia
X Washington
III West Virginia
V Wisconsin
VIII Wvoming
TOTAL
Region I
II
III
IV
V
VI
VII
VIII
IX
X
28161
Titanium
Pigments
1
1
1
1
1
1
2
2
1
11
2
2
2
1
1
28162
Other White
Opaque
Pigments
3
2
1
5
1
2
2
1
2
4
1
2
3
1
30
5
5
2
9
1
2
2
3
1
28163
Chrome
Colors and
Other
Pigments
4
1
2
4
3
1
2
1
3
1
10
4
3
7
. 1
1
1
•>
51
14
12
4
10
1
3
1
5
1
2816
as a
Whole
«
1
1
5
,1
9
4
2
1
5
1
2
4
2
1
16
5
7
10
1
2
1
1
7
92
21
19
9
21
2
6
3
9
2
4-15
-------
Table 4-12. SIC 2816 Inorganic Pigments,
Distribution of Plant Sizes
Plant Size,
Daily Capacity (metrictons]
IV Alabama
X Alaska
IX Arizona
VI Arkansas
IX California
VIII Colorado-
I Connecticut
III Delaware:
IV Florida
IV Georgia
IX Hawaii
X Idaho
V Illinois
V Indiana
VII Iowa
VII Kansas
IV Kentucky
VI Louisiana
I Maine
III Maryland
I Massachusetts
V Michigan
V Minnesota
IV Mississippi
VII Missouri
VIII Montana
VII Nebraska
IX Nevada
I New Hampshire
II New Jersey
VI New Mexico
II New York
IV North Carolina
VIII North Dakota
V Ohio
VI Oklahoma
X Oregon
III Pennsylvania
I Rhode Island
IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII Utah
I Vermont
III Virginia
X Washington
III West Virginia
V Wisconsin
VIII Wyoming
TOTAL
Region I
II
III
IV
V
VI
VII
VIII
IX
X
28161
Titanium
Pigments
A
0
B
1
2
3
2
1
C
1
1
1
1
1
2
1
8
2
2
3
1
28162
Other White
Opaque
Pigments
A
•4
1
1
1
1
6
1
1
2
2
B
1
2
1
4
1
2
1
1
2
3
1
1
2
1
23
4
3
2
7
1
2
2
1
1
C
1
1
1
28163
Chrome Colon
and Other
Pigments
A
I
1
1
1
1
3
1
1
2
13
4
2
T
3
1
1
3
•f.
1
2
3
2
1
1
2
1
6
3
2
4
1
1
1
2
35
9
8
3
7
1
2
1
3
1
C
1
1
1
3
1
2
KEY: A = 0-9 metric tons; B = 10-99 metric tons; C = 100-999 metric tons;
D = 1000 & Over
4-16
-------
Table 4-13. SIC 2816 Inorganic Pigments,
Distribution of Plant Ages
Plant Age (years)
IV Alabama
X Alaska
IX Ari'.'.oria
VI ArXai:!;.-!!;
IX Cili.ri,i':ii.i
Vil I Col.,:'., : •>
I Cn:ini'v(;i : cut
III Hi; lav: .!!-•::
IV Kloru:a
IV Gaor':i.i
IX Hawaii
X Idaho
V Illinois
V Indian'.
VII Ibwa
VII Kansas
IV Kentucky
VI Louisiana
I Maine
III X.irvla:-.-:
I Mcissac.".u:-:otts
V Michi.-:,-s:i
V Mi nr.c. -><•>•.• i
VII Misr,ov.:-'l
VIII ::or.t.i:.:t
VII ::o:jr is.-'..-i
IX Nevada
I ::ow !!•::• :>:;\. ir>:
II r:ovj ,.ipr:;"v
VI ::ow :•.'.!•.: Leo
11 Now Yorl-i
IV ;:<->r-a C1'. rc.J i :n
VII 1 r.orLh ! ;-.:•: tM.:
V Ohio
VI O/.lahor.i
X Oro<:o:'.
Ill iv.-.nsvlv.-.r.i.i
I .».hoir.<:l-o:i
III '.-;cst Vis-crir-.i.i
V '..'i!;co::!:.iri
VIII '•:vo:"ir.(i
TOTAL
Region I
II
III
IV
V
VI
VII
VIII
IX
X
28161
Titanium
Pigments
A
B
1
1
1
1
2
1
8
1
1
3
•>
1
C
1 .
1
1
3
1
1
1
28162
White and
Opaque Pigments
A
1
1
1
5
B
1
1
1
3
1
2
1
1
2
1
1
1
1
17
3
3
1
6
1
1
1
1
C
1
1
2
1
1
2
8
1
2
2
2
1
28163
Chrome
Colors and
Other Pigments
A
1
1
2
1
1
6
2
1
2
. 1
B
2
t
2
2
4
3
3
1
2
28
7
7
2
4
1
2
3
C
1
1
2
1
1
1
1
4
1
1
3
17
5
4
2
4
1
\
KEY: A = less than 5; B = 5 to 30; C = Over 30
4-17
-------
Table 4-14. SIC 2816 Inorganic Pigments,
Distribution of Processes
Process Type,
No. of Facilities
IV Alabama
X Alaska
IX Arizona
VI Arkansas
I* California
VIII Colorado
I Connecticut
ill Delaware
W Florida
IV Georgia
IX Hawaii
X Idaho
V Illinois
V Indiana
VII Iowa
VII Kansas
IV Kentucky
VI Louisiana
I Maine
III Maryland
I Massachusetts
V Michigan
V Minnesota
IV Mississippi •
VII Missouri
VIII Montana
VII Nebraska
IX Nevada
I New Hampshire
II New Jersey
VI New Mexico
II New York
IV North Carolina
VIII North Dakota
V Ohio
VI Oklahoma
X Oregon
III Pennsylvania
I Rhode Island
IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII Utah
I Vermont
III Virginia
X Washington
III West Virginia
V Wisconsin
VIII Wvoning
TOTAL
Region I
II
III
IV
V
VI
VII
VIII
IX
X
28161
Titanium
Pigments
O
5
A
i
i
i
i
2
6
•>
2
1
1
Chloride
1
1
1
1
1
2
1
a
2
3
2
1
28162
Other White
Opaque Pigments
PbSO4 &
PbCOl
1
1
1
2
1
6
3
2
1
01
o -o
.E °x
N O
2
2
1
4
2
1
2
1
1
3
19
1
3
2
6
2
2
2
1
E
1 „
£ -8
=-'x
-------
Table 4-15. SIC 2816 Inorganic Pigments,
Distribution of Production
Annual Production
103 metric tons
IV Alabama
X Alaska
IX Arizona
VI Arkansas
ik California
VIII Colorado
I Connecticut
III Delaware
W Florida
IV Georgia
IX Hawaii
X Idaho
V Illinois
V Indiana
VII Iowa
VII Kansas
IV Kentucky
VI Louisiana
1 Maine
III Maryland
I Massachusetts
V Michigan
V Minnesota
IV Mississippi -
VII Missouri
VIII Montana
VII Nebraska
IX Nevada
I New Hampshire
II New Jersey
VI New Mexico
II New York
IV North Carolina
VIII North Dakota
V Ohio
VI Oklahoma
X Oregon
III Pennsvlvania
I Rhode Island
IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII Utah
I Vermont
III Virginia
X Washington
III West Virginia
V Wisconsin
VIII Wyoming
TOTAL
Region I
II
III
IV
V
. VI
VII
VIII
IX
X
261 61
Titanium
Pigments
22
94
94
66
37
90
134
45
120
700
134
160
250
45
90.
22
28U2
Other White
Opaque
Pigments
8
4.7
31
32
3.8
51
0.6
2.9
5
23
3
9
80
0.4
250
26
81
4.7
48
0.4
SI
5
8
32
28163
Chrome
Colors and
Other
Pigments
53
0-5
25
35
7.5
3
25
4
65
3
52
31
5.3
94
20
4
2
27
460
83
150
32
48
20
AS
0.5
56
2
2816
as a
Whole
83
0.5
94
120
31
f?
11
51
3
92
2.9
h 41
150
5
3
210
34
59
170
120
20
4
2
27
1.400
240
390
280
140
20
200
5
86
33
4-19
-------
SIC 28163 have the majority of plants (77% for SIC 28162 and
69% for SIC 28163) in the 10-99 tons per day range.
Table 4-13 lists the distribution of plant ages in SIC 2816.
Most of the plants in SIC 2816 fall into the 5-30 year age
bracket: 73% in SIC 28161, 57% in SIC 28162 and 55% in
SIC 28163. Twelve percent of the total number of plants in
SIC 2816 are less than 5 years old.
Table 4-14 shows the distribution by process types in
SIC 2816. Titania (SIC 28161) is made by two processes;
sulfate and chloride. Most of the SIC 28162 plants (over
60%) are zinc oxide producers. The processes listed under
SIC 28163 are fairly evenly divided among chrome
pigments/iron blues, iron oxides, lead oxides and others.
Table 1-15 lists the distribution of production in this
industry. The industry as a whole produces about 1,400,000
metric tons per year of products with the heaviest output
being in EPA Regions II, III, IV, V and VII accounting for
about 90% of the total.
According to the 1972 Census of Manufacturers, the
establishments primarily engaged in SIC 2816 manufacture
average 115 total employees per establishment and 81
production employees per establishment. Sixty percent of
the reported establishments have 20 or more employees.
4.5 Characterization of SIC 2819. Inorganic Chemicals,
N-JLQi Industry
Tables 4-16 through 4-20 characterize this industry with the
following information:
Table 4-16 gives the distribution and number of establish-
ments producing the products in the seven 5-digit SIC sub-
categories. The number of establishments covered in
SIC 2819 was 923. EPA Region VI has the most plants, 189.
The next heaviest concentrations are in EPA Regions IV and V
with 156 and 140 plants, respectively. The lowest
concentrations are in EPA Regions I, VIII and X with a total
of 84 for all three regions. The largest number of plants
are in SIC 28199 (almost 50% of the total).
Table 4-17 gives the distribution of plant sizes by daily
production capacity in the seven industry subcategories. In
SIC subcategories 28194, 28196, 28197 and 28199 the
10-99 tons per day range is the most frequently encountered.
SIC 28193 has most of its plants in the 100-999 tons per day
range (about 71%). All of SIC 28198 plants are in the
0-9 tons per day range.
4-20
-------
Table 4-16. SIC 2819 Industrial Inorganic Chemicals,
N.E.C., Distribution of Establishments
Number of
Establishment
IV Alabama
X Alaska
IX Arizona
VI Arkansas
IX California
VIII Colorado
I Connecticut
III Delaware
IV Florida
IV Georaia
IX Hawaii
X Idaho
V Illinois
V Indiana
VII Iowa
VII Kansas
IV Kentucky
VI Louisiana
I Maine
III Maryland
I Massachusetts
V Michigan
V Minnesota
IV Mississippi
VII Missouri
VIII Montana
VII Nebraska
IX Nevada
I New Hampshire
II New Jcrscv
VI New Mc::.i.co
II Mew York
IV North Carolina
VIII North Dakota
V Ohio
VI Oklithonta
X Oregon
III Pennsylvania
I Rhode Island
IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII Utah
I Vermont
III Virginia
X Washington
III West Virginia
V Wisconsin
VIII Wyoming
TOTAL
Region I
II
III
IV
V
VI
VII
VIII
IX
X
28193
Sulfuric
Acid
3
5
6
10
1
15
4
1
3
13
4
1
2
2
11
1
4
1
3
1
1
3
1
1
11
4
7
4
7
2
8
1
1
1
17
1
7
3
1
2
169
3
13
21
31
28
40
6
4
17
6
28194
Inorganic
Acids
2
11
2
3
7
6
2
1
4
10
4
3
5
1
2
13
1
4
2
10
1
1
3
2
_. 4
19
1
3
8
135
3
17
18
24
23
31
2
13
4
28195
Aluminum
Oxide
1
2
2
1
3
1
1
1
1
1
1
2
18
1
2
. 1
4
7
1
2
28196
Aluminum
Compounds
6
3
9
1
1
1
4
6
5
2
9
1
2
1
4
2
3
2
9
4
2
8
1
1
4
2
6
. 5
3
5
2
115
3
13
10
29
23
18
2
2
9
6
28197
Na and K
Compounds
6
2
1
24
1
3
6
12
14
6
3
1
9
1
5
6
6
3
7
1
2
21
9
10
7
12
1
1
15
1
2
6
14
4
5
6
4
2
1
240
8
31
32
43
40
34
11
6
28
7
28198
Chem.
Catalytic
Preparation
1
1
3
2
2
1
2
1
3
1
1
8
1
- 5
2
1
2
1
2
55
1
9
7
5
_ 3
4
1
2
11
2
28199
Other
Inorg.
Chem.
N.E.C.
9
6
41
2
9
7
1
4
26
8
4
5
3
15
1
10
5
9
2
5
13
5
1
3
38
9
17
4
2
23
5 _
1
24
3
11
75
7
2
5
9
5
_§_ _
442
9
55
46
51
70
110
23
19
45
14
2819
as a
Whole
23
7
H
85
2
1
6
34
30
2
7
48
17
5
10
8
40
3
19
16
21
4
11
24
6
2
7
76
26
29
18
2
44
6
4
47
2
9
23
109
If
2
19
20
1£
6
8
923
24
105
107
" 1~56
140
189
41
29
101
31
4-21
-------
Table 4-17. SIC 2819 Industrial Inorganic Chemicals,
N.E.C., Distribution of Plant Sizes
Plant Size,
Daily Capacity AMtric r»m)
IV Alabaina
X Alaska
IX Arizona
VI Arkansas
IX ' California
VIII Colorado
I Connecticut
III Delaware ' " '
IV Florida
IV Georgia
IX Hawaii
X Idaho
V Illinois
V Indiana
VII Iowa
VII Kansas
IV Kentucky
VI Louisiana
I Maine
III Maryland
I Massachusetts
V Michigan
V Minnesota
IV Mississippi-
Vltf " Missouri
VIII Montana
VII Nebraska
IX Nevada
I New Hampshire
II New Jersey
VI Naw Mexico
II New Vork
IV North Carolina
VIII North Dakota
V Ohio
VI Oklahoma
X Oregon
III Pennsylvania
I Rhode Island
IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII Utah
I Vermont
iiX Virginia ' '
X Washington
iil West Virginia
V Wisconsin
VIII Wyoming
TOTAL
Region I
II
III
IV
V
vi •
Vll
VIII
IX
"• • x~
281 M
Sulfuric
Acid
A
B
1
i
2
7
i
|
7
j
I
7
j
1
18
1
i
3
4
1
1
C
2
4
ft
in
i
t
jj
i
2
9
1
2
4
1
1
1
a
i
9.
4
1
7
2
7
t
11
6
7
1
120
2
10
in
13
n
77
J
3
1ft
D
1
11
1
2
1
£
|
]
1
1
4
31
1
14
in
i
i
281 94
Inorganic
Acids
T
1
1
]
1
7
4
2
Mt
l
3
ft
1
2
B
1
3
7
7
4
2
i
i
i
2
3
7
1
7
in
i
i
5
1
]
1
1
ft
]
7
70
3
II
17
1
p
U
,1
2
C
I
7
i
2
J
\
3
2
3
3
7
1
4
I
j
t,
1
45
5
3
1?
10
7
D
2
I
1
4
2
2
28195
Aluminum
Oxide
A
1
1
2
I
1
B
1
1
1
1
A
1
1
2
C
1
1
1
1
4
1
1
7
D
)
1
3
1
A
1
5
28196
Other
Aluminum
Compounds
A
(j
1
1
1
i
1
1
15
'2
3
1
A
B
t
3
{
i
1
2
7
6
7
7
<5
7
3
•
'
54
1
U
3
1R
1*
|
3
3
C
!
2
1
j
2
*
J
1
2
1
?
2
]
•)
7
2
2
|
2
3
•
41!
2
3
7
10
r
2
,'i
0
1
1
7
4
4
28197
No and K
Compounds
A
I
1
3
1
2
1
1
1
1
1
2
1
3
,1
7
1
2
1
27
1
3
4
5_
i
4
4
1
T
3
1
1
12
1,
2
3
7
A
3
2
1
7
|
3
2
7
1
4
1
2
7
2
3
5
A
1
4
1
^
5
3
3
2
1
IUS
3
10
16
J!4
B
0
7
1
15
4
T
2
7
1
4
5
2
1
6
1
3
3
2
3
9_
3
3
2
3
0
2
II
1
1
3
4
3
4
s
1
^
\
t
3
2
2
2
1
1
U/
4
TJ
H
4
t
t
t
X
7
2
7
1
Itt
0
2
3
4
1
2
.28198
Chem.
Catalytic
Preparation
- A
•j
2
?
2
i
3
8
5
1
2
1
' 4
t
t
,, ft ,_
1
9
j
1
i
. . 1
J
r
i
1
1
B
0
28199
Other
Inorg.
Chem.
N.E.C.
'A
9
1
2
S
1
i
1
2
2
1
1
1
1
10
1
2.
1
1
5
2
6
t
1
/I
1
12
y
J
X
6
4
4
in
B
s
5
21
1
2
1
')
IT
4
^
2
2
4
I
i
2
2
T
^j
;
1
\)
U
y
ji
. f
,2
||
1
2
.S
»
3
1
7
n
2
1
21&
5
26
26—
J28
58
In
11
H
C
4
r
M
1
3
_2_
10
y
1
i!
1
J
2
5
1
1
s
2
1
11
6
1
1
y
1
7
1
7
21
1
3
4
2
143
3
17
16
Id
2«
6
12
6
D
4
1
2
1
4
12
2
1
e
i
KEY; A <• 0-9 metric tora; B = 10-99 tons; C • 100-999; D = 1000 & Up
4-22
-------
Table4-18. SIC 2819 Industrial Inorganic Chemicals,
NI.E.C./ Distribution of Plant Ages
Plant Age (years)
IV Alabama
X Alaska
IX Arizona
VI Arkansas
IX California
VIII Colorado
I Connecticut
III Delaware
W Florida
IV Georgia
IX Hawaii
X Idaho
V Illinois
V Indiana
Vti iowa
VII Kansas
IV Kentucky
VI Louisiana
I Maine
III Maryland
I Massachusetts
V Michigan
V Minnesota
IV Mississippi
VII Missouri
VIII Montana
VII Nebraska
IX Nevada
I New Hampshire
II New Jersey
VI New Mexico
II New York
IV North Carolina
VIII North Dakota
V Ohio
VI Oklahoma
X Oregon
III Pennsylvania
I Rhode Island
IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII Utah
I Vermont
III Virginia
X Washington
III West Virginia
V Wisconsin
VIII Wyoming
TOTAL
Region I
II
III
IV
V
VI
VII
VIII
IX
X
28193
Sulfuric
Acid
A
1
2
1
5
1
2
1
3
]
I
2
1
1
3
1
1
27
2
2
2
&
4
fi
2
1
B
2
4
2
R
f,
2
1
3
5
3
2
]
6
2
3
I
2
i
1
6
2
i
3
5
2
5
1
1
9
1
4
1
1
2
101
1
7
1?
1ft
17
71 '
5
4
14
4
C
1
2
1
1
4
1
6
1
2
2
1
3
2
l
1
1
2
1
5
2
1
41
4
7
9
7
II
1
1
1
28194
Inorganic
Acids
A
2
1
1
1
1
1
1
2
1
2
l
4
1
19
1
2
4
4
5
2
1
B
2
4
1
2
3
3
2
5
2
1
2
1
2
6
1
3
1
4
1
1
2
1
'•i
11
1
5
72
1
9
10
14
11
18
1
6
2
C
5
1
1
3
2
4
2
1
2
5
1
4
i
i
4
1
1
3
44
1
6
t)
6
6
8
1
5
1
28195
Aluminum
Oxide
A
1
1
1
B
1
1
1
2
1
1
1
1
1
2
1
13
1
1
3
5
1
2
C
1
1
1
1
4
1
1
2
28196
Aluminum
Compounds
A
2
1
1
1
1
1
1
2
1
l
1
13
1
1
]
2
4
1
2
1
B
4
2
S
1
1
2
4
2
1
4
1
1
3
1
1
1
4
2
1
3
1
1
1
1
2
3.
1
1
2
2
59
2
6
3
IS
12
IQ
1
2
5
3
C
2
1
2
1
2
2
X
T
4
1
1
1
1
4
2
1
3
2
1
3
2
2
2
43
6
6
12
7
7
28197
No and K
Compounds
A
1
.S
1
3
3
1
1
2
1
2
4
2
1
i
2,
4
1
1
1
1
2
43
1
5
e>
fi
6
1 5
1 3
1
2 6
2 7
B
^
1
.
i
\
i
6
1
3
1
1
3
3
1
3
2
10
3
5
•)
5
5
1
T~
3
A
2
2
2
1
11?
5
15
13
?
1
1
•)
p
4
>
4
14
3
C
1
8
1
?
4
•i
1
4
1
i
3
1
2
7
/
t
4
5
6
1
2
7
1
3
2
2
85
2
11
! 5
15
5
3
1
8
2
28198
Chem.
Catalytic
Preparation
A
2
1
1
1
1
1
7
1
1
3
2
B
9
1
?
2
1
2
5
1
3
]
2
1
2
1
2
44
,
6
7
4
8
4
2
9
2
C
]
2
1
4
2
2
28199
Other
Inorg.
Chem.
N.E.C.
A
2
1
5
1
1
1
3
1
4
1
1
1
1
1
5
4
1
5
1
8
]
2
13
1
2
70
1
9
9
16
16
19
2
2
5
3
B
4
4
21
1
4
2
1
2
13
3
_2_
2
1
i
i
5
1
4
1
4
6
3
1
2
n
5
7
2
1
9
2
1
7
1
2
5
41
4
2
5
3
1
2
204
3
'9
13
?2
57
11
16
24
8
C
3
1
15
1
4
4
1
10
4
2
3
6
4
3
4
1
5
1
1
22
4
6
i
1
9
2
9
4
21
2
2
3
2
2
1
168
5
29
47-
-?r
34
10
7
16
3
KEY; A = less than 5 years; B = 5 to 30 years; C = Over 30 years
4-23
-------
Table 4-19. SIC 2819 Industrial Inorganic Chemicals,
N.E.C., Distribution of Processes
Process Typu,
No. of Facilities
IV Alabama
'f. Alaska
IX Arizona
VI Arkansas
IX California
VIII Colorado
I Connecticut
III Dcl'ivarn
IV Flori.ia
IV Gcorqia
IX Hawa i i
X Idaho
V Illinois
V Indiana
VII Iowa
VII Kansas
IV Ki-mtuckv
VI Louisiana
I Maine
III Maryl.-tnil
I MasKarhusectp
V Michi<':.:n
V Mim.L't.ot.a
TV Hisu::,>:im-.i
VII MisMiuri
VIII Moim.'i:-..-!
VII ::<-br is.-:a
IX . NoViitia
I Hew HdrM.r-hi rn
11 Now .nrnev
VI l.'ow .'lexico
II Hew York
IV North Carol ins
VIII north I\il:ot;i
V Ohio
VI OkliiliC.ra
X Oroaon
III Pcnnsvlvania
1 Hhrxl': IsJ.inri
IV South Ciroi in T
VI IL South l.'-kotn
IV Tpnn-.-ss^o
VI Texan
VIII Ut.ih
I Vprmont.
Ill \'in: i nia
X Wash i lull on
1 1 1 \:.-st >': i IT ..:.i ,t
V "'.M':7-. .Ti"i; in
VI 11 '. vi-l-'in.i
Tii.'.M. "" " •"" "
Ron ion 1
1 [
1 I >
7
'.'
v •
. i ' 1
1..
X
•u
<
8 J
S J!
1
C
J
|
P
1
.•i
A
3
1"i
4
3
n
2
I
?
1
7
1
4
I
T
]
3
1
|
1
9
4
]
4
f,
?
ft
JL
_L
1
n
i
2
•>
_J_
_2_
14
3
10
IS.
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2-1
Phosphates
Synthesis
5
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1
2
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L.
Chromotes NEC
Synthesis
1
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Cu Compound
Synthesis
3
7
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Synthesis
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5
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5
4
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Synthesis
5
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Synthesis
1
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6
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1
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19
7
4
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Phosphorus
Compounds
3
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2
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4-24
-------
Table 4-20. SIC 2819 Industrial Inorganic Chemicals,
N.E.C., Distribution of Production
Annual Production
10 metric tore
IV Alabama
X Alaska
IX Arizona
VI Arkansas
Ik California
VIII Colorado
I Connecticut
III Delaware
IV Florida
IV Georgia
He kawali
X Idaho
V Illinois
V Indiana
VII Iowa
VII Kansas
IV Kentucky
VI Louisiana
I Maine
III Maryland
I Massachusetts
V Michigan
V Minnesota
IV Mississippi
VII Missouri
VIII Montana
VII Nebraska
IX Nevada
I New Hampshire
II New Jersey
VI New Mexico
II New York
IV North Carolina
VIII North Dakota
V Ohio
VI Oklahoma
X Oregon
III Pennsvlvania
I Rhode Island
IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII Utah
I Vermont
III Virginia
X Washington
III West Virginia
V Wisconsin
VIII Wyoming
TOTAL
Region I
II
III
IV
V
VI
VII
VIII
IX
X
28193
Sulfuric
Acid
400
1.000
430
1,400
260
9,300
540
30
1.100
7AO
400
400
200
230
4,300
60
410
60
100
90
450
530
260
130
Ir600
260
i4f>
9RO
540
170
830
20
40
870
3,500
1?0
640
130
110
80
33,000
140
1,700
2,200
13,000
1.900
8,700
1.100
460
2.600
1.200
28194
Inorganic
Acids
10
450
120
20
950
80
10
120
250
80
20
120
20
310
1in
10
240
10
50
80
590
10
20
60
3,700
20
420
320
?40
1,400
770
10
0
470
30
28195
Aluminum
Oxide
700
920
40
20
2,200
80
100
20
20
20
2,100
20
6,200
80
20
20
(UO
0
5,200
0
20
40
0
"28196 '
Aluminum
Compounds
80
500
75
30
45
50
60
150
30
400
30
140
30
40
40
(0
-0
150
30
30
120
10
30
80
20
80
600
30
40
50
50
3,200
60
180
320
4nn
430
1.500
40
60
75
80
28197
Na and K
Compounds
200
10
1 .500
150
100
180
800
200
90
420
30
100
450
150
250
50
800
3,000
470
50
300
50
300
2o
40
270
300
600
120
30
80
To
70
11,000
120
1,300
630
flCfl
1 flOO
3,700
340
820
1,500
80
••"SfllW
Chem.
Catalytic
'reparation
10
10
15
40
15
15
10
35
25
10
10
5
200
0
35
30
50
50
25
0
0
10
0
"26199
Other
Inorg.
Chem.
N.E.C.
50
150
900
20
50
80
150
30
250
230
40
100
50
180
400
30
220
100
900
20
100
800
30.
10
30
400
30
300
100
20
300
60
50
250
15
400
400
100
10
100
150
70
30
10
7,000
160
700
690
1,100
1 500
1.000
960
160
260
450
2819
as a
Whole
1.400
1.000
2,000
3,700
180
20
600
9,400
950
60
1.300
2,900
750
500
350
590
B.boff
120
900
390
1,600
150
880
1.600
290
10
230
3,300
3,300
1,100
1,200
20
1.500
2^0
I'D
1,500
40
110
1,700
7.400
870
10
910
380
320
90
160
64,000
580
' 4y4bO
4,200
16,000
7 000
21 .000
2.500
K5QO_
5,000
1.800
4-25
-------
Table 4-18 lists the distribution of plant ages in SIC 2819.
In each of the seven production subcategories, the majority
of plants fall into the 5-30 year age bracket.
Table 4-19 shows the distribution by process types in
SIC 2819. The number of processes employed by this industry
is large and diversified.
Table U-20 lists the distribution of production in this
industry. The industry as a whole produces about 64,000,000
metric tons per year of products with SIC 28193, sulfuric
acid, accounting for over half the total. The two most
heavily concentrated areas are EPA Regions IV and VI with
16,000,000 and 21,000,000 metric tons per year,
respectively.
According to the 1972 census of Manufacturers, the
establishments primarily engaged in SIC 2819 manufacture
average 169 total employees per establishment and 106
production employees per establishment. Seventy percent of
the reported establishments have 20 or more employees.
4-26
-------
iO W£STE CHARACTERIZATION
JJil Introduction
In this section, the processes, the wastes resulting from
each process, and the amounts of hazardous waste generated
are described for each segment of the industry. Projections
are made for the amounts of hazardous wastes to be produced
in 1977 and 1983, and these are based upon two major
considerations:
- Changing production patterns within the industry, due
to a variety of causes such as developments in markets,
in process technology and in raw material supply, and
- the effects of upcoming air and water regulations on
the generation of hazardous wastes destined for land
disposal
The flow diagrams accompanying the process and waste stream
descriptions are presented within the following format:
Raw materials are on the left and products are on the
right. Gaseous emissions are projected upward and waste
products, both solid and liquid, are projected downward.
All diagrams are based on 1000 units of mass of the
principal product; miscellaneous water uses are not
generally quantified. For clarity, several unit operations
have, in some cases, been combined in one block. Heavy
lines represent the main flow from raw materials to product.
The diagrams reflect our technical judgment of typical or
usual operations in the given industrial subcategory, rather
than those associated in the specific, identifiable plant.
Production rate and other data for the assumed typical plant
are given in the text accompanying each diagram.
Both process and cooling water use vary with plant location,
plant management, process, plant age, and product purity.
The exemplary plant water use may often be easily
quantified, but the water use in a "typical" plant is
usually loosely coupled to the technology of the process,
and can therefore differ several fold from specific
operating levels.
The water content of the hazardous waste streams destined
for land disposal can vary widely for a variety of reasons:
e.g., individual operating practice, equipment limitations,
local availability of water, and rainfall. Thus only
reasonable generalizations can be made about this component.
For purposes of estimation, the following water contents
5-1
-------
were found to be generally prevalent in waste streams from
these industries:
(a) filter cake, 20- SOX moisture
(b) sludges from settling ponds, 60-80% moisture
(c) slurries, £90X moisture
(d) retort or furnace residues, less than 10% moisture
ILijJl IM SastsdQus Nature of Waste Streams
The hazardous waste streams selected from these industries
Were selected to be as consistent aa possible with th»
following published definition of EPA (69) : "Hazardous
wastes" means any waste or combination of wastes which pose
a substantial firgsgrji or potential hazard to human health or
living organisms because such wastes are nondegradable or
persistent in nature or because they can be biologically
magnified, or because they can be lethal, or because they
may otherwise cause or tend to cause detrimental cumulative
effects" (underlining added) .
For a detailed discussion of the criteria used to determine
a "hazardous" waste stream, see the earlier Section 1.1.3
concerning methodology. Generally when a waste stream
contains one or more hazardous constituents, in
concentrations judged to be significant, the entire waste
stream is considered hazardous.
The major area of concern is the group containing the most
sgyerej,y hazardous materials generated by the inorganic
chemicals industry. Detailed studies of average, exemplary,
and environmentally adequate disposal practices have been
conducted. However, most solid waste materials generated by
the industry are not severely hazardous, and so are not
emphasized in this study. This should not be taken to imply
that waste streams other than those deemed to be "hazardous"
by virtue of their content of "severely hazardous" or
"moderately hazardous" constituents need no landfill
precautions. Indeed, some of these waste streams could have
detrimental effects on the environment if improperly
handled, as for example large amounts of soluble salts such
as sodium chloride or calcium chloride as moist: solids or
concentrated brines. Normally these materials in moderate
amounts are not considered to be hazardous and are not so
considered in this report, where materials because of their
high concentrations, large amounts, or other special
situations at specific locations constitute potential
hazards , they, have been designated as "hazardous" herein,
this has been the ease for several calcium fluoride-
containing waste streams.
5-2
-------
Waste streams other than "severely hazardous" can be grouped
into two general categories: the totally non-hazardous, and
the moderately hazardous. The general properties of
materials falling into these categories and their
corresponding disposal recommmendations are:
Non-hazardous - Inert solid wastes; i.e. those having no
detrimental environmental effects. These wastes should not
pose a threat to water quality or human contact in any way
(except, possibly esthetic) and hence may be safely disposed
of in landfill sites exposed to ground and surface water.
Examples of these materials from this report are brick and
carbon rubble from process equipment and gypsum solid waste
uncontaminated by toxic materials.
Moderately hazardous - Water may become polluted if such
wastes are placed in water or if water is allowed to pass
through them (discharging a leachate of high mineral
content). Landfill sites accepting these wastes must
provide for separation of the wastes from underlying or
adjacent usable water by natural or artificial barriers.
Subsurface flow in the form of springs or seepage should be
prevented from entering the disposal area. Disposal areas
should be protected by natural or artificial features to
assure protection from any washout or inundation which could
occur as a result of tides or floods. Surface drainage from
tributary areas should be prevented from contacting wastes
in the site. To prevent gases and leachate emanating from
the landfilled material from adversely affecting local
groundwater, natural or artificial barriers should be .installed
and maximum separation should be provided from the highest
anticipated groundwater level.
Implementation of these general recommendations would, in
most cases, be sufficient to prevent leachate of high
mineral content escaping from landfills containing such
wastes.
In some cases in this report wastes streams composed largely
of "moderately hazardous" materials have been identified as
hazardous waste streams because of the potential hazard
involved in the amounts and the locations of the specific
instances. Examples of these from this industry are calcium
fluoride solid wastes, or calcium fluoride mixed with
gypsum.
The following sections discuss each of the segments of the
inorganic chemical industry, the processes and wastes
involved in each, and the types of wastes.
5-3
-------
5.2 Alkalies and Chlorine (SIC 2812D
This segment of the inorganic chemicals industry includes
those facilities producing chlorine, sodium and potassium
hydroxides, synthetic soda ash, sodium bicarbonate, and
potassium and ammonia carbonates. Descriptions of the
processes and wastes involved in these subcategories are
given below.
5...2...1 Chlorine (SIC 28121)
Within the SIC 281 category, chlorine is produced by five
basic processes:
(a) The Mercury Cell and Diaphragm Cell chlor-alkali
processes, in which either sodium hydroxide or
potassium hydorxide is produced as a co-product.
(b) The Down's cell process, which involves the
electrolysis of molten salt and generates metallic
sodium as a co-product.
(c) The Kel-chlor process, which is similar to the
diaphragm cell operation except that hydrochloric
acid instead of a sodium chloride solution is
electrolyzed. Hydrogen is generated as a co-
product. This process is currently operational at
only one facility and, since its hazardous wastes
are similar in nature to those generated by the
diaphragm cell, it will not be discussed
separately.
(d) The Vicksburg Chemical process in which potassium
chloride and nitric acid are reacted to form
chlorine nitrosyl chloride, and potassium nitrate
as co-products. This process is currently
operational in only one facility and, as there are
no wastes destined for land disposal, requires no
further treatment herein.
In addition to the above, some quantities of by-product
chlorine are produced by a process not included in SIC 281,
namely the electrolytic manufacture of magnesium (SIC 3339),
5.2.1.1 Diaphragm Cell Process
Sodium chloride brines are first purified by addition of
sodium carbonate, flocculating agents, and sodium hydroxide
in amounts required to precipitate all the magnesium and
calcium contents of the brine. The brine is then filtered
to remove the precipitated materials and electrolyzed in a
diaphragm cell. Chlorine, formed at one electrode, is
collected, cooled, purified, compressed, and sold. The
sodium hydroxide formed is subjected to partial
5-4
-------
evaporation, (which precipitates most of the unreacted sodium
chloride from the solution) and then filtered. The
collected sodium chloride is recycled to the process, and
the sodium hydroxide solutions are further evaporated to
yield solid products. The flow diagram for the typical
operation of this type is shown in Figure 5-1. An analogous
process uses potassium chloride brine to produce a potassium
hydroxide (caustic potash) co-product. Some values of
materials in this flow diagram have been given ranges, for
example sulfuric acid 12(6-35). The parenthetical values
are range extremes experienced in the industry. The
percentage values given with the sulfuric acid streams refer
to their concentrations.
There are several waste streams generated:
(a) l£ia§ purification muds
The muds generated are primarily calcium carbonate,
magnesium hydroxide, barium sulfate, and water.
Because the solubilities and toxicities of these
waste constituents are low, they are not hazardous,
and stringent landfill requirements are not
appropriate.
(b) Lead salts resulting from waste water treatment
The lead arises in the effluent due to cell
breakdown and corrosion. The wastes generated by
wastewater treatment are lead carbonate (solubility
1.1-1.7 mg/1) and basic lead carbonate (solubility
1.7 mg/1). The composition of the solid waste
generated by wastewater treatment is quite variable
from plant-to-plant and hence the treatment and
effluents of treatment are not given in Figure 5-1.
However, typically a wastewater treatment removes
over 90% of the lead content prior to discharges.
(Appendix A details the properties of these
compounds) . Lead carbonate and basic lead
carbonate comprise the major constituents of the
waste stream, and the overall properties of the
waste are the same as those described for the
individual components. Because of the toxicity and
solubilities of these waste constituents, and
because of the bioaccumulative phenomena for lead,
the waste material must be completely isolated from
the environment upon land disposal.
(c) Asbestos wastes from cell diaphragms Asbestos is
hazardous to man when inhaled and, possibly, when
taken orally . However it is completely insoluble
in a landfill and the only land disposal
requirement is that the surface be protected from
the erosional forces of wind and rain. The
5-5
-------
RAW BRINE
1800(1663- 2150) NaCI
WITH Mg,Ca,S04
IMPURITIES
01
cr>
CELL MATERIALS:
0.04 LEAD
1 0.5 ASBESTOS
AS APPROPRIATE < N°OH 3 OTHERS
AS APPROPRIATE ^ g^ ASH ^£ ^
NaCI BRINE _
» PURIFICATION ,
1 SALT
1 1
15 (UP TO 30) SOLID
DIAPHRAGM — '
CELL
ELECTROLYSIS .
\ I
VIWSTE: WATER
CAUSTIC
SOLUTION-
12(6-35) H2S04
(98% -104%)
VENT
t
-* SCRUBBER
r
COOLING PURIFICATION
-^ AND 1— H MD
DRYING COMPRESSION
I2(6-35)H2S04
(70% -93%)
VENT
t
CAUSTIC
^ EVAPORATION
SALT
RECOVERY
- BORNE WASTES:
PURGATION 3 CARBON AND RUBBLE 35-265 NaCI
MUDS' °'4 ASBESTOS 15 NaOH
MflfOH? CflCO. t 0.04(0-0.22) LEAD
Mg(OH)2, COC03, 0 ASBESTOS
TRACE METAL HYDROXIDES] 0-20 Na, SO*
0.2 FILTER AID 0-0.01 COPPER
1 NOv/l
3 WATER
I
DRUMMED WASTE:
0.4540.H.O)
CHLORINATED
HYDROCARBONS
i
IN<
3 No
IN SOI
^. IOOO CLORINE
"^PRODUCT
2256 CAUSTIC
"^(50%)
lOCI
HCO,
-UTION
FIGURE 5-1
CHLOR-ALKALI MANUFACTURE
DIAPHRAGM CELL PROCESS
-------
chemical, physical, and biological properties of
asbestos are detailed in Appendix A.
(d) Chlorinated hydrocarbon wastes These arise from
reaction~"of chlorine with the carbon anode.
Chlorinated hydrocarbon wastes exhibit the
properties described in Appendix A.
The principal growth in the chlorine industry can be
expected to take place in this segment (65-67). Water and
air regulations have little or no impact on hazardous wastes
generated, and process technology is under rapid development
in several areas having to do with construction materials
for the cells. Lead and chlorinated hydrocarbon wastes are
being reduced by the use of coated metal anodes (otherwise
known as dimensionally stable anodes), and these are
gradually replacing graphite anodes in existing plants.
Indeed, all new construction is being carried out with
coated metal anodes, and asbestos wastes will be reduced
when plastic microporous separators become commercially
acceptable. We estimate this separator changeover to be '•
well under way by 1977, but complete changeover not to be
attained for at least a decade, based on discussions with
industry.
The typical diaphragm plant is large (upward of 500 tons per
day), and the trend in recent times has been to very large
plants with capacities greater than 1000 tons per day. They
tend to be distributed according to local economic factors
for much the same reason as the mercury cell plants
discussed below. The typical plant, while also 5 to 30
years old, is relatively newer than a mercury-cell plant.
JJiJilii Mercury. Cey, Chlor-^lkaii Process
The typical mercury cell plant has a production rate of 275
tons per day and is 5 to 30 years old. A typical location
is near cheap power, a salt source, and a market for the
chlorine; but localization is not otherwise apparent.
In the mercury cell process, caustic and chlorine are
produced from salt or potassium chloride raw materials
depending on whether caustic soda or caustic potash is to be
produced. The raw material is dissolved and purified by the
addition of barium carbonate, soda ash, and lime to remove
magnesium and calcium salts and sulfates prior to
electrolysis. The insolubles formed by addition of the
treatment chemicals are filtered from the brine, and the
brine is then fed to the mercury cell, in which chlorine is
liberated at one electrode and a sodium-mercury amalgam is
formed at the other.
5-7
-------
The chlorine formed is cooled, dried in a sulfuric acid
stream, purified to remove chlorinated organics, compressed
and sold. The mercury-sodium amalgam (also formed during
electrolysis) is sent to a "denuder" where it is treated
with water to decompose the amalgam. Sodium hydroxide and
hydrogen are formed in the reaction. The mercury liberated
is returned to the electrolysis cells. The hydrogen in a
typical plant is flared through, in others, it is cooled,
scrubbed to remove traces of mercury, compressed, and sold.
The sodium or potassium hydroxide formed at the denuders is
filtered, concentrated, and cold, and waste brlft«M emerging
from the electrolysis cells are re-saturated and recycled.
In some instances, the weak brine is treated to precipitate
mercury before recycle, but not typically.
The flow diagram for the usual operation of this process is
given in Figure 5-2. There are several waste streams
involved, some of which are hazardous:
(a) Brine purification muds - These are often
contaminated with mercury in a typical amount of
0.005 kg per metric ton of chlorine and a range of
0-0.015 kg/kkg. Whether or not these muds are
hazardous varies from plant-to-plant in this
industry depending on process details. They range
from no mercury content to an average top value of
100 ppnt. This latter is judged to be hazardous.
(b) Sludges from treatment of brine to remove mercury
compounds. They contain free mercury or mercury
sulfide. The mercury content is typically 0.058 kg/
metric ton of chlorine.
(c) Chlorinated hydrocarbons from chlorine purification
in the amounts shown in Figure 5-2.
Other losses of mercury in these plants include losses to
the atmosphere as an impurity , in products, and in the
waste water discharge.
Of the waste streams which are potential candidates for
land disposal, two definitely fall in the severely hazardous
category. They are the chlorinated hydrocarbon waste (c)
and the sludges from mercury removal treatment (b). For
both waste streams the concentration of hazardous constitu-
ents is high enough that the overall biological properties
of the wastes are very similar to the individual
constituents. Specific data on both the properties of
mercury and its compounds and on the chlorinated
hydrocarbons is given in Appendix A.
5-8
-------
BRINE RECYCLE
I NoOH
AS APPROPRIATED NOjCOs
I BaCI2
RAW SALT
1730(1663-1915) —
NaCI WITH Mg,
Co,S04 IMPURITIES
i
SATURATOR
BRINE
PURIFICATION
tn
I
ID
2(UP TO 20)
GRAPHITE
MAKE-UP MERCURY
WATER
VENT
TO ATMOSPHERE
1
12(8-18) SULFURIC
ACID(98%)
ELECTROLYTIC
CELL
AND
DENUDER
CELL AREA
DRAINAGE
SULFIDE-
I
I
1
COOLING,
DRYING,
PURIFICATION
AND
COMPRESSION
FILTER
1000 CHLORINE
16(8-25) SPENT
ACID BY-PRODUCT
(70-80%
> 2240 CAUSmC(5O%)
28.5 HYDROGEN
WASTE TREATMENT
BRINE
PURIFICATION
SOLID WASTES
I7(UPT050)
T
SOLID WSTES
2(UP TO 20)
GRAPHITE
«=l FILTER AID
MUDS CONTAINING MERCURY SULFIDE
DRUMMED
WASTES
O.I (UP TO 0.7)
CHLORINATED
HYDROCARBONS
WATER-BORNE
BaS04, NaCI,
ANDHgCIf
FIGURE 5-2
CHLOR-ALKALI MANUFACTURE
MERCURY CELL PROCESS
800 WATER
«=! SUSPENDED
SOLIDS
87 NaCI
Hgci;
-------
The mercury contamination of brine purification muds varies
throughout the industry. Some plants separate electrolysis
cell wastes from primary brine purification wastes, and thus
the large quantities of such wastes (composed primarily of
calcium carbonate, magnesium hydroxide and barium sulfate,
which are non-hazardous) do not contain mercury and may be
landfilled with less strenuous requirements. These plants
then apply mercury removal technologies to the smaller, more
concentrated waste stream from electrolysis and denuding
operations and these can therefore be disposed of in a
secure landfill.
Facilities segragating the two waste streams generate
significant tonnages per year of brine sludge containing as
much as 100 ppm mercury (68) . Although diluted in the
waste, the problem of controlling the escape of mercury to
the environment remains. The mercury concentration in
surface runoff and leachate from this landfilled waste would
exceed acceptable limits, and, consequently, safeguards to
prevent contamination of surface and groundwaters are
required. These wastes are considered to be hazardous.
Because of the danger associated with mercury pollution,
mercury cell production is being shifted to diaphragm cell
production (65-67). Through the period to 1977, conversion
or shut-downs in mercury cell operations are occurring in
Texas, Louisiana, New York, Washington, and Tennessee (64,
67) . New capacity is being added (in this period) in
Alabama and Maine (64, 67). Between 1971 and 1983, it can
be assumed that mercury cells production in several states
will be completely abandoned.
Waste generation at operating facilities can be expected to
experience the following trends:
(a) Mercury in water discharge - by 1977, this will be
reduced to 0.00014 kg per metric ton of chlorine
production and by 1983, the discharge of mercury to
water overall will be an order of magnitude lower,
reaching effectively zero in some plants.
(b) Brine sludges - the relative mercury content will
be reduced to 50 percent of the current level by
1977 and to 20 percent of the current level by
1983.
(c) Process sludges - mercury-rich precipitates not
reclaimed will be reduced to about one-half of the
current level by 1977. By 1983, 99 percent
recovery of mercury in these sludges will be
achieved in some plants, and approximately
90 percent in the others.
5-10
-------
(d) The chlorinated hydorcarbons generated will be
reduced to 50 percent and 20 percent of the present
levels, by 1977 and 1983, respectively.
5.2.1.3 Downls Celj. Process
Down's Cell chlorine is produced in 5 plants in five states.
The typical plant has a daily capacity of about 200 tons of
chlorine. All five plants are 5 to 30 years old.
In the Down's cell process, sodium and chlorine are
manufactured by electrolysis of molten sodium chloride.
After salt purification to remove calcium and magnesium
salts and sulfates, the sodium chloride is dried and fed to
the cell, where calcium chloride and other minor bath
components are added to give a low-melting CaC12*NaCl
eutectic, which is then electrolized. Sodium is formed at
one electrode, collected as a liquid, filtered, and sold.
The chlorine liberated at the other electrode is first water
washed (for SiCljf hydrolysis) and then dried with sulfuric
acid purified, compressed, liquified, and sold.
The molten sodium-calcium metal mixture is then cooled and a
calcium sludge is separated by filtration. At two plants
this material is wasted and goes to sea disposal in drums.
At the other three plants proprietary processes treat these
materials, return part or all to the process, and any
residue left over has been stated by the manufacturers to be
non-hazardous. Details of this have not been divulged.
The flow diagram for the usual operation of this process is
given in Figure 5-3.
There are several wastes generated by this process:
(a) Brine purification sludges - these consist of
calcium carbonate, magnesium hydroxide and in some
cases barium sulfate. The brine purification muds
operated by Down's cell facilities are similar to
those described earlier and are non-hazardous.
(b) Sodium-calcium sludges - These arise from the
filtration of product sodium. These wastes are
considered hazardous because of their reactivity
with water. These sludges must be disposed of
under carefully-controlled conditions to avoid
explosions or fires. We envision no technology
changes which will alter the amounts of sodium-
calcium sludges generated through 1983. The impact
of air and water regulations on the wastes
generated appear to be negligible.
5-11
-------
AS APPROPRIATE
INoOH
SODA ASH
BoCI2
RAW BRINE
1760(1663-1915) NaCI,
WITH Mg, Co, S04
IMPURITES
1
BRINE
PURIFICATION
i
M
fO
SOLID WASTE
4(0-30) BRINE
PURIFICATION
MUDS
(Mg(OH)2,CaCOj,BaS04)
WATER
VAPOR
VENT
I
IO CaCI-
4-9
SULFURIC ACID
(98%)
1.5 LIME
EVAPORATE,
FILTER
AND
DRY
1 1
J PERIODIC TE
AND CLEAN
WATER-BORNE
AND RUBBLE
CONTAMINATED
WITH SODIUM
WASTE '
50(40-90) NaCI
DOWN'S
CELL
ELECTROLYSIS
— ^
PRODUCT
COOLING,
DRYING
AND
PURIFICATION
ARDOWN^ 1
t V
4 ALKALINE SALTS 5-12
60 NaCI WASTE- WD
10 CARBON (70-80%) i
^1000 CHLORINE
^PRODUCT
^^^^^fc|~
-------
(c) Wastes from cell maintenance and replacement are
contaminated with small amounts of sodium metal.
This waste is allowed to remain in the open in an
isolated area exposed to the weather to allow
moisture to penetrate and react with the sodium.
(d) sodium chloride fines from steps prior to fusing
are landfilled on-site, where dry salt is used as
raw material.
(e) Excess calcium hypochlorite is decomposed in ponds.
(f) Effluent from washing area goes to wastewater
treatment system.
All producers are faced with providing a dedicated storage
because of the potential for sodium inclusion. Storage is
on-site initially until weathering is complete, then the
waste could be removed to a commercial disposal site as a
non-hazardous waste.
5±2±2 Synthetic Sodium Carbonates (SIC 28122)
5A2i2il Synthetic Soda Ash JSolyay Process^
The typical synthetic soda ash plant has a capacity of about
1500 tons per day and is over 30 years old.
Soda ash is produced either by the mining and refining of
impure sodium sesquicarbonate (from ore - SIC 1U74), or by
the Solvay process-where soda ash is produced from limestone
and salt with the aid of ammonia. This process is shown in
the accompanying flow diagram (Figure 5-<4) . The Solvay
process involves a reaction in aqueous solution (under
pressure) between ammonia, brine (NaCl), and carbon dioxide
to yield sodium bicarbonate, which is then converted to soda
ash by heating. Ammonia is recovered by the addition of
slaked lime to the used liquor. The saturated brine is
purified of other metal ions by precipitation, and then
picks up ammonia in an absorber tower. Ammoniated brine is
reacted with carbon dioxide in a carbonating tower, and the
resulting bicarbonate precipitates as the sodium salt,
forming a slurry. The slurry is filtered to remove the
solid bicarbonate which is calcined to yield the light ash
product. Dense ash is made by successive hydration and
dehydration of the light ash. The carbon dioxide and
ammonia are recycled. The wastes consist of salt brine
purification muds which contain calcium carbonate and
magnesium hydroxide and the ammonia distiller bottoms which
consist predominantly of calcium carbonate with lesser
amounts of magnesium carbonate, silica, and alumina. The
waste brines are always discharged as a water effluent
except when evaporated to dryness for sale. The solids are
5-13
-------
STEAM
120-1,025 CO2
en
I
I
RAW BRINE
CONTAINING: fc BR
1,500 NaCI ^ PURIFI
!20-250MgCI2
1
COLLi
Al
SET
r~
SOLID WASTES
0.15 NH3
1 1
11 t RECYCLE NH3 ^ SPENT BRINE
C°2VX
1
1 ,200 LIMESTONE »
IOO IOOOCOKE— ^ LIME fc 01 fLLfco _. . ._^ "Hj
100 I.OUOCOKC— •> K||_N » oLAKCR » ST|LL
AIR ••
f
iCTION DISTILLER WASTES
xu « 1
FLING 1 OPTIONAL CaCI2 RECOVERY
r' " 1 |
I f '
| 1 EVAPORATOR - DRYING '
WATER-BORNE , \
75-150 Mg(OH)2 WASTES Ail
50-200CaC03 1,090 CaCI2 * » '
60Si02 510 NaCI /K| WASTE CaCI2 •
3 SUSPENDED SOLIDS (NaCI,CaCI2) PRODUCT I
16,000 WATER I 1
0.15 NH3(IN THE FORM OF N^CI) ' '
30 CaS03 FlftllPF fi-4
SODIUM CARBONATE MANUFACTURE
BY THE SOLVAY PROCESS
-------
land disposed in extensive settling bed systems. These land
destined wastes are not hazardous.
5.2.2.2 Sodium Bicarbonate Process
All such production is located either at Solvay process soda
ash plants or at Trona refineries. The typical plant is 150
tons per day, and is the same age as the parent plant — that
is, namely over 30 years for Solvay locations and less than
10 years for Trona locations.
This item is produced by reaction of soda ash with carbon
dioxide in water under pressure. The bicarbonate
precipitates from the solution and is filtered, washed,
dried, and packaged. The only process wastes are water-
borne and consist of aqueous solutions containing
bicarbonate and soda ash. These are neutralized prior to
discharge. There are no hazardous wastes generated. The
flow diagram is shown in Figure 5-5.
5^.2^3 Sodium Hydroxide I SIC 28123)
This product is produced solely as a co-product of chlorine
manufacture. The associated wastes are wholly attributed to
SIC Code 28121.
5^.2^, U Other Alkalies (SIC
lLs.2iJl.rl Ammonium and Potassium Carbonates
Potassium carbonate is made in conjunction with the produc-
tion of chlorine at plants electrolyzing potassium chloride
(see SIC 28121). The caustic liquor is carbonated by carbon
dioxide under pressure. No wastes other than those
attributable to the Diaphragm Cell Process are generated.
Ammonium bicarbonate is recovered from process streams of
the Solvay Process for manufacture of soda ash (see
SIC 28122) . No additional wastes are generated.
5±2*J**2 Potassium Hydroxide
This product is produced solely as a co-product of chlorine
manufacture. The wastes associated are wholly attributed to
SIC Code 28121.
5-15
-------
Ut
I
I-1
-------
5.2.5 Aggregate Sip 2812 Hazardous Wastes to Land
The amounts of the constituents of the several waste streams
containing hazardous materials in sufficient quantities to
be hazardous in total are shown for the typical or usual
operation in the flow diagrams in the preceding sections.
The values given are relative to the product rate; that is
they are numerically equivalent to either kilograms per
metric ton of product or pounds per 1000 pounds of product.
The hazardous waste streams from this industrial category
are all from SIC 28121 and are:
- mercury-contaminated brine purification muds from the
Mercury Cell process,
- mercury-rich wastes from treatments and cleanings
elsewhere in the Mercury cell process,
- chlorinated hydrocarbons from both the Mercury Cell
and Diaphragm cell process,
- asbestos separator wastes from the Diaphragm Cell
process,
- lead-containing treatment wastes from the Diaphragm
Cell process, and
- explosively reactive or flammable metallic sodium and
calcium sludges from the Down's Cell process.
The amounts of moisture in these waste streams are given
generally as:
no water; chlorinated hydrocarbonstsodium-calcium
sludges.
30-60% water; mercury, lead, and asbestos containing
muds, filter cakes, and sludges.
The Table 5-1 lists the aggregated hazardous waste streams
of SIC 2812 on a state-by-state, regional, and total U.S.
basis and the amounts of the various hazardous constituent
materials.is estimated as currently valid. Local situations
in each state which deviate from the "typical" are taken
into account insofar as possible. The data of this table is
a mix of the most reliable and the more consistent entries
from several sources:
- calculated from consistent manufacturers data
- estimated from fragmentary or equivocal manufacturer's
data
- vol. XIV of EPA-670/2-73-053 (August 1973)
- estimated from waste disposal contractor's data
- our own estimates
5-17
-------
Table 5-1 . Hazardous Wastes Currently Destined for Land Disposal From
Alkalies and Chlorine, (metric tons per year, dry basis)
IV Alabama
X Alaska .
IX Arizona
VI Arkansas
IX California
VIII Colorado
I Connecticut
III Delaware
'IV Florida
IV Georgia
IX Hawaii
X Idaho
V Illinois
V Indiana
VII Iowa
VII Kansas
IV Kentucky
VI Louisiana
I Maine
III Maryland
I Massachusetts
V Michigan
V Minnesota
IV Mississippi
VII Missouri
VIII Montana
VII Nebraska
IX Nevada
I Now Hampshiro
II Now Jersev
VI New Mexico
II New York
IV Nor tli Carolina
VIII North Dakota
V Ohio
VI Oklahoma
X Oregon
III Pennsylvania
I Rhode Island
IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII Utah
I Vermont
III Virginia
X Washinqton
III West Virginia
V Wisconsin
VIII Wyoming
TOTAJ,
Region I
11
III
IV
V
VI
VII
VIII
IX
X
Diaphragm Cell Solids
Total
20
30
100
1,000
300
50
100
100
20
1P300
40
50
Ir900
20
100
300
10
5.400
'200
320
100
1.600
2,900
100 •
70
140
Asbestos
Content
6
14
29
800
196
19
29
55
7
80
20
25
830
7
70
160
5
2.300
84
170
46
280
1 .600
29
25
90
Lead
Content
3
8
16
220
50
11
16
30
4
45
460
4
15
90
3
980
46
94
12
100
680
16
14
15
Mercury Cell Solids
Total
4,600
4,400
4,200
1.1W
6,000
7,000
500
5,500
5,106
50
660
5,000
100
1 .700
2.200
2.900
48,000
500
7,600
6,600
20rOQO
4.700
7,100
1,700
Mercury
Content
30
13
14
*
6
32
31
12
16
13
6
4
20
20
13
15
22
270
12
29
28
100
32
51
13
Chlorinated
Hydrocarbons
110
4
50
60
11
16
70
510
20
110
11
75
100
50
80
ssn
60
150
20
2,000
20
175
65
320
200
1.100
16
15
13
Sodiurr/
Calcium
Sludge
810
640
1,500
810
640
Total
Hazardous
Wastes
4,700
0
0
0
24
0
0
4.400
0
4,300
0
0
1,100
6
6
120
6,000
8r500
0
0
400
0
0
0
0
0
60
0
5,700
0
3rOOO
70
0
2,000 '
0
40
0
0
0
0
5,800
2 600
0
0
2b
1,966
2,700
2,900
0
57,000
500
8,700
7,100
21,000
6.400
11,000
120
84
1,900
5-18
-------
The hazardous constituents in two cases (lead and mercury)
are given in terms of the amount of the chemical element
since the hazardous nature of these materials is specific to
the chemical elements, whether or not they are actually in
elementary or combined form in the waste stream.
Chlorinated hydrocarbons are a generic class of chemical
compounds hazardous because of their combined chemical form
and are given as suclh. Asbestos is a natural fibrous
mineral material of complex chemical structure, and is given
as such. The sodium-calcium sludge is a flammable mixture
that is given in total.
The data are collected into four groups of waste streams as
given in the following table. Essentially, this represents
the four hazardous waste stream problems from these
industries:
(a) The asbestos and lead-contaminated solid wastes
from the brine treatments and cell cleanouts and
repairs of the Diaphragm cell process,
(b) The mercury-contaminated solid wastes from brine
purification, process waste treatment, and cell
room cleanup of the Mercury Cell process.
(c) The chlorinated hydrocarbon waste separated from
both the Diaphragm Cell process and the Mercury
Cell process.
(d) The explosive, flammable, sodium-calcium sludge
cleanout from the Down's cell process.
The asbestos, lead, and mercury contents of the first two
streams are also given, as is the total of the hazardous
waste streams from this industry subcategory (SIC 2812).
The largest amounts of hazardous waste streams now disposed
of on land from the alkalies and chlorine industries (SIC
28121) are from the Mercury Cell process and amount to nearly
50,000 metric tons (55,000 short tons) per year, dry basis.
This is nearly 88 percent of the estimated total from the
whole SIC subcategory of 57,000 metric tons (63,000 short
tons) per year, dry basis. Since a large fraction of these
wastes^re located at the bottoms of settling ponds, the
estimated total weight (moisture included) is of low
significance, but for purposes of record are given as
110,000 metric tons (120,000 short tons) per year for
SIC 2812 as a whole.
5-19
-------
s. 6 £l2iection. 2l SlfiLJfiii Hazardous Wastes £fl ^971 §nj|
1983.
An overall growth in the chlorine-producing industries is
expected through 1983 because of the expanding use of
chlorine in the treatment of drinking water, the treatment
of wastes, and the manufacture of plastics. This
subcategory is responsible for the hazardous wastes in SIC
2812. The other segments of 2812 (i.e., synthetic sodium
carbonates and miscellaneous other alkalies) are not
expected to develop any processes ot treatments in this
period that will generate hazardous wastes destined for land
disposal.
The individual growth factors used in the forward projection
of the SIC 2812 wastes were mentioned earlier in the
individual process descriptions and include:
- no new starts in the Mercury cell process.
- all new growth (for chlorine) in the Diaphragm Cell
process,.
- the gradual replacement of carbon anodes with coated
metal anodes,
- the eventual use of synthetic separators to replace
asbestos separators,
* little growth in the Down's Cell process,
- increasingly effective recovery of mercury in the
Mercury Cell process*
The major effects of water and air regulations have already
been experienced by these Industries insofar as generation
of large amounts of hazardous wastes for land disposal is
concerned. The further amounts of mercury, lead and
asbestos that will be removed from discharges due to the
application of the 1977 and 1983 restrictions will be small
compared to that already removed to land-destined wastes.
The reduction in the use of carbon anodes will also cause a
reduction in the generation of chlorinated hydrocarbon
wastes.
Tables 5-2 and 5-3 give the projected amounts of wastes in
the same format as was presented in Table 5-1. state-by-
state, regional and total U.S. aggregates are given for the
four types of waste streams and for the total hazardous
waste to land disposal. The trend of total amounts of
hazardous wastes in metric tons per year (short tons per
year) projected for SIC 2812 are summarized as follows*
5-20
-------
Table 5-2. Hazardous Wastes Expected to be Destined for Land Disposal
1n 1977 From SIC 2812,,Alkalies and Chlortne
(metric tons per year, dry basts)
iV Alabama
X Alaska
IX Arizona
VI Arkansas
IX California
VIII Colorado
I Connecticut
m belaware
W Florida
IV Georgia
iX Hawaii
X Idaho
V Illinois
V Indiana
Vif Iowa
VII Kansas
IV Kentucky
VI Louisiana
I Maine
III Maryland
I Massachusetts
V Michigan
V Minnesota
IV Mississippi
VII Missouri
VIII Montana
VII Nebraska
IX Nevada
I New Hampshire
II New Jersey
VI New Mexico
II New York
IV North Carolina
VIII North Dakota
V Ohio
VI Oklahoma
X Oregon
III Pennsylvania
I Rhode Island
IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII Utah
I Vermont
III Virginia
X Washington
III West Virginia
V Wisconsin
VIII Wvoming
TOTAL
Region I
II
III
IV
V
VI
VII
VIII
IX
X
Dim
Total
00
20
30
60
10
50
40
1,500
300
40
90
200
in
180
40
70
1,800
15
100
300
30
5.000
300
350
7AO
520
3.330
50 •
60
150
iragmCell Solids
Asbestos
Content
53
9
22
45
6
40
34
Ir200
260
27
70
120
IB
120
21
53
Ir300
10
80
260
15
3,800
200
300
900
400
2.500
50
40
100
Lead
Content
3
6
12
320
74
8
12
22
3
33
330
3
11
65 .
2
900
35
70
9
110
650
12
11
11
Mercury Cell Solids
Total
4,600
4,400
4.200
1,100
6.000
7.000
500
5.500
2.100
50
660
5.000
100
1,700
2.200
2,900
48,000
500
7.600
6.600
20.000
4.700
7.100
1,700
Mercury
Content
19 "
7
8
2
11
7
' 4
9
7
6
2
10
5
5
9
5
120
4
16
16
54
9
12
5
Chlorinated
Hydrocarbons
60
3
24
33
6
12
• 35
350
15
75
8
40
W
T3
40
8
360
14
64
10
1,200
15
90
90
150
130
710
12
11
14
Sodium/
Calcium
Sludge
X
830
660
1,500
830
660
Total
Hazardous
Wastes
4,700
0
0
0
20
4r400
0
4.300
0
0
1.100
0
0
60
6.100
8.900
500
0
0
400
0
0
0
0
5
50
0
0
3f100
100
' 0
900
0
40
0
0
0
0
5,700
? 300
0
0
15
1,800
2,600
2,900
0
56,000
500
8,700
7.000
21,000
5.300
11.200
60
70
1,800
5-21
-------
Table 5-3. hazardous Wastes Expected to be Destined for Land Disposal
In 1983 From SIC 2812, Alkalies and Chlorine
(metric tons per year, dry basis)
IV Alabama
X Alaska
IX Arizona
VI Arkansas
IX California
VIII Colorado
I Connecticut
III Delaware
IV Florida
IV Georgia
IX Hawaii
X Idaho
V Illinois
V Indiana
VII Iowa
VII Kansas
IV Kentucky
VI Louisiana
I Maine
III Maryland
I Massachusetts
V Michigan
V Minnesota
IV Mississippi
VII Missouri
VIII Montana
VII Nebraska
IX Nevada
I New Hampshire
II New Jersey
VI New Mexico
II New York
IV North Carolina
VIII North Dakota
V Ohio
VI Oklahoma
X Oregon
III Pennsylvania
I Rhode Island
IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII Utah
I Vermont
lit Virginia
X Washington
if.t West Vinii ilia
V Wisconsin
VIll Wyominq
TOTAL
Region I
II
III
IV
V
VI
VII
VIII
IX
X
Diaphragm Cell Solids
Total
40
16
15
30
5
30
20
900
200
20
50
80
1.5
100
20
40
1.000
8
60
180
10
2.800
130
?00
150
310
1 ,900
30 •
30
80
Asbestos
Content
' 28
5
12
24
3
22
18
630
140
14
37
65
10
,_ 66
11
28
690
5
42
140
8
2,000
100
160
110
220
1,300
22
29
53
Lead
Content
5
1
3
6
3
170
40
4
6
12
1
18
180
1
6
35
1
490
18
36
7
An
350
6
5
6
Mercury Cell Solids
Total
4.600
4,400
4.200
1.100
6JJOO
7,000
ioo
5,500
50
5,000
2.200
41,000
500
5,500
6.600
20.000
1.100
7,000
Mercury
Content
1
0.3
0.4
0.1
0.4
0.6
U.^
0.4
0.1
0.4
0.3
A
0.2
0.4
0.6
2.3
0.1
0.6
Chlorinated
Hydrocarbons
5
1
2
3
1
1
3
36
1
8
1
4
2
1
4
3
36
1
6
35
1
160
1
6
38
15
14
72
1
2
6
Sodiunv
Calcium
Sludge
880
700
iy4oo
880
700
Total
Hazardous
Wastes
4,600
0
0
0
l6
0
0
4.400
0
41200
0
0
1.100 •
0
0
i_ 30
6,000
7.900
500
0
0
200
0
0
0
0
0
20
0
s;<5oo '
0
1.000
70
0
100
0
20
0
0
0
0
5,700
1,000
0
0
10
70
2,400
TO"
0
45,000
500
6,600
6,800
21,000
1,400
8,900
30
0
30
90
5-22
-------
Period Current 1977 1983
dry basis 57,000 56,000 45,000
(63,000) (62,000) (50,000)
moisture 110,000 109,000 89,000
included (121,000) (120,000) (98,000)
Thus, although the industry as a whole is expected to grow
very significantly, the amounts of hazardous wastes destined
for land disposal are expected to decrease-principally
because of process technology developments within the chlor-
alkali segment. The above wastes consist principally of
sludges, filter cakes and dewatered muds and the overall
moisture content estimate was based on these (approximately
50%).
5il Industrial Gases JSIC_28131
The gases produced in this industry segment are those
generally intended for sale in compressed, liquid or solid
form. These are: acetylene, air separation products
(including the noble gases), carbon dioxide, hydrogen,
carbon monoxide, helium, and nitrous oxide. The other gases
are in other SIC categories, e.g., fluorine and sulfur
dioxide which are in 2819, ammonia in 2842 and 2873, and
chlorine in 2812.
5-.3..1 Acetylene iSIC_28123j.
Until recently, most acetylene was made by the reaction of
calcium carbide with water:
Ca2C2 + 2H2O = Ca(OH)2 + C2H2
When carried out as a batch process, the calcium hydroxide
wastes consist of a lime slurry containing about 90% water.
In the dry generation process, more nearly stoichiometic
quantities are used and the heat of the reaction is largely
dissipated by water evaporation, leaving the by-product lime
in a dry, fairly easily handled state. This lime may be
recycled to the carbide process. In neither case are the
wastes hazardous. The calcium carbide process is the only
one principally carried out in SIC Code 281 establishments
and is shown in the accompanying flow diagram, see
Figure 5-6. The production from this process is the
principal volume and is detailed earlier in the Section 4
tables.
5-23
-------
VEST
1385 WATER
01
ro
*».
t
:ARfflDE »
REACTOR
SOLID WASTE
2850 Co(OH)t
DRYER
COMPRESSION
AND
BOTTLING
EFFLUEKT
-------
Other methods of acetylene production include (1) from
paraffin hydrocarbons by pyrolysis (Wulff Process), (2) from
natural gas by partial oxidation (Sachsse Process), and (3)
from hydrocarbons by Arc Process.
The Wulff Process is described (for a butane feed) by the
following reactions:
C4H10 + steam C2H2 + C2H4 + CO + H2
C2H4 = C2H2 •*• H2
2CH4 = C2H2 * 3H2
Most off-gases, (principally ethylene, carbon monoxide,
hydrogen, and methane) are gases used as fuel for the steam
boiler, for combustion chamber and heating, or other in-
plant use. There is a small amount of organic tar originat-
ing in the furnace and the electrostatic precipitator, but
these wastes are not severe hazards. This process, the Arc
Process, and the Sachsse Process generally are carried out
in SIC Code 286 (Industrial Organic Chemicals)
establishments.
The Sachsse Process may be described by the following
reactions:
CH4 + 202 = C02 + 2H2O
2CH4 = C2H2 + 3H2
This cracking process may be carried out using a variety of
hydrocarbon feed stocks; e.g., natural gas, LPG, naphtha,
fuel oil or even crude oil. The sooty waste emanates from
the burner and the soot filter. A widely used variation of
the Sachsse process is the BASF process.
The Arc Process is generally not favored for U.S. production
of acetylene because of the high power requirements and
associated costs. The Huck Process, which employs one
design of an arc furnace, is not operated in the U.S. In
fact, the DuPont arc process is the only arc process used in
the U.S., and it is currently shut down.
The typical acetylene plant has a 50 ton per day capacity
and is 5 to 30 years old.
5-25
-------
£ Carbon Dioxide (SIC 281331
This product is recovered from limestone calcination and as
a by-product of hydrogen generation. These by-product gas
streams are the raw materials for carbon dioxide production.
Two variations of the purification process for carbon
dioxide manufacture are given in Figure 5-7. Permanganate
scrubbing is used where elimination of organic impurities by
oxidation is required, with relatively pure gas streams the
standard process involves separation of "knockout" water
(drying) ais the primary purification step. Neither process
produces any hazardous wastes for disposal on land. The
typical plant has a 250 ton per day capacity and is 5 to 30
years old.
S.-.3.3 Elemental Gases and Other Industrial Gages
(SIC 2813if
Sil-J-jL Helium
Helium is extracted cryogenically as a by-product of natural
gas production. Many plants are owned and operated by the
U.S. Bureau of Mines. There are no hazardous wastes
attributable to the production, the flow diagram for the
usual helium operation is given in Figure 5-8. Natural gas
is cooled, liquified and rectified to separate the helium,
which is then purified as shown.
The typical plant is located near a natural gas well in the
Texas-Oklahoma area. Total production is small and, for the
typical plant, is less than 10 tons per day. Practically
all facilities are post World War II (30 years or less) .
5... 3. .,3.2 Air Distillation Products
The principal products produced from air distillation are
oxygen and nitrogen.
The rare gases argon, neon, xenon, and krypton are also
obtained from the same process. The usual composition of
air is shown below:
5-26
-------
1100 IMPURE
CARBON DIOXIDE
COMPRESSOR
45 KNOCKOUT
WATER
PERMANGANATE SCRUBBING
2.5 WATER
0.086 KMn04
0.09 NaOH
SCRUBBING
T
WASTE WATER
0.046 Mn02
0.0025 KMn04
0.115 Na2C03
2.5 WATER
55 VENT GASES
CARBON
DIOXIDE
PRODUCT
FIGURE 5-7
CARBON DIOXIDE MANUFACTURE
-------
270 CARE
DIOXIDE
10-30 AIR
HO CHARCOAL
54,000 RAW
NATURAL GAS
SCRUBBER
AND GAS
CLEANER
1
i
MEA
ABSORER
AND
DRYER
CHIL
Af
RECT
J.ER
ID
1FIER
CATALYTIC
REACTOR,
UnTtrC,
AND
COMPRESSOR
HEAT
EXCHANGER
AND
CHARCOAL
ABSORBER
Ut
to
00
1
I-IO WATER
I-10 CONDENSABLE HYDROCARBONS
I-IO PIPELINE DUST
1000
HELIUM
•PRODUCT
(99-99.?
PURITY)
I-IO WATER
36O-4OO
NITROGEN
(LIQUIFIED)
I-IO
SPENT
CHARCOAL
52j4OO
, NATURAL
GAS TO
PIPELINl
FIGURE 5-8
HELIUM MANUFACTURE
-------
Gas Volume Percent
Air 100
Nitrogen 78.03
Oxygen 20.99
Argon 0.94
Hydrogen (up to) 0.01
Neon 0.0015
Helium 0.0005
Krypton 0.00011
Xenon 0.000009
Carbon dioxide 0.03-0.07
The rare gases are separated by side rectification columns
from takeoffs at various points in an air separation plant,
as shown in Figure 5-9. T?he wastes involved are only oil
and grease from cooling compression seals.
No hazardous wastes are generated by these processes. The
typical plant has a 500 tons per day capacity and is less
than 30 years old.
•4
5.3.3.3 Carbon Monoxide
Carbon monoxide is made by reforming methane with steam.
The currently typical operation is shown in Figure 5-10.
Hydrogen is a by-product, and there are no significant
wastes produced. One plant accounts for about half of the
U.S. production and the rest are small (about 50 tons per
day). These plants are 5 to 30 years old.
5.3.3.U Hydrogen
Hydrogen is produced as a co-product with carbon monoxide as
shown in Figure 5-10, from natural gas by catalytic
processes and by purification of refinery by-product gas.
No significant amounts of wastes are generated in any case.
5i3.r3.i5 Nitrous Oxide
This gas is produced by thermal decomposition of ammonium
nitrate followed by removal of co-product water vapor from
the product gas stream. No hazardous wastes are generated
and the flow diagram is given in Figure 5-11. The process
reaction is:
NH4N03 = N2O + 2H2O
5-29
-------
TO RARE GAS RECOVERY
in
CO
o
4320
1
I_
FIL1
(NECN ARGON
STREAM STREAM
t t
I ^3262 NITROGEN
•» KXX) OXYGEN
•* 0.013 KRYPTON STREAM I TO RARE GAS
/RECOVERY
•» 0.00173 XENON STREAM [
* 1 1
CONDENSATE
WATER
. ,
* H ^
| .•,_
^ WATER m • NIIROGtN
•ER COOLING RECYCLE
»> TOWER » REFRIGERATION
1 1 1 '
| BACKWASH SLOWDOWN I
JCOOLNG WVTER SYSTEM |
FIGURE 5-9
OXYGEN, NITROGEN AND RARE GASES MANUFACTURE
-------
<2 MAKE-UP
METHANOLAMINE
6.4 OXYGEN FROM AIR.
633 METHANE-
REFORMER
715 STEAM
Ul
HYDROGN
CLEAN-UP
SYSTEM
PROCESS
CONDENSATESxf^
1850 WATER'
II ION EXCHANGE*
CHEMICALS
WATER
TREATMENT
H
BOILER
METHANOLAMNE
SLUDGE
C02 SCRUBBER
WASTES
ION EXCHANGE REGENERANTS
•^220 HYDROGEN PRODUCT
CARBON
MONOXIDE
CLEAN-UP
.1000 CARBON MONOXIDE
PRODUCT
COOLING
TOWER
<-— SEPARATED COMPRESSOR
+> WASTES
COLLECTION
BOX
T
RGURE 5-K)
CARBON MONOXIDE AND HYDROGEN MANUFACTURE
WATER-BORNE EFFLUENT
16 ION EXCHANGE AND BOILER SLOWDOWN SALTS
as COMPRESSOR OIL
I ftETHANOLAMINE
145 CO2
II3QWTER
-------
MOISTURE
CAUSTIC
SOLUTION
ui
I
u>
N)
1830 HIGH PURITY _
AMMONIUM NITRATE"
RETORT
COOLER
1
1
i
REGENERATION
DRYING
MEDIUM
NITRIC
SCRUBBER
O
DRYER
COMPRESS,
COOL,
AND
PACKAGE
1000 NITROUS
PRODUCT
800-820
KNOCKOUT
WATER
SPENT CAUSTIC
SOLUTION EFFLUENT
CONTAINING
I-10 SODIUM NITRITE
FIGURE 5-11
NITROUS OXIDE MANUFACTURE
-------
JL3._U Aggregation o£ SIC_2811 Sasa£<22!i§ Wastes to Land
None of the processes producing the SIC 2813 industrial
gases were found to generate hazardous wastes for land
disposal.
5^.3^5 Projection of SIC^ 2813 Hazardous Wastes to Land
DigBosal
No process change or impact of air or water regulations is
expected to cause a significant generation of hazardous
wastes for land disposal from the SIC 2813 category through
1983.
Lti Inorganic Pigments (SIC 2816)
SiibJ. Introduction
This industry was subcategorized into three five-digit SIC
industries; 28161 (Titanium Dioxide Pigments), 28162 (Other
White opaque Pigments), and 28163 (Chrome Colors and Other
Inorganic Pigments) .
The pigment products produced in each five-digit SIC
subcatoregory are listed and discussed in Section 3 of this
report. The purpose of the present section is to detail the
processes by which the pigments are made, characterize the
land destined wastes currently generated by the processes,
and estimate the quantities of land destined waste expected
from these processes in the years 1977 and 1983. The
amounts of hazardous waste streams and the amount of
hazardous constituents in them are presented on a state by
state and EPA regional basis.
5..ii2 Titanium Dioxide Pigment (SIC 28161)
This material is generated by two processes - one involving
the acidification of ilmenite ore in sulfuric acid and the
other involving chlorination of rutile ore to produce Ticltl
which is then converted to TiO2. These processes will be
discussed separately. Two facilities differ from the above
generalizations in that they have the unique characteristic
of simultaneously upgrading ilmenite ore and chlorination of
the mineral, thus allowing use of a lower grade of ore than
rutile with the chloride process.
5-33
-------
Sulfate Process
In the sulfate process, titania-bearing ilmenite ores are
dissolved in sulfuric acid to produce titanium sulfate as an
intermediate product. The acid solution is clarified, a
portion of the iron sulfates is removed by crystallization,
and the titanium sulfate is hydrolyzed to form a white, non-
pigmentary hydrate. The hydrate is calcined to form
crystalline titanium dioxide, which is milled, surface
treated, and packaged for sale. Product quality from the
sulfate process is not so dependent on ore quality as is
that from the chloride process.
A general reaction scheme for the sulfate process using
ilmenite ore containing various iron oxides (FeO and Fe2O3)
is as represented by the equations:
(a) acidification
FeO(Fe2O3«Ti02 «• 5H2SOU=
FeSOU + Fe2(S04)3 + TiOSOft + 5H2O
(b) hydrolysis to form hydrate
TiOSO4 * 2H2O = TiO2»2H2O + H2SOJJ
(c) calcination
TiO2«2H2O + Heat = TiO2 + H2O
A typical mass-balanced flow sheet for the manufacture of
TiO2 by the sulfate process is shown in Figure 5-12. There
are two types of solid wastes produced by this process; ore
residues and solids generated by wastewater treatment.
(a) Ore residues. In the sulfate process, ore residues
consist of non-hazardous sulfuric acid insolubles
such as :silica, coke, and non-soluble ore impurities.
The fact that impurities such as oxides .of chromium
and vanadium-in the ore have not been dissolved by
the strong acid treatment .is-direct evidence that
they are not potentially hazardous upon land disposal,
in the physical and .chemical .form that they have in
the ore.
(b) Solids Generated by. Wastewater Treatment.
Plants which use the sulfate process which do not
dispose of their acidic water-borne wastes by ocean
dumping must, to meet future water quality
standards, neutralize their wastewater effluents.
This can be expected to generate large volumes of
non-hazardous solid waste consisting of oxides and
hydroxides of some of the water-borne ore
impurities present in the ilmenite ore. The large
solid waste loadings generated can be expected to
5-34
-------
01
I
u»
01
ORGANIC
FLOCCULANTS
WATER 1 0-ISb203
i -i t
3,553 H2S04 £= mr«rr COOL,
UI\?tO 1 OOV^T* A I 1 I7C* LJVT\O/*\1 VOI<5
59 SCRAP IRON & AMD =£: CRYSTALLIZE ^^ HYDROLYSIS _
DSbuwiwN _ <.™r AND FILTERING
1,988 ILMENITE.. ., ^ SETTLE CENTRIFUGE
4 \
WASTE. niGFS-nnsu si IIOGF RY-PR
80 UNDIGESTED ORE: 948 CO
(A) (I) o-,9
SiOa 56% H%
Co 1.3% 9%
AlgOs 38% 69%
Cr203 0.3% 10%
S 4% 1%
59 SCRAP IRON
1 FLOCCULANTS
3.1 H2S04
WATER
I
WATER »*
SCRUBBER
WATER
f f
REPULP,
^ WASH
^ AND
FILTER
| |i O
ODUCT STRONG AC!D(I5%-30%) WEAK ACID (2%)
PPERAS 2,125 H2S04
H2S04 644 FeS04
32 Ti02
35 ORE IMPURITES:
(A) (I)
V20s 4% 13.5%
P20g 1% 6.4%
CaO 17% 2%
MgO 63% 21.3%
MnO 14% 57%
WATER
0.67 SbJO,
*
IKbAI
WA
=CB CALCINE =C= DF
AC
GRI
SCRUB VWER RECOVER
420 H2S04 20 H2S04 17 '
317 FeS04 WATER 32 Nt
21 Ti02 WAI
17 ORE IMPURITIES:
(A) (I)
V20g 4% 13.5%
P205 % 6.4%
CaO 17% 2%
MgO 63% 21.3%
MnO 14% 57%
WATER
0.33 Sb-,0,
9 NaOH
•WENT,
rT' =*F~>[OO° T'°2
JD ^^ PRODUCT
ND
J
r WASTES
no2
J2S04
PER
TREATMENT:
DISPOSAL:
EQUALIZATION
AND SETTLING
(DRYING FOR SALE)
SETTLING
i
LANDFILL SOLIDS
DISHARGE LIQUID
SALE AND/OR BARGING
I
EQUALIZATION
AND SETTLING
NONE
DISCHARGE
OR BARGING
DISCHARGE
LIQUID
1
DISCHARGE
NONE
DISCHARGE
TYPICAL ORE IMPURITIES COMPOSITION:
25-35% AI203
5-35% S/Oz
/0-27% MgO
0-6% Cr203
0-5% Co
4- 28% MnO
2-7% V206
FIGURE 5-12
TITANIUM DIOXIDE MANUFACTURE
BY THE SULFATE PROCESS
-------
contain mostly iron oxides (or hydroxides) with
trace amounts of the hydroxides of manganese and
chromium.
Assuming neutralization will be by lime treatment, calcium
sulfate would be the major precipitate. The concentration
of trivalent chromium in the resultant sludge solids is
estimated to vary between 0 to 185 ppm (w/w dry basis).
This material would be present in the form of insoluble
Cr203. Considering the large amount of the water that would
probably be in the sludge (approx. 75 percent), the overall
concentration of trivalent chromium in the waste would be
less than 40 ppm. Lime precipitation of dissolved vanadium
salts probably would form vanadate compounds and would be
inefficient in removing dissolved vanadium since such
compounds are fairly soluble in the water-borne effluent.
Therefore, it is assumed that virtually no calcium vanadate
will be precipitated, and most of the trace amounts of the
vanadium present will be in the water-borne effluent. Thus
the only potentially hazardous constituent of the TiO2!
sulfate process sludge from wastewater treatment would be
trivalent chromium hydroxide in trace amounts. Antimony
trioxide is not considered in these figures since its use is
optional and its presence is not representative of the
entire industry. Calcium sulfate, ferric hydroxide, and
titanium dioxide would comprise over 99.9 percent of the dry
waste stream.
The concentration of potentially hazardous constituents in
the sulfate process waste stream destined for land disposal
would then average less than 0.004 percent. The physical,
chemical, biological, and environmental properties of
trivalent chromium hydroxide is detailed in Appendix A. The
concentration of chromium in this waste stream is such that
the overall toxicological properties of the waste are
reduced in comparison to a highly concentrated chromium
containing waste.
There are several factors which were considered; the first
being the ease of solubilization upon land disposal. The
gradual percolation of water from the top to the bottom of a
land disposed waste maximizes the potential for equilibrium
saturation of the water. Upon exiting from the waste, the
leachate should be saturated with waste component. The
expected concentration of Cr(OH)3.nH2O may be as much as
50mg/l at pH 5.5, because the dissolved CaSO4 will maintain
the leachate at this pH value.
A second factor is surface solubilization and erosion
resulting in surface runoff. This factor varies depending
upon the degree of protection the waste material has from
5-36
-------
wind and rain. Because of the sizeable quantities which may
be generated by neutralization of TiO2 water-borne waste
streams, the effects of no protection are discussed.
Surface solubilization of waste constituents is again pH
dependent, but now the length of contact time between the
waste and the water is much shorter. Therefore, a
saturation concentration would not be expected for Cr, and
the amount of dissolved hazardous material should not be
environmentally significant. Chromium in the surface runoff
from the precipitated Ti02 water-borne waste stream will
have no greater affect on the surrounding environment than
that caused by other constituents, e.g. CaSO4 with its
greater solubility.
In summary, the precipitates from TiO2 sulfate process
wastewater neutralization will contain a small amount of
hazardous constituents. However, the dilution factors of
the other waste constituents minimizes the danger of
environmental contamination due to these hazardous
constituents. Thus it was concluded that little if any
hazardous wastes destined for land disposal is currently
generated by the sulfate process for the manufacture of TiO2
pigment. Also, in the light of the foregoing discussion and
the fact that no new sulfate process plants are planned for
the foreseeable future, this situation should not experience
any significant change through 1983.
5^.Jiili2 Chloride Process
In the chloride process, titanium (TiO2) ores are
chlorinated to produce titanium tetrachloride as an
intermediate. One manufacturer has a proprietary process at
two plants which can use low grade ore (about 65 percent
Tio2) but the other manufacturers using the chloride process
use rutile ore which is about 95 percent TiO2 . The
upgrading process to convert ilmenite (65 percent TiO2) to
rutile (95 percent TiO2) mainly removes iron oxides from the
ore. These two facilities generate one hundred times the
waste load of pollutants generated by conventional chloride
processes, as stated by the manufacturer. This is the
result of the simultaneous, on-site beneficiation of low
grade ore that takes place.
Coke is included to promote the reaction of the ore to
titanium tetrachloride, which is then oxidized to titanium
dioxide and chloride (which is recycled) . A general
reaction scheme using ileminte as the raw material is shown
below:
5-37
-------
(a) Chlorination reaction
Ti02»(Fe2o3) + 2C12 + C = TiCl<* •»• CO2 + (FeCl3)
(b) Oxidation reaction
TiClJJ + O2 = Ti02 + 2C1J
The chlorination reaction above is only approximate because
the iron chloride which results may be a mixture of several
chlorides, and some carbon monoxide is formed as well. The
actual products and product ratios will depend on the raw
material and the reactant ratios used.
Impurities in the system including the iron and other metals
(Al, V, etc.), chlorides, entrained coke and ore, carbon
monoxide and dioxide, and hydrogen chloride (HC1) all have
to be removed prior to the oxidation reaction, which creates
significant effluent waste control problems. After
chlorination, the products are cooled to condense the
undesired metal chlorides. Solids are separated by
centrifugation or filtration, and the gaseous titanium
tetrachloride is condensed. A number of techniques are used
to further purify the tetrachloride.
After purification, the titanium tectrachloride is vaporized
and passed into a reactor with heated air or oxygen. The
solid titanium dioxide particles are mechanically separated
from the gas stream, calcined, ground, surface-treated, and
packed.
Figure 5-13 shows a typical mass-balanced flow sheet for the
manufacture of TiO2 by the chloride process using both types
of ore.
As in the sulfate process, the chloride process yields two
types of solid waste; ore residues and solids generated by
wastewater treatment.
(a) Q£§ residues
Irt the case of the chloride process, the residues
from initial chlorination consist of non-hazardous ,
non-solubilized ore residues resistant to strenous
chlorination (e.g. carbon, and unreacted ore and a
number of non-volatile chlorides of metallic
impurities in the ore such as, Fecl3) . Land
disposal of these solid materials requires no
special precaution to guard against environmental
contamination. The fact that these metallic
impurities have not been reacted and altered in
chemical form by the harsh chlorination process is
direct evidence that they are not hazardous upon
land disposal in this form. The non-volatile
5-38
-------
CHLORINE RECYCLE
WATER
460(850)
CO VENT
62 COPPER OR
mu c r\o
t\fS wn —
I60RGANICS
L
320(920) CHLORINE-
I63(300)COKE
I,090(I,600)ORE • »i
CHLORINATION
t
SCRUBBER
COOL,
CONDENSE
AND
PURIFY
ORE RECYCLE
WASTE:
WATER-W
01
i
CO
vo
PURIFICATION AND
COOLING TOWER WASTES
16(25) ORE
37(68) COKE
3(6) Si02
10(1) ZrO2
25 TiCU
4 CrCI3
2(380) Fe AS FeCI,, + FeCI,
6(2) V208
4(24) AlgOa
62 COPPER OR
IOH..S OR
16 ORGANICS
I3O HCI
WATER
TREATMENT:
DISPOSAL:
4OO OXYGEN
VAPORIZE
AND
OXIDIZE
SCRUB WTER
25 TiCI4
50 HCI
WATER
I
1
.LIZATION AND SETTLING
* PARENTHETICAL VALUES
CHLORINE
RECOVERY
I
COOL
AND
COLLECT
W&TER
IO NoOH
TREATMENT
MILLING
TITANIUM DIOXIDE PLANT WASTE
10 Ti02
16 NaCltNa2S03
WATER
I
I
IOOO Ti02
PRODUCT
1
NONE
DISCHARGE
LANDFILL SOLIDS, DISCHARGE LIQUID OR DEEP-WELL, OR BARGE TO SEA
FIGURE 5-13
TITANIUM DIOXIDE MANUFACTURE
BY THE CHLORIDE PROCESS USING 95% ORE OR 65% ORE*
-------
metallic chlorides are present in the water-borne
effluent.
(b) Solids Generated by Wastewater Treatment
In the case of the chloride process wastes similar
to those in the sulfate process are generated by
treatment of the acidic, heavy metal salt-
containing, water-borne waste streams. The solid
waste can be expected to contain mostly titanium
hydroxide and small amounts of compounds of
vanadium, aluminum, copper, chromium, zirconium,
and niobium, where copper is added in the
purification stage, it will be the major
constituent in the waste. The use of copper is not
considered representative of the industry and is
not discussed here.
Assuming wastewater treatment is by lime neutralization, the
following possibly hazardous constituents will be present in
the resultant slurry: chromium, zirconium, vanadium and
niobium. The properties of these elements and their
compounds are detailed in Appendix A of this report. The
most hazardous constituent is chromium, which comprises
about 3 percent of the dry waste (1 percent on a wet weight
basis). This is sufficiently concentrated that the overall
biological properties of the wastes are very similar to
those of the individual constituents, and stringent
precautions will be necessary to protect surface and ground
waters upon land disposal. The concentrations and forms of
the other three metallic materials listed above are not
judged to be hazardous.
There are six chloride process and five sulfate process
plants. The typical plant produces 300 tons per day and is
5 to 30 years old. Production growth in this subcategory is
expected to take place only in those geographic locations
presently producing titanium dioxide. No new sulfate
process plants are expected to be built. New capacity
installation will be solely in the chloride process and will
accompany technological developments to upgrade ilmenite ore
to be compatible with the chloride process.*701 The
principal impact of air and water regulations will be to
cause more of these heavy metal constituents of the acid
waste streams to be precipitated for land disposal or for
deep-welling or barging, depending upon regulations
operational in these areas.
5-40
-------
Si^i^S Aggregation of SIC 28161 Hazardous pastes to Land
Disposal
The amounts of the constituents of the waste streams
containing hazardous materials in sufficient quantities to
be hazardous in total are shown for the typical or usual
operation in the flow diagrams in the preceding sections.
The values given are relative to the product rate, that is,
they are numerically equivalent to either kilograms per
metric ton of product or pounds per 1000 pounds of product.
The hazardous waste streams from this industry subcategory
are all from the chloride process and consist of chromium
compounds generated by process wastewater treatment.
The amount of water in these waste streams can be expected
to vary from 30-60 percent depending on the dewatering
method employed.
The Table 5-1 lists the aggregate hazardous waste streams of
SIC 28161 on a state-by-state, regional, and total U.S.
basis, and the amounts of the hazardous constituents
estimated to be currently valid. This table also includes
projections of waste quantities take expected in the years
1977 and 1983, The local situation in each state (where
deviations from the "typical" occurs are taken into account
insofar as is possible.
The data in this table is a mixture of the most reliable and
the more consistent entries from three sources:
-calculated from consistent manufacturers1 data
-estimated from fragmentary or equivocal manufacturers1
data
-our own estimates
The hazardous constituent (chromium) is given in terms of
the amount of the chemical element since the hazardous
nature of this material is specific to the chemical element
whether or not it is in elementary or combined form in the
waste stream. Thus the only waste stream destined for land
disposal considered to be potentially hazardous in SIC 28161
is the solid fraction of the treated wastewater stream from
the chloride process,, and this only because of its chromium
content. The table gives the total amount of wastes in the
stream and also the amount of the hazardous constituent on a
dry basis.
The total of the waste stream in the U.S. currently amounts
to 151,000 metric tons per year with the hazardous chromium
constituent comprising 348 metric tons per year. These
wastes occur in EPA regions III,, IV, V, and IX, with region
5-41
-------
Table 5-4. Hazardous Wastes Destined for Land Disposal Generated by
Industry Subcategoru 28161, Titanium Pigments
(metric tons per year, dry basis)
IV Alabama
X Alaska
IX Arizona
VI Arkansas
ix California
VIII Colorado
I Connecticut
III Delaware
IV Florida
IV Georgia
IX Hawaii
X Idaho
V Illinois
V Indiana
VII Iowa
VII Kansas
IV Kentucky
VI Louisiana
I Maine
III Maryland
I Massachusetts
V Michigan
V Minnesota
IV Mississippi
VII Missouri
VIII Montana
VII Nebraska
IX Nevada
I New Hampshire
II New Jersey
VI New Mexico
II New York
IV North Carolina
VIII North Dakota
V Ohio
VI Oklahoma
X Oregon
III Pennsylvania
I Rhode Island
IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII Utah
I Vermont
III Virginia
X Washington
III West Virginia
V Wisconsin
VIII Wyoming
TOTAL
Region I
II
III
IV
V
VI
VII
VIII
IX
X
Current
Chromium
Content
28
42
26
46
56
150
350
26
240
56
28
Total
Hazardous
Waste
17rOOO
10,000
6.000
11.000
13.000
94,000
150rOOO
6,000
115,000
13,000
17,000
1977
Chromium
Content
38
82
55
62
39
76
210
560
55
350
76
39
38
Total
Hazardous
Waste
23,000
19.000
13.000
14.000
9,000
17,000
127.000
220.000
13,000
160,000
17,000
9,000
23,000
1983
Chromium
Content
49
131
89
82
86
99
270
810
89
480
99
86
44
Total
Hazardous
Waste
3f)rOOO
30,000
21.000
19.000
20,000
23.000
167,000
310,000
21,000
220,000
23,000
20,000
30.000
5-42
-------
IV having about 75 percent of the total. The wastes from
the one plant that barges its wastes to sea were not
included in the table since it is not land disposed.
Approximately 60 percent of the total waste streams is
disposed of by deep welling while most of the remainder is
sent to settling ponds. It would therefore be very
difficult to estimate the exact amount of water present in
these waste streams although a range of from 30-80 percent
water is estimated. The amount of hazardous waste stream
barged to sea at present is estimated to be 36,000 metric
tons per year (dry basis) from a chloride process plant in
Delaware (Region III).
5^1-.1=J Projection of SIC 28161 Land Destined Hazardous
Wastes to "1977 and J983
The following assumptions were made in predicting the
amounts of hazardous wastes destined for land disposal
arising from the titanium pigment industry in the years 1977
and 1983:
- no new sulfate process plants will be built,
- all growth in this industry will take place in those
states now having Tio2 production,
- all chloride process plants will grow proportionally
at a rate of 3 percent per year,
- the one chloride process plant using ocean barging
will continue to do so, and
- implementation of 1977 and 1983 water effluent
guidelines will not add significant quantities of
hazardous constituents to the solids destined for
land disposal.
Table 5-4 also lists the projections for 1977 and 1983 land
destined hazardous waste streams from the chloride process
for the manufacture of titanium pigment using the
assumptions noted above.
The trend of total amounts of hazardous waste streams and
hazardous constituent on a dry basis in metric tons per year
projected for SIC 28161 are summarized as follows:
»
Period Current 1977 1983
Chromium 350 560 800
constituent
Total waste 151,000 222,000 310,000
stream
5-43
-------
Whereas about two-thirds of the present production of
titanium pigment is manufactured by the sulfate process, it
is expected that, by 1983, two-thirds of this pigment's
production will be made by the chloride process.
Various grades, purities, and surface finishes in several
crystalline forms are sold commercially. The pigment is
also sold mixed with 50 to 70 percent calcium sulfate.
Although the paint industry is the major user, various types
of titanium dioxide are used in paper, inks, fabrics,
rubber, and floor coverings. Total U.S. production in 1972
was 639,700 metric tons (705,300 tons). Domestic ore is
found in New York and Florida, plus lesser amounts in North
Carolina, Virginia, and Idaho. The remaining ore supply is
imported, much of it from Canada and India. Most of the
production of this pigment is captive to the large paint
manufacturers.
5_i.^i3 Other White Qgague Pigments (SIC 28162)
This five-digit SIC subcategory includes the pigments, lead
sulfates, lead carbonates, zinc oxide, antimony oxide, and
lithopone (coprecipitated barium sulfate and zinc sulf ide) .
Although these pigments contain very hazardous constituents,
this industry group yields very small amounts of hazardous
waste that is destined for land disposal. Because of their
value, practically all of the waste streams containing lead,
zinc, and antimony are recovered and either recycled back to
the process or sold to recover metal values.
5_s.iUlil Lead Sulfates iWhite Lead)
Normal lead sulfate (PbSO4) is prepared by reaction of
dilute sulf uric acid with lead acetate solutions. The
product is recovered by filtration. Basic lead sulfate
(PbSOU»PbO) is prepared by several methods:
(a) by flash roasting of the finely divided lead sulf ide;
(b) by reaction of lead, sulfur dioxide, and oxygen and in
special furnaces
(c) by reaction of litharge (PbO) with dilute sulfuric acid
and the product recovered by filtration.
A mass-balanced flow sheet showing the manufacture of basic
lead sulfate by a dry process and the manufacture of normal
lead sulfate by a wet process appears as Figure 5-14. For
those processes involving furnace oxidations, all wastes are
air-borne and are generally recovered by bag filtration
methods and recycled. For the aqueous processess, treatment
of water-borne waste streams with base or sulfide generates
small amounts of insoluble lead salts, which are generally
5-44
-------
Ul
I
*k
en
c
COLL
GASES j
750 LEAD METAL »
DRY PROCESS
BASIC LEAD SULFATE
330 SULFURIC ACID fcT ' '
740 LEAD OXIDE M RE
5 NITRIC OR J
WET PROCESS
NORMAL LEAD SULFATE
6.3 NaOH SCRUBBER LIQUID
)RY
.ECTOR
1 SOLIDS
RNACE »[ PACKING
ACTOR »| FILTER
SCRUBBER
WASTE EFFLUENT
10 NaeS04
, SOLIDS
-J + onYcn V000 Pbso-
1 FILTRATE
SETTLING
, t
SOLID WASTE EFFLUENT
1-2 PbS04 60 WATER
(RECYCLED)
FIGURE 5-14
LEAD SULFATE MANUFACTURE
-------
recycled. The waste lead sludge could be hazardous, and if
the waste was not recycled, disposal on land would require
stringent safeguards to protect surface and ground waters.
The properties of lead sulfate and lead hydroxide are
described in Appendix A.
One company produces the majority of this material in four
states across the country. Plants are relatively small (ca
10 tons per day) and generally occur as part of paint
manufacturing complexes.
5^4.3^2 Lead Carbonate^ Lead Basic garbonate .{also White
Normal lead carbonate is prepared either by reaction of lead
acetate solutions with C(>2 or by reaction of this same
material in solution with ammonium carbonate. The product
is recovered by filtration. Basic lead carbonate is
prepared by partial calcination of the normal material. All
wastes are airborne (in the form of dusts) and are generally
removed from vent gases by bag collection methods and
recycled. Treatment of water-borne wastes from the normal
carbonate manufacture generates small amounts of insoluble
lead salts as solid wastes and these are generally recycled.
The same remarks about lead sulfate production apply to the
lead carbonates. Figure 5-15 show a typical mass-balanced
flow sheet for the manufacture of lead carbonate.
The precipitated lead salt waste resulting from treatment of
wastewater effluents could be hazardous. If the waste was
not recycled, disposal on land would require stringent
safeguards to protect surface and gr oundwaters . The
properties of lead carbonate, basic lead carbonate, and lead
hydroxide are discussed in Appendix A.
5.U.3.3 Zinc Oxide
This material is made by two processes:
(a) those involving oxidation of zinc, and
(b) those involving precipitation from solution followed by
calcination.
In the first case, all solid wastes produced are either in
the form of furnace slags or as dusts. Contacts with
several producers using the first type of processes have
shown that all of the flue dusts are collected by dry
collection methods and sold or reprocessed for their lead
and cadmium content. The various slags produced are also
generally utilized to recover residual zinc. There are no
other wastes involved.
5-46
-------
Ul
I
1331 LEAD
ACETATE —
>I85 WATER-
185 CARBON-
DIOXIDE OR
SODA ASH
EQUIVALENT
REACTOR
FILTER — • DR
FILTRATE
490 ACETIC A)
>lll WATER
116 CONVENT
t
DRY
COLLECTOR
t 1
YER — fcCALCINATOR
975 PbC03-2PbO
CID
_ WASTE
m TREATMEN
r
/
r
100 WATER
REACTOR — ^ FILTER
FILTRATE
1-2 PRODUCT
75 WATER
DRYER
IOOO
-PbC08-2PMDH)j,
PRODUCT
SOLIDWASTE EFFLU
1-2 BASIC LEAD
CARBONATE
(RECYCLED)
EFFLUENT
RGURE 5-15
LEAD CARBONATE MANUFACTURE
-------
In the wet type processes, crude zinc oxide is leached with
caustic soda to remove sulfate and dissolve the lead salts
present. The undissolved zinc oxide is then recovered,
washed, neutralized, and calcined. Treatment of the waste
aqueous caustic streams with barium salts and sulfides
removes sulfate (as BaSO<4) and lead (as PbS) from the
effluent prior to neutralization. Most of the PbS generated
is recovered and sold, and some of the barium sulfate is
also recovered.
Figure 5-16 is a typical mass-balanced flow sheet for the
manufacture of zinc oxide by the thermal oxidation process.
The solid wastes from zinc oxide production are composed of
barium sulfate, lead sulfide, cadmium residues. The lead
and cadmium compounds could be hazardous, but they are
recovered to reclaim heavy metal values. The^properties of
zinc oxide, lead sulfate and cadmium are detailed in
Appendix A.
This chemical is made throughout the United States. Largest
production occurs in Kansas and Pennsylvania. The typical
plant is not easily quantified, since there are a number of
relatively large plants, these latter averaging from 30 to
120 tons per day.
SjJUldL Lithogone
Lithopone is produced by reaction of barium sulfide and zinc
sulfate solutions. The product, a mixture of BaS04 and ZnS,
both of which are insoluble, is recovered by filtration.
There are no hazardous land-destined wastes generated from
this process, and no mass-balanced flow sheet is presented
to avoid disclosure of process details of the one U.S.
manufacturer."
5ii-3i5 Zinc Sulfide
Pure zinc sulfide is also categorized by the U. S. Census as
being a part of the Sic 28162 industry. However, there is
presently no pigment grade zinc sulfide production in the
U.S. This pigment has been completely replaced by titanium
dioxide because of cost and pigment quality.
5.4.3.6 Antimony, Oxide
This material is prepared by an ore extraction process,
wherein the ore is first dissolved in sulfuric acid and the
antimony 1 sulfate formed then converted to product Sb2O3.. A
typical mass-balanced flow sheet appears as Figure 5-17.
The solid wastes generated by the process are of three
types:
5-48
-------
VENT
WATER
1
MILLING
450-834
— ^
'
950-1,100
1
PREdRTATOR
SULFUR i
AIR DIOXIDE
J T
ROASTING
— »
^2 CADMIUM WASTES (RECOVERED
^FOR RECLAMATION OF METAL VALUES)
COAL AIR AIR VENT GASES
1 1 J
SINTERING
GANGUE WASTE
^REDUCTION .^COMBl
^* HEARTH CHAK
2.5 LEAD RESIDUE
(RECOVERED FOR
t
ISTION..^ DRY
USER ^^ COLLECTOR
KXX)
PRODUCT
RECLAIMATION OF
METAL VALUES)
FIGURE 5-16
ZINC OXIDE MANUFACTURE
BY THE THERMAL OXIDATION PROCESS
-------
VENT
NOTE:
ALL SOLID WASTES ARE SOLD OR
REPROCESSED FOR METAL VALUES.
3442
-I ANTIMONY
:!!%As203)
i
i 342 SULFURIC-
ACID
DIGESTION
AND
FILTRATION
I
SOLID WASTE
2379 ORE RESIDUE
I8H2S
PURIFICATION
282 NoOH
FILTRATION — ^ HYDROLYSIS —
WATER
BAG
FILTER
1 DUSTS^ U^ SOLIDS
FILTRATION
^ AND
WASHING
1
W\STE LIQUOR
DRYING
AND
RACKING
^
632 SODIUM SULFATE
30 Sb203
^^~ n
Sb203
PRODUCT
43 As2S3
BY-PRODUCT
(SOLD)
FIGURE 5-17
ANTIMONY OXIDE MANUFACTURE
-------
(a) Ore residues containing acid insoluble inert materials
such as silica. These are non-hazardous.
(b) various product purification sludges. These contain
arsenic compounds; e.g., As2S3 in small amounts.
Arsenic sulfide is a hazardous compound whose chemical,
physical, and biological properties are described in
Appendix A.
(c) A small antimony oxide waste results from solids removed
during waste water treatment. Antimony compounds are
potentially hazardous. The chemical, physical and
biological properties of antimony trioxide are described
in Appendix A.
Of the six plants in the U. S. producing antimony oxide,
only one does not recover their solids wastes for
reclamation of metal values. These plants are located in
four states and are less than 30 years old. The present
total production of antimony oxide in the U. S. is about
8000 metric tons per year.
Liitilil Aggregate of SIC_281 62 Hazardous wastes to Land
Disggsal
Of all the hazardous wastes generated by this five-digit SIC
industry, only one antimony oxide plant1 s waste is not
recovered for reclamation of metal values. These wastes are
listed in Table 5-5 and currently amount to 12 metric tons
of antimony compounds per year and 0. 24 metric tons of
arsenic compounds per year on a dry basis. The total waste
stream (including innocuous ore residue wastes) currently
amounts to 240 metric tons per year on a dry basis. Because
these wastes are mostly filter cake residues, the water
content of the waste streams would probably range from 20 to
40 percent.
5. 4.3.8 Projection of SIC 28162 Land. Destined Hazardous
to J977 and 1983
The one antimony oxide plant accounting for the land-
destined hazardous waste currently being generated by this
industry is stockpiling the solids for possible future
reclamation of metal values. Because specific plans have
not been formulated along these lines, the projection of
future amounts of wastes were based on a three percent per
year growth pattern through 1983. Recommended effluent
limitations guidelines will not add significant quantities
of land-destined hazardous wastes to this industry
subcategory. Table 5-5 also lists the amounts of land-
destined hazardous waste projected for the years 1977 and
1983 provided the one plant generating these wastes does not
recover them to reclaim metal values before this time.
5-51
-------
Table 5-5. Hazardous Wastes Destined for Land Disposal Generated by
Industry Subcategory 28162, Other White Pigments, Currently
and Projected for the Years 1977 and 1983 (metric tons per
year, dry basis)
IV Alabama
X Alaska
IX Arizona
VI Arkansas
IX California
VIII Colorado
I Connecticut
III Delaware
W Florida
!tV Georgia
IX Hawaii
X Idaho
V Illinois
V Indiana
VII Iowa
VII Kansas
IV Kentucky
VI Louisiana
I Maine
III Maryland
I Massachusetts
V Michigan
V Minnesota
IV Mississippi
VII Missouri
VIII Montana
VII Nebraska
IX Nevada
I New Hampshire
II New Jersey
VI New Mexico
II New York
IV North Carolina
VIII North Dakota
V Ohio
VI Oklahoma
X Oregon
III Pennsylvania
I Rhode Island
IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII Utah
I Vermont
III Virginia
X Washington
III West Virginia
V Wisconsin
VIII Wyoming
TOTAL
Region I
II
III
IV
V
VI
VII
VIII
IX
X
Current
Total
Hazardous
Waste
24C
240
240
Antimony
Compounds
12
12
12
Arsenic
Compounds
0 24
0.24
0.24
1977
Total
Hazardous
Waste
270
*
270
270
Antimony
Compounds
'14
14
14
Arsenic
Compounds
/
Total
Hazardous
Waste
0.28 ; 320
!
0.28
320
0.28 320
1983
Antimony
Compounds
16
16
16
Arsenic
Waste
0.34
0.34
0.34
5-52
-------
5..U...U Qhromg Colons and Other Inorganic Pigments
This industry subcategory includes two broad groupings of
pigments; Chrome Colors and Other Inorganic Pigments. The
chrome colors include chrome yellows and oranges, molybdate
chrome orange, zinc yellow,, anhydrous and hydrated chrome
oxide greens, chrome green and iron blues (not a chrome
pigment, but usually produced in chrome pigment complexes) .
The other inorganic pigments include barium sulfate, cadmium
colors, colored lead pigments,, cobalt colors, iron dxide
pigments, carbon black, and mercury sulfide.
The manufacture of all pigments in the chrome color group
generates hazardous wastes destined for land disposal. Only
cadmium colors and mercury sulfide manufacture of the other
inorganic pigment group contributes hazardous wastes
destined for land.
SiiLt^ii Chrome Yellows and Oranges (Lead Chr ornate)
Chrome yellow is produced by reaction of sodium dichromate
with a soluble lead salt. The product is recovered by
filtration. Treatment of wastewaters generates a solid
waste containing lead salts and chromium hydroxide. The
properties of chromium hydroxide, lead hydroxide, and lead
chromate are given in Appendix A«
A typical mass-balanced flow chart for the manufacture of
lead chromate is shown in Figure 5-18. As indicated on the
flow chart, the amounts and types of reactants and wastes
will differ depending on the color being produced.
S.j.Ujj.UjjZ Molybdate Orange {Lead Molybdate Lead Chromatey
Molybdate orange is made by dissolving molybdic oxide in
aqueous sodium hydroxide prior to the addition of sodium
chromate. This solution is mixed and reacted with a
solution of lead oxide in nitric acid. The reacting
solution is then fed to a holding tank wherein the reaction
goes to completion. The resulting suspension is filtered
and the recovered product is washed, dried, milled and
packaged.
The waste problems involved in the manufacture of molybdate
orange are essentially the same as those for chrome yellow.
Appendix A describes the properties of these waste
constituents.
5-53
-------
714
LEAD OXIDE
WATER
DISSOLVING
403 NITRIC AOD-
(OR ACETIC ACID)
or
I
UT
263 50% NoOH-
490 SODIUM
DICHROMATE
DISSOLVING
MIXING
AND
DEVELOPMENT
H
IRLTRATION
AND
I WASHING
DRYING,
MILUNG
AND
PACKAGING
JOOO Pt»CrQ»
PRODUCT
• VALUES WILL DIFFER DUE TO DIFFERENT
REACTANTS USED TO MAKE DIFFERENT
SHADES OF CHROME YELLOW
I
VKftSTE
TREATMENT
3OPbCrQ»
IO.4 CrtOH),
26.1 CoSQj-ZHjO
2,5
EFFLUENT
544 NoN03
14.3
1.7
OR Co(Ac)2)
RGURE 5-18
CHROME YELLOW MANUFACTURE
-------
Figure 5-19 shows a typical mass-balanced flow sheet for the
manufacture of molybdate orange.
isl.di.i3 Zinc. Yellow
Zinc yellow is a hydrated tine potassium chrornate
(UZno«K20»t»cro3«3H2O). It is usually made by the reaction
of zinc oxide, hydrochloric acid* sodium dichromate and
potassium chloride to give a zinc yellow slurry. This
slurry is then filtered, washed, dried, milled and then
packaged for sale. (See Figure 5-20)
Treatment of the waterborne wastes from the process
generages insoluble zinc salts, chromium hydroxide, and
unrecovered zinc yellow, all of which require careful
disposal. The properties of zinc yellow, zinc oxide and
chromic hydroxide are described in Appendix A.
Siib.^ chrome. Green.
chrome green is produced (as shown in Figure 5-21) by miking
a slurry of chrome yellow and iron blue. The slurry is
washed, filtered, dried, ground, blended and packaged for
sale. The waste problems are similar to those encountered
tor the two individual constituent pigments, which become
wastes to land disposal as the suspended pigment particles
(chrome green) are removed in wastewater treatment* These
compounds are described in Appendix A*
SilaJiiS £hr.ome Oxide Green JAnhvdrous and Hvdratedl
Chrome oxide green is produced by two methods. The first,
(for the anhydrous product) thermally reduces sodium
dichromate with either sulfur or carbon or both* The
recovered oxide material is then washed free of other
compounds, dried, and packaged. The washwaters require
treatment and this generates sludges of chromium compounds
which require careful disposal. Figure 5-22 is a mass-
balanced flow sheet for its manufacture. Appendix A
describes the properties of chromic oxide and chromium
hydroxide.
The second process produces a hydrated product. A mixture
of boric acid and sodium dichromate is heated, the product
is separated by filtration, washed, dried, and packaged.
Treatment of wastewaters is required and this is expected to
generate some chromium containing solids requiring disposal.
Figure 5-23 describes this process, and the properties of
the hazardous constituents are described in Appendix A.
5-55
-------
235 SODIUM
CHROMATE
212
MOLYBDC I
OXIDE »
236 50% to
CAUSTIC
SODA
644
LEAD
OXIDE to
NITRIC
ACID
• IMPURITY COM
OXIDE RAW MA
WftltK
DISSOLVER
— nSe -| 1T-5r
I-*
MIYFB —» HOLDING
MIXER - TANK
r»
DISSOLVE
1 1
9.9 ^Q» »
arsOj — » CHEMICAI
l2Ca£OHlp to.
TOJWED IN MOLYBO/C _ SLUDGE
TEWAi.
VENT
RLTRATION SfTIS WOO
— • AND — ^ hsf^ » PfaCrQ»-Pr
WASHING PACKAGING "^^^
|
>_ TREATMENT
^
SEPARATION
SOUPS TU LANDFILL
\2S. Si
20
[Q Cr(OH)s
ZM
ir.5
5O2
VCTER
BSURE 5-®
MOLYBDATE ORANGE MANUFACTURE
-------
404 ZnO
185 HCI
218 KCI
765
REACTION
TANK
DEWATER,
CENTRIFUGE
AND
WASH
-4
WATER
VAPOR
VENT
1
DRYING,
MILLING
AND
PACKAGING
m
en
TREATMENT
SOLID RESIDUE
20 ZINC YELLOW
24 ZnO
48 Cr(OH)3
LIQUID EFFLUENT
44 KCI
131 NdgSQ,
433 NaCI
WATER
FIGURE 5-20
ZINC YELLOW MANUFACTURE
-------
WBCTtH
V8ETEK
TTSLEAQi
N£IKdHE>
JSGSQBtQM.
•-USE.
E
GEE-
SOLHBE:
i
Zfi5 WOKBLUE-
WKFER
E^ACTEJBI
LKKCB
4QO
SHffOE OF GREEK
OB5:
RESLUf^Y
1
SHADE
RUER
DRY
5OSKMEGREEW PIGMEFifT
(AS SUS>ENDED SDUDS IN WATER)
GFQNO,
BL£NO
AND
PACK
tOOO
PRODUCT
5-21
N4ANUFACTURE
-------
i
01
vo
63 CO^.CO SO
WATER
WATER
VENT
DiCHROMATE ^j
WATER »
198 SULFUR »
22 WHEAT »
BLENDER
— »
KILN
— »
SLURRY
TANK
— ^
FILTER
— •»
DRYER
— »
GRIND,
SCREEN
AND
PACKAGE
FLOUR 1
33 S02
666
TREATMENT
SOLID RESIDUE LIQUID EFFLUENT
22 Cr(OH)3 993 Na2S04
PRCXXJCT
FIGURE 5-22
ANHYDROUS CHROMIC OXIDE PIGMENT MANUFACTURE
-------
I
a>
o
258 0, WATER WATER VENT
t i 1 t
1695 SODIUM — \
DICHROMATE ^ 01 \tooy
BLENDER — *• OVEN — *> ™£ — »• WASH — »• FIL
1630 BORIC ACID — ^
SOLID WASTETO LANDFILL
10 Cr203- 2H20
646 SULFURIC ACID
BORIC ACID
BORIC ACID RFCOVCRY «
BFrvri F KtUUVtKT ^
RECYCLE UN|j
936 Na,S04l [^
300 H3B03>xnU^
95 NOgCr^y^HgOf ^
61 S02 * TREATMENT
76 NaOH »
SOUP LIQUID
RESIDUE EFFLUENT
££&
PER -^* DRYER ^ ^wn ^Cr2o3 • 2H2o
PACKAGE PROOUCT
66Cr(OH)3 1117
300
FIGURE 5-23
HYDRATED CHROMIC OXIDE MANUFACTURE
-------
5.4. U.6 Jron Slues
Iron blues are produced by the reaction of sodium ferro-
cyanide, ferrous sulfate, and ammonium sulfate in solution.
The product is separated by filtration, dried, and packaged
as shown in Figure 5-24.
The water-borne wastes from this process contain a
considerable amount of suspended product which is settled
out prior to discharge. This material is then recovered as
a solid waste which should have special handling due to its
cyanide content. The properties of ferric ferrocyanides are
discussed in Appendix A.
Chrome pigments are made in ten major locations in seven
states. Average production is 17 tons per day. In five of
these complexes, iron blues are also produced at an average
rate of about three tons per day. These latter facilities
are somewhat older, ranging in age from 20 to 60 years.
5±!±±£.±2 !§£iiJHJ Sulfate .{White Extender Pigment\_
Barium sulfate is produced by the reaction of barium sulfide
solution with sodium sulfate as shown in Figure 5-25. It
may be noted here that the product is made entirely in
plants producing barium carbonate-where the sulfide is
produced as an intermediate product.
In the case of barium sulfate production, the sodium sulfide
is generally recovered as a salable co-product. In this
case, wastes are entirely water-borne and are generally
treated by aeration to oxidize soluble sulfides. There are
no hazardous wastes destined for land disposal.
In one case, as shown on Figure 5-25, the soluble sulfide
waste is treated by precipitating insoluble ferrous sulfide.
This solid waste is considered to be non-hazardous because
of its low solubility.
5.U.U.8 Cadmium Pigments
Cadmium pigments (red, orange, yellow and cadmium lithopone)
are all generally produced by the method described on
Figure 5-26. The amounts and types of reactants are varied
to produce the desired color. Cadmium red is essentially
cadmium selenide; the yellow is a mixed cadmium-zinc
sulfide, and the orange is somewhere in between. Cadmium
lithopone is a mixed barium sulfate-cadmium sulfide co-
precipitate made by using barium sulfide to precipitate the
product instead of sodium sulfide used for the other cadmium
colors.
5-61
-------
l
-------
WATER
Ol
609 t 1
SODIUM SULFATE—**
3300 WATER •» REACTOR P
726 BARYTES • •>
BAKIUM SUU-IOt * - "J
651
FILTRATE \pJ
(335 No^S) 1 1
FeSo4 » SETTLING
SOLIDAWUSTE EFFLUENT
377 FeS 3300 WATER
609 NOgSQ,
« nnviwc — ^I00° BoSOx
-M DRYING h -^PRODUCT
FIGURE 5-25
BARIUM SULFATE MANUFACTURE
-------
VENT
0-512
BARIUM SULFIDE
(CADMIUM LITHOPONE)
0-547
SODIUM SULFIDE
(CADMIUM YELUOWS)
1
DRY
COLLECTOR
WATER
0-542 ZINC SULFATE
(CADMIUM YELLOWS)
WATER -
0-552 CADMIUM SULFATE-
10 SELENIUM (CADMIUM -
REDS)
DISSOLVER
i
GAS T FINES
REACTOR
T FINES
FILTRATION
AND
WASHING
DRYER
CALCINATION
Ul
I
-------
In plants producing only cadmium colors, the solid waste
generated by wastewater treatment can1 be (and is) recycled
back to the process. This cannot be done at large chrome
pigment complexes where cadmium colors are made and a single
large treatment facility exists for the entire complex.
The other solid waste stream destined for land disposal
contains slightly contaminated dry chemical bags and in-
plant product transfer containers (non-metallic) .
5. 4 ..4. 9 Colored Lead Pigments 4 Litharge (PbO) and Red Lead
A mixture of powdered lead and partially oxidized powdered
lead is melted and oxidized with air in a furnace to form
lead monoxide directly. This is discharged by a water
cooled screw conveyor to the milling operation. The product
is discharged through a bag collector for storage, use, sale
or further processing into a superfine grade. The only
process wastes are dusts, which are collected by bag
filtration and recycled. A process flow sheet is given in
Figure 5-27. Red lead (Pb3O4) is produced by a similar
process in which lead is oxidized to litharge in air, and
further oxidized by heating to approximately 700°F. There
are no wastes from either process.
5.4. U. 10 Cobalt Pigments
Cobalt black (cobaltic oxide, Co203) is produced by the
reaction shown in Figure 5-28 and is used primarily as an
intermediate in the production of other cobalt compounds
(These are discussed in the section on SIC 2819 chemicals.)
Wastes are small and cobalt containing values are generally
recycled because of the cost. Cobalt oxides have a fairly
low level of toxicity, and their properties are described in
Appendix A.
Cobalt blues are generally not used in ordinary paints
because they are very expensive. One is a compound oxide of
cobalt (30 to 35% Co3O4(Co2O3 * CoO) ) and alumina (70 to 65%
A12O3) ; another is a powdered glass colored by cobalt oxide.
5.4.1.11 Iron Oxide Pigments
Iron oxide pigments are generally produced by the two
methods described in Figure 5-29.
(a) Ferrous sulfate is calcined in air to the oxide which is
then recovered and packaged for sale. All of the wastes
arise from vent gas scrubbing and all are innocuous
5-65
-------
en
ov
O-,
950 PIG LEAD-
VENT
I
DRY
COLLECTOR
AIR
n
MILL
ROTARY
nviniTiKifi
UAIUI^IIWJ
FURNACE
COOLER
MILL
STORAGE
IOOG
-POWER
PRODUCT
SOUP WASTE,
I PbO,Pbs04
RECYCLED
FIGURE 5-27
LEAD MONOXIDE MANUFACTURE
-------
Ul
I
a\
VENT
1158 NITROGEN
EXCESS AIR
t
BAG
FILTER
GASES
SOLIDS
711 COBALT POWDER
F POWDER »|
1447 AIR m\
FURNACE
PACKAGING
PRODUCT
(COBALT BLACK)
WASTE RECYCLE
FIGURE 5-28
COBALTIC OXIDE MANUFACTURE
-------
UT
I
-------
sulfates (i.e. Na2SO4 or CaS04). There are no hazardous
wastes destined for land disposal.
(b) Ferrous sulfate is reacted with caustic in solution.
Iron hydroxide is recovered by filtration and calcined
to the oxide. Here, all wastes are also non-hazardous.
5.4.4..12 Carbon Black Pigments
Carbon black pigments are produced by the two methods shown
in Figure 5-30. In the first, coal tar distillate is burned
in air and the carbon formed is collected by bag filtration.
In the second, acetylene is thermally decomposed to carbon
and hydrogen. The carbom is recovered as the product by
both processes, and there are no hazardous wastes associated
with either process.
5.4.4.13 Mercuric Sulfide
This pigment is generally made by one of the two processes
shown in Figure 5-31. The first involves the reaction of
hydrogen sulfide gas with a solution of mercuric chloride to
precipitate the product, black mercuric sulfide. This
process requires wastewater treatment which generates about
1.5 kilograms of mercuric oxide solid waste per metric ton
of product.
The other process is a direct reaction of mercury metal with
sulfur to form the black mercuric oxide product. No water
in involved. Further sublimation steps on the black product
produces red mercuric sulfide. This process does not
generate land-destined hazardous wastes.
5.4.1.14 Ultramarine Pigment
Ultramarine is a blue, complex sodium aluminum silicate and
sulfide, made by heating together sodium carbonate, kaolin,
charcoal, quartz, sulfur, sodium sulfate, and resin. It is
absolutely essential that iron not be present in .all raw
materials, as it appreciably dulls the color. The melt is
cooled, ground, washed free of water soluble salts, and
heated with more sulfur until a blue color develops. A
darker blue may be produced by substituting sodium sulfate
for sodium carbonate.
The manufacture of this product is illustrated in
Figure 5-32. Only waterborne wastes of sodium salts are
generated in the production of ultramarine pigment. No
wastes are disposed of on land, nor are any hazardous wastes
generated by treatment of air or water wastes.
5-69
-------
VENT
AIR
1100 COAL TAR —
DISTILLATE(ASSUME
90% CONTENT)
LAMPBLACK
BURNER
1
COLLECTION
CHAMBER
BAG
FILTER
1
— J PACKAGING
JOOO CARBON
PRODUCT
1105 ACETYLENE-
ACETYLENE BLACK
FURNACE
GAS FILTER
I
PACKAGING
FIGURE 5-30
CARBON BLACK MANUFACTURE
• 105 HYDROGEN PRODUCT
1000 CARBON PRODUCT
-------
146 H2S GAS
50LUTION)— -»
REACTOR
Pll TPR
riL.1 en
1000 MERCURIC SULFDE
BLACK PRODUCT
E
313 HCI
TREATMENT
*
SOLID WASTE
1.5 HgO
VHOTER
EFFLUENT
862 MERCURY
138 SULFUR -
REACTOR
1
1
t
SUBLIMATION
-^1000 MERCURIC SULRDE BLACK PRODUCT
RESUBLIMATION
^lOOO MERCURIC SULFIDE
RED PRODUCT(ALTERNATE)
FIGURE 5-31
MERCURIC SULFIDE MANUFACTURE
-------
940 SODIUM
CARBONATE " »
AND SULFATE
457 KAOLIN* »
1-10 CHARCOAL »
1 -10 RESIN »
222 QUARTZ »
(ji
1 33.4 SULFUR »
NJ
REACTOR
VENT:
WATER
200 S02
115 C02
t
— * COOLING — P« GRIN
WATER
f
DING — »• WASHING —
I
WATER-BORNE WASTES
10-30 SOLUBLE SALTS
(SODIUM SALT,SULFATES,
r AoartMATCc ',
33 SULFUR
I
•^ FURNACE
1000 ULTRAMARINE
'BLUE PRODUCT
• KAOLIN: 245 s/o2, 2/2 /w2CL/DRY BAS/S;
FIGURE 5-32
ULTRAMARINE BLUE MANUFACTURE
-------
liiLdiilJSJ Aggregate of SIC_28J.63 Hazardous Wastes to Land
Disposal
The amounts of the constituents of the several waste streams
containing hazardous materials in sufficient quantities to
be hazardous in total are shown for the typical operation in
the flow diagrams in the preceding sections. The values
given are relative to the product rate, that is, they are
numerically equivalent to either kilograms per metric ton of
product or pounds per 1000 pounds of product. The hazardous
waste streams from this industrial subcategory come
primarily from the manufacture of chrome pigments and iron
blues, with lesser amounts accumulative from the manufacture
of cadmium and mercury colors. The hazardous constituents
in these waste streams are chromium compounds, lead
compounds, cyanide compounds, zinc compounds, cadmium
compounds, and mercury compounds. Practically all of these
waste streams are the result of wastewater treatment to
remove the undesirable constituents from the plants1
effluent. The water content of these waste streams can
range from 30-60 percent depending on whether they are
filter cakes or sludges.
Table 5-6 lists the aggregate hazardous waste streams of
SIC 28163 on a state-by-state, regional and total U. S.
basis and the amounts of the various hazardous constituent
materials which is estimated to be currently valid. The
local situations in each state when they deviate from the
"typical" are taken into account insofar as is possible.
The data of this table are comprised of the most reliable
and more consistent entries from several sources:
(a) calculated from manufacturers' data that has been found
to be consistent and hence reliable
(b) estimated from fragmentary or equivocal manufacturer's
data
(c) estimated from waste disposal contractors's data, and
(d) our own estimates.
The hazardous constituents in all cases are given in terms
of the compounds shown on the flow diagrams.
The largest amount of hazardous constituents arise from the
chrome pigments and iron blues sector of the industry. This
amounts to about 4300 metric tons per year on a dry basis
which is about 54 percent of the total dry basis waste
stream (approximately 8000 metric tons per year). The other
colored pigments part of the industry contributes only 54
metric tons per year of hazardous constituents or less than
1 percent of the total for the industry. Over 90 percent
(on a dry basis) of the total hazardous waste streams
5-73
-------
Table 5-6. Hazardous Wastes Destined for Land Disposal Currently Generated
by Industry Subcdtegory 28163, Chrome Colors and Other figments
(metric tons per year, dry basts)
Jtf Al.1b.iru
V" "M.iJi'k.i
}X nrlznn.i
VT Arkaltaas
IX" I'.ili Ten nl ;i
VIII rolor.ldc
1 C'anm'cl i cliC
III |ii.]awan>
tV I-1 lor Id.i
IV i:»orni..i
IX I1 wall
X J.l.ihu
V 111 i.tioi :
V 1 iidi .'in.i
vTt "I ,VM-~
Vii K.iiisaH
TV ~ I i~iiTif. •!:"'•"•
V? " 1 >ul:.a';,i- i "
i Mi IMP
ifl CiryVm.'
1 N iituaclmsud j
V Michiil.ll.
V viimi iiiii-i
IV v ! :'•! i ;;:' i ' >r 1
VII l-l'isouri " " "
VllT 11. Mil. lll.'l
VII" " . •CrTi»T: , " '
IX K^v'.ul.i
I *. •-•/ fi.inn -'hn c
11 f, -.1 .'en: -v
VI N.'W fioxi :O
11 H.'W Vol-k
IV iv.n.'tll L'.irb.! t:vl
V Ohio
VI li?lnhonui
X itrcqon
n_l__J'-;nn;_i/Jv.'JUH
IV ;- 'iit-h Caral inn
VIII !' -uth I\ .ota
TV '1 ••nnpssi'i:
VI '1 -xas
VI,f ] I'1, .ill
] V -rmunf
II) Virni.'ii.i
X I.' i:*h i '.'.<:'. -)ll
III v..-"!t Virtiin.la
V V. i ficx'iii: J u
VI fi V -rainu" '" ' ~
TOTAL
Rca ion I
.... ... it . ..
Ill
IV
\:
VI
V.U
VIII
IX "' •
X
Chrome Plqmenr! 4 Iron hlues
1otal
Hcfjardous
Wusles
2'0
740
. 1,800
.1, .100
2AO
-110 —
1.500
8,000
c yon
2.000
21(J
260
Clirumium
Confounds
120
^~ T|o
r~
070
760
20
I'O
' "130
2,500
1 630 '
77JJ
120
2q
Innd
CorrfxHJndi
98
200
530
M. „
16-
1/tb
1 400
'SO
340
9Q
16
•
Zinc
150
•
130
12
290
I 12
'50
— • --- — . --
Cyanide
Coitipotihds
to
75
7,5
?_..
T3o
85
7 5
Order Colored Pigments
told!
Hazardous
Wastes
?4*
0.3J
.... .3,B2/i; .
-
3 oyo*
3,024*
24*
Cadmium
Compounds
IB
. 0.22 .
36
54
36
fa
Mercury
Compounds
0.3
*
0.3
0.3
Zinc
CoMpoUndi
b.ls
0.06
0.3
0,5
0.36
0.16
Total
28163
Mdtardous
Wastes
2lO
740
1.800
3,400
240
no
1.500
. 8,000 .
5.200
2 000
210
2AO
*Does not ri1 Fleet tHu actual numerical Jotal since it fnclud-ss compounds
From the other category (i.e., Chrome Pigments and Iron Bluest
5-74
-------
destined for land disposal are currently generated in EPA
Regions II and III.
LtiLJLs-16 ProjestigQ oj SIC_28J6,3_ flazardpjis Haste.8 to 1977
J983
The chrome colors and related pigments industry is a stable
and well-developed industry that is expected to grow at
about the same rate as the whole economy. The impact of air
and water regulations will to bring more of the hazardous
wastes generated by these processes to land disposal.
Recycle or reuse of wastes is now practiced wherever
possible. Purity and quality of product is paramount in
this industry, so recycling of contaminated materials is
generally not possible.
The individual growth factors used in the forward projection
of the SIC 28163 hazardous wastes include:
(a) an assumed 3 percent per year normal growth of the
industry, and
(b) the additional solid wastes generated by recommended
1977 and 1983 treatment technology to improve effluent
water quality which is expected to be significant in the
chrome pigments industry.
Tables 5-7 and 5-8 give the projected amounts of wastes in
the same format as was presented in Table 5-6. State-by-
state, regional and total U. S. aggregates are given for the
various waste streams for the total hazardous waste to land
disposal.
The total amounts of hazardous waste streams (on a dry
basis) in metric tons per year projected for SIC 28163 are
summarized as follows:
Current
Total Hazardous 1300
Constituents
Total Hazardous 8000 9100 11,000
Waste Stream
5.4.5 Summary, of Waste Streams Destined for Land Disposal
From SIC 2816
The total amounts of hazardous waste destined for land
disposal from the three five-digit SIC industry
subcategories are summarized as follows (metric tons per
year, dry basis) :
5-75
-------
Table 5-7. Hazardous Wastes Destined for Land Disposal Expected to be Generated
ih 1977 by Industry Subcated,ory 28163, Chrome Colors and Other
Pigments, (metric tons per year, dry basis)
IV Al.iluinu
5T Ai.-isk.'i
IX Alrl.:
IV Fieri 1.1.1
TV .loon, i.i
IX ~" Uau-HY ~ ~
X~ liUilicT •"
v iirriuns
V Indian.'
Vi f luwa
«Tt IMtv;.i:i
IV Kcnl'i:.-! \>
VI Loui;; i.iii.i
f ruiii'iu
til ' Mai-vLin.!
I '.{,i!-.«.-u-lm:u-H.s
VT .flciilc: in
V Mip.Mt-iiutia
IV Mlll.-ii -1:1 J tv.- i
VI J y.lanoin i
VII "i Motr..'m.,
VII '.'fib-.i:;' :l
IX Ncv.itl.i
1 Now '! v-.-.j^FiLj-o
It '.'PW ,Il 1 Hl-V
VI Nc'W M.:.-. ic-li
II Mew ¥,;•'<
IV .•'ion.li '.'jrolinn
VIII Wtli rnkora
VI uia.iho.-.i
X Ore1 :c:i
111 l'nn:uv . uarrj .T
I 'Shcx'.i; if!(,ini
IV SouLh f.irC'1 !n<\
VIII .ic-utlT ' .iTTol.. 1
IV JV!ii:c";. ,-p
V! I'ny.i'.n
VJM 'iL.-'h
J \'i:\'l O'i<-
111 '/iu ir: i.i
X .-isiiiri '. yn
1'i 1 , •::• ^ i - i r: n
V h'J K'-O:" in
VIII Mviiniii'-
¥OTAJ.
Recrion 1
11
.t J I
IV
V
vt
VII
VIII
IX
X
fotnl
Hdzdrrlous
W,isl,.s
2-'-U
r" 8/0
1.71X1
3 Rim
Mi
-. -.ua
1.700
R,7()C:
5.500
2.700
24 0
300
_
Cilronl
Cliloinlum
u'o
560
.. UUQQ- .
B'X)
24. ..
.. . 122...
230
... 1.QQQ-....
1,900
720
!4Q
24
i ^lyniurifs ^t In
U-iid
^ IIP
230
.— -fell).. .
J
530
. " ";;:ii"z
. -_ j
.
i
160 {
.... ....
1 700
... _ ...^
-
--.,-»•-
'no '"
18
in Bluer.
/in,:
Conifjciunds
.._
1/0 J
"^
iw
.
u
.. _. ... ..
1
..
.323
(60
170
CynnMo
CoMlpolliKls
11
84
8
50
1.30
95
50
8
Hti^ulrJulll
Wmtes
2?'
0.35'
"" 3,800-
3,800*
3,800-
OfliotColu
Cailmlutn
Comjiounns
20.
0.2S
40
.
60
40
20
11
'
(;(, piolr](,.hll
Mercuty
Compoiin<)'i
.
0.34
••
0.34
0.34
Ztnc
CompouikJs
~ - —
..... ......
.
.....
— B;IT —
0.07
0.35
0.6
0.4
o!2
total
28)63
Hazurdous
Wasltii
*
1 ~ " •"
...
240
BTff"
'
1
2.000
3,800
300
lid
1,700
9,100
5,800
2.700
240
300
s not roflecl Hit,
t the .'ther cat'-
trynl num-jiicut totyl iince If includes cortlpounds
i) {[.*:., Onom-- Piymentj tind Iron Bk'es).
5-76
-------
Table 5-8. Hazardous Wastes Destined for Land Disposal Expected to be
Generated in 1983 by Industry Subcategory 28163, Chrome
Colors and Other Pigments, (metric tons per year, dry basis)
IV Alabama
X Alaska
IX Arizona
VI Arkansas
ix California
VIII Colorado
I Connecticut
III Delaware
W Florida
IV Georqia
IX Hawaii.
X Idaho
V Illinois
V Indiana
VII Iowa
VII Kansas
IV Kentucky
VI IxmisLina
I Maine
III Maryland
I Massachusetts
V Mich.iqan
V Minnesota
IV1 Mississippi
VII Missouri
VIII Montana
VII KRljr.iskn
IX Nevada
I New JJamnshire
II Now Jersey
VI New 1'icxico
II New York
IV North Carolina
VIII tlorth Dakota
V Ohio
VI Oklahoma
X Oregon
III Pennsylvania
I RhmlR I island
IV South Carolina
VIII south nakota
IV Tennessee
VI Texas
VIII tif.th
I Vermont
III Virginia
X Waslunnt on
III Wi-iir Virni.iii.1
V uiisi-oiiuin
VTM Uvoinimi
TOTAL
Kcoiim 1
11"
1 11
IV
V
VI
VI I
vru
IX
X
Chrome Pigments & Iron Blues
Total
Hazardous
Wastes
290
1.000
2.400
4,500
340
ISO
2.000
11,000
6,900
3,100
290
360
Chromium
Compounds
170
660
1,226
1.070
28
150
250
2,500
.i^3QO_.
1.100 _..
170
28
Lead
Compounds
130
260
750
630
21
m
2.000
I.3QO
470
130
21
Zinc
Compounds
200
!70 "
16
390
190
200
Cyanide
Compounds
'
n
100
10
.. .. 59
ISO
'__ no"
10
Other Colored Pigments
Total
Hazardous
Wastes
32-
0.42'
4.050'
4.100'
uar.._
32-
Cadmium
Cornpounds
24
0.3
48
72
24
Mercury
Compounds
0.4
0.4
0.4
Zinc
Compounds
0.2
.._ 0.08
__ 0.4
0.7
n i
n •>
Total
28163
Hazardous
Wastes
290
1.006
2.400
4.500
360
150
2.000
11.000
f. oon
.1 100
790
3AO
*Does not reflect the acrual numerical total lince It includes compounds
from the othet category (i.e., Chrome Pigments and Iron Blues).
5-77
-------
current .1
SIC 28161 Haz. Const. 350 560 800
Total Stream 151,000 222,000 310,000
SIC 2H162 Haz. Const. 12 1U 16
Total Stream 240 270 320
SIC 28163 Haz. Const. U300 5200 6100
Total Stream 8000 9100 11,000
It is obvious that SIC 28163 (Chrome Colors and Other
Inorganic figments) generates the most hazardous
constituents while Sic 28161 (Titanium Dioxide Pigments)
generates the largest amount of total waste stream
containing hazardous constituents.
5^5 Other Industrial Inorganic Chemicals (Sic 28191
This category of the industrial inorganic chemicals
manufacturing industries covers a large number of
miscellaneous inorganic chemicals broken down into the
following subcategories:
sulfuric acid (SIC 28193)
other inorganic acids (SIC 28194)
aluminum oxide (SIC 28195)
other aluminum compounds (SIC 28196)
potassium and sodium compounds (SIC 28197)
chemical catalytic preparations (Sic 28198)
other inorganic chemicals, not elsewhere classified
(SIC 28199)
In this section, the discussion is limited to those SIC 2819
chemicals having a volume of manufacture that is of
significant economic importance and wastes sufficient to
merit consideration* Product value below one million
dollars annually was considered insignificant for this
purpose. Commodities in this volume category Were judged
not to produce significant quantities of waste since their
manufacturing volume is so low. This does not preclude a
single manufacturer at a single location in one of these low
volume commodities from having a hazardous waste problem.
However none of this sort were found.
L-,5^.1 Sulfuric Acid 1SIC_281931_
In the contact process, which is the principal process for
manufacturing sulfuric acid, purified and dry sulfur dioxide
is mixed with air, heated, and introduced into a reactor
containing a platinum or vanadium pentoxide catalyst. The
resulting gas mixture is cooled and sent to a series of
internally-cooled towers where the sulfur trioxide is
5-78
-------
absorbed by oleum (acid plus excess sulfur trioxide) of
successively decreasing sulfur trioxide concentrations.
Acid less than 97 percent concentration cannot be used to
absorb sulfur trioxide because of mist formation and
resulting sulfur trioxide losses. Various products ranging
in acidic strength from battery acid (33.5 percent H2SO4) to
70 percent oleum (70 percent free SO3 in H2SOU) are
produced. The only wastes are those generated by alkaline
scrubbing of tail gases and neutralization of product leaks
and spills. The wastes generated by these operations are
either waterborne or solid (gypsum) , and are not hazardous.
The following diagram for the principal process (Contact
Process]) is given in Figure 5-33, and that of the outmoded
(but still used) Chamber Process in Figure 5-34. SIC 281
production of sulfuric acid results from burning of sulfur
in the above processes. By-product sulfuric acid from other
industries is also produced. Spent acid from the oil
refining industry is burned with fuel in a modified contact
process to reclaim the acid. The non-ferrous metal industry
produces by-product sulfuric acid from the sulfur dioxide
recovered in ore roasting processes.
5_-.5_i2 other Inorganic Acids (SIC 2819U)
5iHsJ2.il Hydrochloric Acid
Hydrochloric acid is produced either as a by-product of
organic chlorinations or by direct synthesis, in the
reaction of chlorine with hydrogen. The former process is
not in SIC 281. In the latter process, hydrogen and
chlorine gases are reacted in a vertical burner. The
product hydrogen chloride is cooled and then absorbed in
water. Exhaust gases are scrubbed and acid values are
recycled. End products may include strong acid (22°Be) from
the cooler, weak acid (18 °Be) from the absorber column, a
mixture of these (20°Be), or anhydrous HC1. The anhydrous
acid may be prepared by stripping gaseous HCl from strong
acid. The condensate and column bottoms may then be
recycled to the process. All wastes originate from wet
scrubbing of tail gases to remove acidic gases and are
waterborne. They consist of alkali metal or alkali earth
chlorides. No hazardous wastes are generated by these
processes. The major process is given in Figure 5-35, and
two minor (and outmoded) processes that are still practiced
in a few locations are given in Figures 5-36 and 5-37. Note
that the concentrations of commercially standard
hydrochloric acid solutions are given in the flow diagrams
in terms of degrees Baume (°Be). These are measurements of
density on a hydrometer scale and are standard terminology
in this industry.
5-79
-------
VENT
2J8I NITROGEN
\WCTER-
i
SCRUBBER
SOHgSO* AND
IN DILUTE SOLUTION
2850 AIR
(699 OjJ
3VWTER
Ui
I
CO
o
340 SULFUR-
MELTTNG
BURNING
FILTER
CONVERTER
COOLER
!Wftl
AtiSOd&R
— ^
COOLER
t
»IOOO
98% PRODUCT
RGURE 5-33
SULFUR1C ACtD MANUTOCTURE
BY THE CONTACT PROCESS
-------
w/rr&e
M-q \
3+0 S
in
00
. P/Z
('<*>%
-ZOO
S-34
SULFUFUC ACID
BY THE CHAU&ZZ.
-------
in
oo
I
1
I
i ACID |
I
^|
I I
\
HYDROCHLORIC ACID MANUFACTURE
-------
GAS
Ol
I
00
U)
i/T
,Sfc/£/T«2/C
/?
<<*5-? /^S-CU)
*«s*/7~
_L_ i
1
1
f
AC/O(*
HYDROCHLORIC ACID MANUFACTURE.
BY ~TH£ SALT-5ULRJ&C ACID PROCESS
-------
276
ff&KTT&Z
UT
r
00
HCl
I
HYDROCHLORIC ACID
BY' THE HARGHEAVES PROCESS
-------
5iS .2.2 Boric Acid
This product is made by acidulation of borax. From the
acidulator, the boric acid solution is fed to a vacuum
crystallizer, where boric acid crystals are formed, and then
to a filter. The sodium sulfate is removed in the filtrate,
and the technical grade boric acid is dried and packaged.
The technical grade product can also be diverted upstream of
the final drying step, redissolved, crystallized, filtered,
and dried to produce a higher purity product. Sodium
sulfate is a co-product and most of the wastes are
water borne. There are small amounts of arsenic-bearing
wastes which are potentially hazardous upon land disposal,
but at present they are all discharged in the plant
effluent. The properties of arsenic are described in
Appendix A. This waste occurs at only one plant. The
impact of effluent discharge limitations should cause
arsenic wastes to go to land disposal in 1977. The flow
diagram for this process is given in Figure 5-38.
IrJLsJjJ Chromic Acid
This chemical is discussed in SIC Code 28199 under chromate
production. There are no wastes that are not attributable
to the manufacture of sodium dichromate. The flow diagram
for chromic acid manufacture is given in Figure 5-39.
J>i5._2.._«» Hydrogen Cvaqide
Hydrogen cyanide is produced from methane, ammonia, and air
by a catalytic process (Andrussow Process) whose flow
diagram is shown in Figure 5- 40. This reaction occurs at
elevation temperatures over a platinum catalyst. Other
products and product contaminants include residual ammonia
and organic nitrites. Unreacted ammonia is removed from the
products by scrubbing with sulfuric acid. The crude cyanide
is then further purified by scrubbing with water and
distillation of the aqueous solution. The purified product
is compressed and liquified. All of the hazardous wastes
(cyanides) are water borne and are generally removed by
either chemical oxidation or biological treatments. No
hazardous wastes destined for land disposal are generated by
the treatments.
Small amounts of HCN are also generated as a co-product of
acrylonitrile manufacture, and there are no hazardous wastes
attributable to this process.
5-85
-------
(720 BORAX
ut
L
Off
at
SULFURIC AOD-
SOLUTTQN
REACTOR
FILTER
COOUNG
AND
SEPARATION
1
REJHJLPER
— »
CENTRIFUGE
VENT
1
DRYER
275
—•^SULFATE
BY-PRODUCT
WASTE LIQUOR A
WASTE LIQUOR *
^WASTE UQUOH CONTAINS:
0.036 ARSENIC
94 SODIUM BORATE:
300 SODIUM SULFZTE
£,800 WATER
WWJER
REPISLPER
AND
REDISSOLVER
— »
RLTER
AND
COOLER
— ^
CENTRIFUGE
VENT
f
DRYER
JOOO BORIC
"ACJD PRODUCT
WASTEUOUORA VWSTELIQUOR -
FIGURE 5-38
BORIC ACID MANUFACTURE
-------
EXCESS
SULfWtiC ACI&
SODJUM
CHf&M/C
ACID
REACTOR
or
I
o>
UQUOR
ACfD
LIQUOR TO
t
SODIUM BISULFATE
TO O/CHf=tOMATEi
CHROMIC ACID .MANUFACTURE
-------
AC/0
AC/0
UATUKAL GAS
&3O
310
\
CATALYTIC.
\
H
UM/T
t
HCM
/-Z SO^AS JmBUJSBK
U1
I
GO
00
U&OH
Oz
a .&-
\
25T-75"
SOL/OS
HYDROGEN CYANIDE MANUFACTURE
BY THE AUDRUSSOW PROCESS
-------
S Hydrofluoric
This material is made by the reaction of fluorspar (CaF2)
with concentrated suIfuric acid irt a furnace. The
hydrofluoric acid leaves the furnace as a gas, which is then
cooled and absorbed in water prior to purification. In the
purification system, the crude acid is redistilled and
either absorbed in water to yield aqueous hydrofluoric acid
or compressed and bottled as anhydrous acid. Final drying
of the anhydrous gad is accomplished with concentrated
sulfuric acid. This process is shown in Figure 5-41* There
are large amounts of co-product gypsum contaminated with
fluorides which occur as a waste. This material is
generally slurried and pumped to lagoons where lime is added
to precipitate CaF2 and neutralize any acid present. The
waste water is then either discharged or recycled. These
wastes closely resemble others from phosphorus production ih
terms of the fluoride problems encountered.
The concentration of CaFg ih the solid waste from HF pro-
duction is sufficient to render the toxicological properties
of the total waste very similar to the properties of CaF2
described in Appendix A. The leachate from the CaF2-
containing waste will exceed water quality standards.
Furthermore, the leaching of high concentrations of fluoride
ion (above 10 ppm and as high as 1,000 ppm) is possible by
contacting with leach water of low pH and particularly with
solutions of mineral acids, as may easily occur in an
industrial landfill used over a long period of time* Bee
Appendix A, Figure 1 for data on release of fluoride by acid
contact. This additional potential hazard, together with
the substantial present hazard to drinking water quality, is
judged to be sufficient to regard these waste streams as
hazardous although the material, calcium fluoride, is itself
in the "moderately hazardous1* category.
5.5.2.6 chlorosulfoaic Acid
Chlorosulfonic acid is manufactured by the reaction of
sulfur trioxide and hydrogen chloride. The only wastes
arise from the scrubbing of vent gases, and consist of
dilute solutions of alkali metal salts which are discharged
as waterborne wastes. No hazardous wastes are involved.
The flow diagram is given in Figure 5-U2.
5j.5j5.2i7 Aggregate of SIC_2j§i.9.4 Hazardous Wastes
The only currently land-disposed hazardous wastes from
SIC 28194 are the fluoride-contaminated wastes from hydro-
fluoric acid manufacture. Table 5-9 gives the water stream
amounts (dry basis) and fluoride content on a state-by-
5-89
-------
2013 CALCIUM FLUORIDE
COOLER
tn
i
VD
o
3620
120 HgSO^
63 CaF2
1.5 HF
I
EFFLUENT SOUP WASTE
3600 CaSQ}
69
L-4
CONDENSER
1
CONDENSER •—•
CRUDE
HF
STORAGE
SOHJBBER
VKKTER
TAILS
TOWER
i
EJECTOR
J
2* UME-
H*
r»-^—**
DISTILLER
T
I
jr
STRIPPER
ACID
STORAGE
WATER
I
JL
ACID
ABSORBERS
u
EJECTOR
T
WKTEW
VWISTE TREATMENT
saz
I HF
3OUO VMKSTE
40
TO ACID
STORAGE
IOOO HF
IHYOROUS
PRODUCT
I-S Ul
WASTE
TREATMENT
EFFLUEWT SOLID VHftSTE
t-tt
ROIRE
BYDRDFLUORfC ACID WANUFACTUf^
-------
veur
tn
i
vo
$36 HCI
^j
£""1
>
P&ODUCT
MC/D
+M»CI
CHLOROSULFOHIC AMD
-------
Table 5-9» Hazardous Wastes Destined fol- Land Disposal frbhi the
SIC 28194 Inorgdritc Acids Industries (metric tons
per year, dry basis)
IV Alabama
t Alaska
:x Arizona
"t Arkansas
X California
Til Colorado
Connecticut
tl Delaware
tV Florida
W Georgia
[Jt Hawaii
[ Idaho
t ' ' Illinois '
/ Indiana
711 Iowa
/I I Kansas
tV Kentucky
/I Louisiana
I Maine
til Maryland
t Massachusetts
V Michigan
V Minnesota
CViTOKt
Total
Hazardous
Wastes
40.DOO
W.boo
49.000
84.000
350,000
IV Mississippi
VII Missouri
VIII Montana
VII . Nebraska
IX Nevada
I New Hampshire
li New Jersey
VI New Mexico
II New York
IV North Carolina
VIII North Dakota
V Ohio
VI Oklahoma
X Oregon
III Pennsylvania
I Rhode Island
IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII Utah
I Vermont
III Virginia
X Washington
III West Virginia
V Wisconsin
Vlfl. Wypinihg
Iroi'AL
rtegion I
II
III
IV
V
VI
Vll
VI it
IX
X
37.000
60.000
17.000
180,000
.tf.OOO
1.4(0.000
;7rooo
17Q.OOO
f 4,000
ir 9.000
9;0.000
40; 000
Fluoride
Content
sSd
l.jjflfl
670
1,200
4,900
510
830
240
B.OOO
" 9»a '
19.000
510
!,400
f?00 -
.500
.000
550
Total
Hazardous
Wdst«S
SS.dbfl
W.060
54.000
94,000
400,000
42.000
68,000
19,000
Md.Oott
7i,666
i .600,000
42,000
19C,000
9^000
]20rOOO
i.i 06.000
50,000
1977
Fluoride
Content
<4id
1,300
750.
l,3t)0
5,500
580
930
260
.
9,000"
1,000
i\. ooo
580
2.600
,300
1' ,000
620
Arsenic
Content
.i4 '
2.6*
2.6*
,. tbfai
Hazardous
Wastes
oS.OOd
120.000
6^.000
120.0ft)
500. OCO
53.006
W.doD
24. dM
850,000
96,000
2,000,000
53rOOO
240. op )
120.00 )
i50
t ,6od
6,900
7"$
UiOfi
"" 330
1 11,006 "
IJoo
26,000
i
2,OPO
18^000,
820
Arsenic
Gbnteht
l
19*
-
2.9*
i.9*
'Arsentc-contalntng wastes generated by boric acid manufacture only.
Total wastes from tnls segment 4,900 In 1977 and 6,400 In 1983,
5-92
-------
state, regional, and national basis* The values given are
based on both manufacturer supplied data and our estimates.
The overall reliability is judged to be about 3051.
i«.5i2i8 Proiectign Qg SIC 26194 Hazardous Wastes
By 1977r the effluent discharge limitations should cause
arsenic-containing solid wastes from boric acid manufacture
to be disposed of on land. No other process changes or
treatments to reduce discharges are expected in this
category which would affect land-disposed hazardous waste
levels through 1983. The estimated production growth in
both boric and hydrofluoric acid will probably average 4
percent per year in this period. The projections for 1977
and 1983 for SIC 28194 are given in Tables 5-9.
The overall trends for the amounts of hazardous wastes from
SIC 28194 destined for land disposal in terms of metric tons
per year (short tons per year) are summarized as:
Period Current 1977 1983
dry basis l.UxlO* 1.6x10* 2.0xlO«
(1.5x10*) (1.7x10*) (2.2x106)
moisture 1.9x106 2.1x106 2.7x10*
included (2.1x10*) (2.3x10«) (2.9x10*)
It should be noted that this subcategory is responsible for
approximately 70X of the hazardous waste tonnage generated
by the inorganic chemicals industry.
5.5.3 Aluminum Oxide and Aluminum Hydroxide (SIC 28195)
These two materials are produced from bauxite by the process
shown in Figure 5-43. The raw bauxite ore is first reacted
with alkali under pressure to yield a sodium aluminate
solution. The insolubles (red muds) are separated from this
and discarded, and the solutions are then decomposed by
dilution to yield an alumina trihydrate (aluminum hydroxide)
which is then recovered by filtration and dried.
The pure oxide is prepared from this material by
calcination. There are numerous wastes coming from this
process. These include:
(1) The ore residues ("red muds") which consist of silica
and iron oxides contaminated with spent caustic. These
are generally neutralized prior to disposal and are non-
hazardous in their final form.
5-93
-------
(2) The spent weak caustic resulting from decomposition of
the sodium aluminate liquors. Thid is a Water-borne
waste stream which is either reeoneetttrated and reused
dr neutralized prior to discharge*
(3) Dusts from calcination operations* These are chiefly
alumina and are recycled.
the flow diagram of Figure 5-43 is constructed with the
latter two streams internally recycled.
Hilt!,.! Aggregate of g;il±^ Aluminum tluorj.de
A1P3 iri produced, as shown in Figure 5-U5, by the reaction
of alumina with hydrofluoric acid. The hydrated alumina and
anhydrous hydrofluoric acid are added to a reactor* The
solid product is cooled collected, and readied for shipment*
5-94
-------
in
I
vo
U1
HEATING
STEAM
A
WATER
T
MUD
/7
35
3 MISC.
40
FILTER
FILTER
KlUd
ALUMINA MANUFACTURE
BAUXITE
-------
WATER
\
Ut
I
va
at
I
>/
(ALUMINUM,
S3.3
net
CHLORIDE MANUFACTURE
-------
WATER
977
ALUMIUA
LA
HEACTOH n
UI
I
vo
CYC
WATER
I
\ \
SOUP WASTE LIQUID
DI /** r~
&l La h*
ALUMIUUM
FLUOHIDZ PRODUCT
ALUMINUM FLUORIDE MANUFACTURE.
-------
In some plants the reaction takes place in aqueous solution*
from whidh the water must be driven off to effect recovery
Of the solid product. All of the wastes arise front the
scrubbing of vent gases, and the waste waters generated (tdt
the three facilities producing this product) are either
discharged without treatment or treated in conjunction
other waste streams <
The solid waste generated by waste water treatment consists
Of d.ticium hydroxide and calcium suifate, neither of which
are hazardous* and calcium fluoride which is a hazardous
constituent. The concentration of eaF2 as fludride in the
waste is about 20 percent (w/w dry basis) , thus rendering
the overall biological properties of the waste similar to
those described in Appendix A for Caff2, Protection against
edntai ideation of ground and surface waters is required » fof
leaching can develop fluoride concentration in excels of
drinking Water standards* Furthermore, the leaching of high
doncJert rations of fluoride ion (above 10 ppm and as high afl
1,000 ppm) is possible by contacting with leach water of low
ptt and particularly with solutions of mineral acids $ as1 may
easily occur in an industrial landfill used over a long
period of time. See Appendix A, Figure 1 for data on
release of fluoride by acid contact. This additional
potential hazard,, together With the substantial present
hazard to drinking water quality * is judged to be sufficlettt
to regard these waste streams as hazardous although the
material* calcium fluoride, is itself in the "moderately
hazardous" category.
5^5* **A3 Aluminunj S
As shown in Figure 5-46, alum (aluminum sUlfate) is produced
by reaction of alumina, bauxite, or clay With sulfUric acid*
Ground ere and acid are reacted in a digester, from which
the products, aluminum sulfate in solution plus muds and
other insoluble materials from the ore, are then fed into a
settling tank. The aluminum sulfate solution is then
clarified and filtered to remove any remaining insolubleS.
This may be used as solution or evaporated td yield a solid
product* There are solid wastes consisting of ore residues
(silica, etc.), but these are extremely insoluble materials
of a non- hazardous nature.
Aggregate oj StC gQl§6 Hazardous
The only &1C 28196 process generating hazardous wastes
destined for land disposal is that for the manufacture of
aluminum fluoride. The waste stream is fluoride-containing
gypsum and lime, which is similar to the haaardous Waste
stream from hydrofluoric acid manufacture (SIC 28195)
5-98
-------
1
SO
en
vo
vo
WASH&JT
WAST&3
SZTTUUG
FILTRATION
WASTE
WASTE
T&7XL MISTS' MUD
48
/9
W/LfXTE&&0UCT
1
SUL&T& PR0DUC T
SULFATTE
-------
discussed earlier* Table 5-10 lists the current situation
on a state-by- state , regional , and national basis, the!
values given are baaed on both manufacture-supplied data and
our estimates t and is expected to be accurate to within
30 percent.
grgjestiort oj ii£^igi9|> Ha.2§rjo.uj| Mas teg
Cot the period through 1983, ho process changes
anticipated that will affect the hazardous Wastes destined
for land disposal in 6lC 28196- A minor effect will ensue
with the imposition of air and water regulations* since the
largest portion of the fluoride waste is already removed to
land disposal by treatment* Table 5-10 also gives the
projected situations in 1911 and 1983. The growth iti
aluminum flouride manufacture is estimated to average
4 percent per year through this period*
The trends in hazardous Wastes for land disposal from
SIC 28196 can thus by summarized as below. The Values are
total amounts in terms of metric tons per year (short torts
per year) s
£§£103 eUrrent 19tt .1.383
dry basis 32,000 37,000 40,000
(33,000) (41,000) (44,000)
moisture 43,000 49,000 53,000
inclUdeid (47,000) (54,000) (59,000)
5^J. Potassium Met§i
This material is produced by reaction of sodium metal with
potassium chloride vapors as shown in Figure 5*47. The
molten potassium chloride flows over Raschig rings in the
packed column, where it Contacts ascending sodium vapors
coming from a gas-fired reboiler. An equilibrium is
established between the two, yielding sodium chloride and
elemental potassium. The sodium chloride formed is
contlnuoasly withdrawn at the base Of the apparatus and may
be sold. The column operating conditions may be varied to
yield either pure potsssium metal as an overhead product or
to vaporize sodium along with the potassium to produce
sodium-potassium (NaK) alloys of varying compositions.
According to the one manufacturer of this chemical in the
U.S., the sodium chloride co-product is utilized at the same
facility and is not a waste. There are ho other wastes
involved.
S-100
-------
Table 5-10. Hazardous Wastes Destined for Land Disposal from the
SIC 28196 Aluminum Compounds Industries (metric
tons per year, dry basis)
IV Alabama
X Alaska
IX Arizona
VI Arkansas
IX California
VIII Colorado
I Connecticut
III Delaware
IV 'Florida
IV Georgia
IX Hawaii
X Idaho
V Illinois
V Indiana
VII Iowa
VII Kansas
IV Kentucky
VI Louisiana
I Maine
III Maryland
I Massachusetts
V Michigan
V Minnesota
IV Mississippi
VII Missouri
VIII Montana
VII Nebraska
IX Nevada
I New Hampshire
II New Jersey
VI New Mexico
II New York
IV North Carolina
VIII North Dakota
V Ohio
VI Oklahoma
X Oregon
III Pennsylvania
I Rhode Island
IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII Utah
I Vermont
III Virginia
X Washington
III West Virginia
V Wisconsin
VIII Wypming
TOTAL
Region I
II
III
IV
V
VI
VII
VIII
IX
X
Current
Total
hazardous
Wastes
3,200
14.000
3.200
12,000
32,066
3.200
29.000
Fluoride
Content
BOO
3.500
800
3,000
6,100
800
7.300
1*77
Total
Hazardous
Wastes
3,600
16.000
3.600
14.000
37.000
3.600
34,000
Fluoride
Content
900
3.900
900
3,400
9.100
900
8,200
1983
Total
Hazardous
Wastes
4,100
_,
17.000
4,100
15,000
40.000
4,100
36,000
Fluoride
Content
1,000
4.400
1,000
3,800
10.266
1.000
9,200
5-101
-------
MO&EAJ At:/
A/aC/
o
hj
POTASSIUM MANUFACTURE
-------
5-.5±5±2 Potassium sulfate
This product is produced by the reaction in solution of
potassium chloride with langbeinite ore (K2SOf*.MgSOf») , as
shown in Figure 5-U8. Mined langbeinite is crushed and
dissolved in water to which potassium chloride is added.
Partial evaporation of the solution results in selective
precipitation of potassium sulfate which is recovered by
centrifugation or filtration, dried, and sold* The
remaining brine liquor is either discharged to an
evaporation pond, reused as process water, or evaporated.
Sodium chloride impurities in the ore and, in many cases,
the MgCl2 co-product, are the only Waste products. These
exit the plant in the form of brine solutions which are fed
to evaporation ponds. All of this material is produced
close to areas where it is mined (in New Mexico) and the
solids generated by evaporation are not hazardous (i.e.,
sodium and magnesium chlorides) .
5/>553 Potassium Iodide
As shown in Figure 5-19, this chemical is produced, by reac-
tion of iodine with potassium hydroxide. The iodate
precipitates out and is removed as a by-product. The iodide
solution is evaporated to dryness and fused in a gas-fired
furnace to decompose residual iodate. The fused iodide is
redissolved in distilled water, and barium carbonate,
hydrogen sulfide, ferrous iodide, and carbon dioxide gas are
added to precipitate impurities and adjust the pH of the
solution. The solution is filtered and fed to
crystallizers, from which the potassium iodide crystals are
centrifuged, dried, screened, and packaged. The mother
liquor from the crystallizers is recycled. An iodate co-
product is recovered, and there are small amounts of solid
wastes generated by product purification steps. However,
the quantities of these wastes are very small, and only two
locations are involved. The solid wastes contain barium
sulfate and small amounts of insoluble sulfides. Because of
its virtually total insolubility in water and body fluids,
barium sulfate is a nonhazardous waste constituent. Thus
these waste streams are judged not to constitute a signifi-
cant hazardous waste when land-disposed.
Jb.5i5.-Ji Potassium Chloride
This material is produced from natural brines and from
sylvinite ores. In the former case there are no hazardous
wastes for disposal since the spent brine is returned to the
well, which constitutes recycle. In the sylvite process
(which is shown in Figure 5-50) , the ore is mined, crushed,
screened, and wet-ground in brine to dissolve most of the
5-103
-------
ue»r
J_
AAJ
t
I
RTTASSIUM SULF~A-TE
-------
WATER
OXYGEN
VENT
ui
o
Ul
920 IODINE
405 CAUSTIC
POTASH
DISTILLED
WATER
«•
•»
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i 1 t
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t
» FlITFfl ^ CRYSTALLIZER ^ CENTRIFUGF" A DHYFR
SOUP WASTE
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POTASSIUM
IODIDE
PRODUCT
POTASSJUM
IODATE
GO^PROfflJCT
RGURE 5-49
POTASSIUM IODIDE MANUFACTURE
-------
r
UT
o
en
1
i
JE&4&9T&AJ
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TO
1400 -
l
AAJD
FROM
-------
soluble salts. Clay is removed by settling,, as are the
other undissolved materials in a separate step. The brine,
saturated in sodium chloride, is fed to a flotation cell
where air is passed through the solution (to which flotation
agents such as tallow amines, polyalkyl glycol, starch, etc.
have been added) in order to carry sodium chloride into the
froth. The potassium chloride brine is then vacuum-
crystallized, and the potassium chloride crystalls are
centrifuged, dried, screened and packaged. There are large
amounts of waste generated due to the presence of sodium
chloride and silica although these are not hazardous in
these amounts at these locations. These wastes are slurried
and fed to evaporation ponds and all processing this occurs
in a sparsely populated arid region (New Mexico).
5.5.5.5 Borax (Sodium Tetraborate Decahydrate)
Borax is extracted either from Searles Lake brines or from
natural ores. In the first case, there are no solid wastes
produced. With ore extraction, however, there are ore
residues produced which contain small amounts of a naturally-
occurring arsenic sulfide mineral called "Realgar". It is
chemically As2_S2_. Generally, these arsenic containing wastes
are disposed of in lined evaporation ponds. The mining
operations involve a single plant location in an arid and
isolated area. The ore is crushed and conveyed to
dissolvers where water and recycled mother liquor are added
to dissolve the borax. The insolubles are settled out in
ponds, and the clarified borax solution (mother liquor) is
fed to crystallizers where a slurry of borax crystals in
water is formed. The borax is separated from the water by
centrifugation, dried, screened and packaged. The product
borax is a hydrated sodium tetraborate, Na2BUO7«lOH2O. For
boric acid manufacture the pentahydrate, Na2B407«5H2O, is
produced. The flow diagram is shown in Figure 5-51.
The arsenic is present in the mine run ore and associated
shales as "Realgar", a natural form of arsenic sulfide. The
occurrence is intermittent, and a given ore horizon can vary
from 0 to over 1000 ppm as arsenic. Because of low
solubility, most of the Realgar remains in solid form and is
deposited in ponds with clay.
Water and air discharges are already regulated by stringent
state requirements. There is no likelihood of percolation
into ground water because there is none in the area. Water
.in the ponds above the gangue material eliminates the
possibility of blowing dust. Thus there is judged to be no
5-107
-------
/80G>
8Q&AX
\
IT
I
H
AAJD
Sao
GAfiWE
i
v#/be
BOtfAX MANUFACTURE PROM ORE
-------
environmental problem at this location due to the disposal
of these ore wastes on land.
The total amounts of these wastes are very large, about
900,000 metric tons per year (1,000,000 short tons per year)
on a dry basis containing approximately 45 ppm of arsenic as
Realgar. Because of the localization of this industry, the
natural mineral form of the waste, problem imposed, its
waste stream will not be considered hazardous for the
purpose of aggregation with the other SIC 28197 streams in
this study.
5^5^5.2.6 Sodium Fluoride
This material is produced by two processes as shown in
Figures 5-52 and 5-53. The first involves reaction of soda
ash with hydrofluoric acid. Anhydrous hydrofluoric acid
(hydrogen fluoride) and soda ash are reacted, and hydrogen
fluoride fumes and carbon dioxide are scrubbed with a soda
ash solution. The product from the reactor is a slurry of
sodium fluoride which is vacuum filtered to recover the
fluoride. The product is then dried and packaged. No
wastes are generated in this process. The second involves
recovery from impure phosphoric acid. Sodium silicofluoride
is recovered and then converted to the fluoride by reaction
with caustic soda. The wastes from this process are water-
borne and contain silicates and fluorides. Wastewater
treatment generates moderate amounts of calcium fluoride as
a solid waste. Calcium fluoride, a moderately hazardous
material, is the major constitutent of the waste stream, and
the overall properties of the waste are the same as those
described for the individual components (Appendix A) .
Protection against contamination of ground and surface
waters is required. See Section 5.5.2.5 for detailed
discussion of hazard.
SiSiSjJ Sodium Sulfide and Hvdrosulfide
These products are made, as shown in Figure 5-54, by re-
action of hydrogen sulfide with caustic soda. The wastes
from this process are chiefly water-borne and contain
sulfides. Depending on whether aeration or chemical
precipitation is used to treat the wastewater, solid wastes
may or may not be generated. For cases where they are,
small amounts of iron sulfide are the solid waste. This
waste is not hazardous.
5_=.1L5.=_§ Sodium Hydrosulfite
This material is made by two processes as shown in Figures
5-55 and 5-56. In the first, zinc and sulfur dioxide are
reacted in solution to form zinc hydrosulfite. The
5-109
-------
SODA
ASH
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SODIUM FLUORIDE MANUFACTURE
FROM UYDROFLUORiC ACID
-------
I08S
5&%
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PRODUCT
WET
WATER
SODIUM rLUOf?/DET
FROM CAUSTIC SODA AktD SdDIUM SILICOFLUORIDE
-------
72? FLARE
4 f
CAUSTIC
CAUSTIC
ST0RAQ£
kBSQR&ER
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TOTAL SULFIDE: tM
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REACTOR
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WASTE
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PRODUCT
MANUFACTURE OF SOPIUU UYDROSULFTDE
AMD SQDIUM SULRDE
-------
WAT&?
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738
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FIGURE S-
HYDROS ULFIJE MANUFACTURE
-------
resulting zinc hydrosulfite in solution is treated with
caustic soda to precipitate zinc hydroxide. The sodium
hydrosulfite solution is filtered and evaporated, and the
hydrosulfite is crystallized out, centrifuged, washed,
dried, and packaged for sale. Most of the wastes from this
process are waterborne. The only solid waste generated is
zinc oxide or zinc carbonate formed as a co-product during
the conversion of the zinc hydrosulfite intermediate to the
sodium salt. The zinc oxide or carbonate is recovered and
sold as a coproduct. No hazardous Wastes are destined for
land disposal, and no solid wastes are generated that are
not sold or recycled.
In the second process, sodium hydrosulfite is also produced
by a reaction of SO2 with sodium formate in an alcohol based
solvent. All of the wastes from this process are waterborne
and no hazardous wastes are generated.
S..5.5.9 Sodium Metal
This material is made by the Down's cell process and is a
co-product of chlorine, SIC Code 28121.
5.5.5.10 Sodium Silicofluoride
This product is made by two processes as shown in
Figures 5-57 and 5-58. In the first, fluosilicic acid,
H2S1F6, is reacted in solution with sodium chloride. The
product is then separated by filtration, dried, and
packaged. All of the wastes from this process are water-
borne, and treatment of this effluent does generate a small
amount of some calcium fluoride containing wastes. This
treatment consists in general of precipitation with lime and
settling or filtering of solids.
In the second process, soda ash is added to impure
phosphoric acid. Sodium silicofluoride precipitates and is
collected by filtration, washed, dried, and packaged.
Wastes from this process are all water-borne, and their
treatment generates a solid waste-containing calcium
fluoride by a treatment process as described above. This
second process is used in only one facility, and the amount
of waste material is small.
For both processes, the concentration of CaF2 in the solid
waste is such that the overall biological properties of the
waste are similar to those described in Appendix A for CaF2.
Protection against contamination of ground and surface
waters is required. See Section 5.5.2.5 for a detailed
discussion of the potentially hazardous nature of such wastes,
5-.115
-------
FLUOSlUCtQ AC/D
FGtCToG
H
1
serrtee
-
\
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H
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72?
-50
SODIUM ^lUQOFLUORlDE MANUFACTURE
-------
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SOPIUM SILICOTLUORIDE MANUFACTURE
FROM AM IMPUfte PHOSPHORIC ACID S77?£AM
-------
^•.5^5^11 Sodium Phosphates
The manufacture of sodium orthophosphates (monobasic,
dibasic, and tribasic sodiumphosphates) is shown in
Figure 5-59. These materials are made by the reaction of
phosphoric acid with soda ash or caustic soda. No hazardous
wastes are generated, the only significant wastes being
leaks and spills of reactants or products. Sodium
tripolyphosphate is manufactured (as is shown in
Figure 5-60) from the orthophosphate solution by molecular
dehydration with heat. No hazardous wastes are generated by
this process.
Food-grade sodium phosphate is prepared from high purity,
food-grade phosphoric acid. The only wastes are dilute
solutions of phosphoric acid due to equipment washdown,
scrubbers, spills and the like that are not recycled due to
the food-grade requirements. These wastes are not
hazardous; several widely sold soft drinks are also dilute
solutions of phosphoric acid. The facilities responsible
for production of food-grade phosphoric acid from phosphorus
are covered under a different classification, SIC 2874 (see
pp. 124,609 and 610 reference 71) and hence any wastes
associated with those operations are not attributable to the
industries of this study (SIC 281).
5i5.i5i.i2 Sodium Borohy,dride
The manufacture of sodium borohydride is shown in
Figure 5-61. Sodium metal and hydrogen are reacted in an
oil medium to yield the hydride. The oil solution of this
material is then reacted with methyl borate to yield sodium
borohydride, which is separated from the oil into a aqueous
phase and recovered by evaporation. The oil is recycled.
Most of the wastes from this process (sodium borate and
methane) are not hazardous. The only hazardous waste
consists of unreacted sodium sludge in the first process
step. This sludge is not a candidate for land disposal
because of the potential for explosion upon contact with
water. It is currently (and for the foreseeable future)
disposed of by barging to sea. The amounts so disposed
presently are estimated to be 20 metric tons per year from
Massachusetts and 10 metric tons per year from Pennsylvania.
Sodium Sulfite
As shown in Figure 5-62, sodium sulfite is produced by
reaction of S02 in solution with soda ash under pressure.
Small amounts of iron sulfide solid waste are produced from
waste water treatment. This material is extremely insoluble
5-118
-------
DIBASIC:
746 SODA ASH
690
VENT
310 C0t
126 WATER
REACTOR
CRYSTALLLIZING
A Kin
DRYING
MILLING
TRIBASIC:
VENT
123 C02
in
I 297 SODA ASH
t-j
vo 275 H3P04
SH »
REACTOR
— »
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112 NoOH
CAUSTIC SODA
(SOLUTION)
i
REACTOR
t
— •+•
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CRYSTALLIZER
VENT
1
DRYER
1000
H^O
PRODUCT
MONOBASIC:
355 H3P04
514 DISODIUM PHOSPHATE
: g
VENT
REACTOR »"
f
RLTER
CRYSTALLIZER
—
DRYER
lOOONaHgPCJ, PRODUCT
FIGURE 5-59
SODIUM ORTHOPHOSPHATES MANUFACTURE
-------
^^o STEAM
Ul
NJ
O
1
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COLLECTOR
72O
ASM
800 PHOSPHORUS
ACID
MIX TANK
GASES AND DUSTS
SPRAY
DRY EH
AND
I9 O&G STP PftXXJCT
SODIUM rRIPOLYPHOSPHATE MANUFACTURE
-------
(To
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I
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T
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MeTHAUOL
SODIUM BOF3OHYDRIDE. MANUFACTURE
-------
&&S5T/C
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SODIUM
FIGURE.
-------
in water, and dilute acid and is not hazardous. The
properties of iron sulfide are given in Appendix A.
itltSiiii Sodium. Silicate
As shown in Figure 5-63, sodium silicate is produced by
reaction of silica sand with caustic soda. These mixed in
the desired proportion and charged to a furnace. Water and
steam are added to the product under pressure to completely
dissolve the silicate. The liquid product is then stored or
used to produce silicate in solid form. The production of
solid silicate from silicate solution essentially involves
evaporation of the water, although the silicate in solution
may be further reacted with a caustic solution during the
process if a higher sodium crude content is desired in the
solid product. This is typically the case in the production
of sodium met a silicate (anhydrous) from tetrasilicate water
glass. The dried anhydrous silicate is screened and milled
to achieve the desired particle sizes. The only solid
wastes generated are due to treatment of water*- borne waste
streams and consist of silica and silicates. These are not
hazardous.
5.5.5.15 Sodium Thiosulfate
As shown in Figure 5-64, this material is made by reaction
of sodium sulfite with sulfur. The feed solution to the
reaction may also contain sodium bisulfite and sodium
carbonate. The resulting hypo solution may be sold at
30 percent solids or may be further processed to yield
anhydrous solid hypo or the pentahydrate. The hydrate is
crystallized out during vacuum evaporation, and is washed,
dried and packaged. In the manufacture of the anhydrous
material, the hydrate is melted, treated with caustic soda,
sodium hydrodulfide, and copper chloride, then filtered.
Anhydrous crystals are formed in a high-temperature crystal-
liaer, centrifuged, dried, and packaged. Generally there
are no process wastes; leaks and spills are water borne and
not hazardous.
5 •, 5 ±.5^1 6 chlorates and Perchlorates
The manufacture of sodium and potassium chlorate is shown in
Figures 5-65 and 5-66. Sodium or potassium chloride is
dissolved in water and impurities are removed by the
addition of soda ash and caustic. Calcium carbonate and
magnesium hydroxide precipitate out and are removed by
filtration and discarded as non-hazardous wastes. The brine
is acidified and dichromate is added and it is electrolyzed.
Chlorates and hydroggp gas are the products.
5-123
-------
SILICA
4ZOS6DA
ro
H
STEAM
CH/LL
H
DISSOLVEff
K
SCRUBBER
30L/D
\ \
6> SiO?
, &L /£4 TE)
SOOIUkA SILICATE MANUFACTURE
-------
I
i
7V7
f £V9P&£4T0*
i oey^7?^^/a£3e
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SODIUM THIOSULFATE
-------
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SODIUM
s?
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1 I
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SOt- 1 OS
1
SOLID
-------
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Barium chloride is added to the solution coining from the
cell to remove sulfates and chromates. This small amount of
material is then removed by filtration and discarded as a
solid waste.
The constituents in this waste are barium sulfate which is
non-hazardous and barium chromate which is hazardous. The
properties of barium chromate are discussed in Appendix A.
The solutions are then partialy evaporated to recover
unreacted chlorides which are recycled and then fed to
crystallizers to recover the product (KC103 or NaClO3).
There is also an additional solid waste consisting of spent
carbon electrodes contaminated with chlorates. JThese are
probably combustible and must be disposed of with care, but
are not otherwise hazardous.
As shown in Figure 5-67, sodium perchlorate is prepared by
further electrolysis of chlorate solutions. Hydrogen is
again formed as a co-product, and small amounts of barium
chromate hazardous waste is generated and goes to disposal
on land, insofar as is known. The amounts in any one
location would be very small, less than one metric ton per
year, and hence are not considered further. These would be
expected to be found principally in Nevada.
Potassium perchlorate is produced by reaction of KC1 with
the sodium salt in solution as shown in Figure 5-68. As
KC10U is very sparingly soluble, it is recovered by
filtration, No hazardous wastes are produced or destined
for disposal on land.
SiSiSj^l? Potassium Nitrate
This material is manufactured by two processes, as shown in
Figure 5-69. Only one process, the reaction of potassium
chloride with sodium nitrate, has any significant wastes,
and these are salt (sodium chloride) solutions which are not
hazardous in these amounts at these locations. The other
process, combining potassium chloride with nitric acid in
air, generates no wastes.
5.5.5.18 Sodium Bisulfite
This commodity is produced from sulfur dioxide and soda ash
by reaction in aqueous solution. The raw materials are of
high purity and introduce no hazardous wastes by virtue of
impurities. Sodium bisulfite manufacture has only a water-
borne discharge of dilute sodium sulfate. No hazardous
wastes are generated., The flow diagram is given in
Figure 5-70.
5-128
-------
0/&37&K
M^TTSfc
I . V
2*5-
SODIUM
-------
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CHLORIDE.
en
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-------
1
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6>34 HUG3
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SODIUM NITRATE
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P0TASS/UM Ay/77?ATE MANUFACTURE
-------
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-------
5.5.5.19 Sodium Bromide
Sodium bromide is produced from hydrobromic acid and soda
ash or caustic soda in aqueous solution as shown in
Figure 5-71. Mo significant wastes are generated.
5.5.5.20 Sodium Cyanide
This commodity is produced from hydrocyanic acid solution
and caustic soda. Although sodium cyanide is itself a
hazardous material, the manufacture of it is carried out
very carefully using stoichiometric amounts of reactants
and no wastes are generated from the process. The flow
diagram is given in Figure 5-72.
5.5.5.21 Aggregate of_ SIC 28197 Hazardous Wastes, to Land
Disposal
The processes in SIC 28197 generating significant amounts of
hazardous wastes for land disposal are the manufacture of
sodium silicofluoride and borax. However, the wastes from
borax manufacture are not further considered because of the
special conditions discussed earlier with regard to the sin-
gular location in an arid region that poses no environmental
difficulty under present or future operation.
The aggregate of the fluoride-containing hazardous waste
streams of SIC 28197 are given in Table 5-11 on a state-
by-state, regional and national basis. The values are
based on both manufacturer-supplied data and estimates,
and are reliable to within 30 percent of the given values.
5.5.5.22 Projection of_ SIC 28197 Hazardous Wastes Destined
for Land Disposal
The projections given in Table 5-11 take into account the
growth of these industries (estimated as 4 percent per year
over the period) and the impact of air and water regulations
(which is minor) on the total amounts. NO process changes
are anticipated that would significantly affect the land-
destined hazardous waste generation.
The trend of hazardous waste destined for land disposal
in SIC 28197 can be summarized in terms of metric tons
per year (short tons per year) as:
5-133
-------
V&A/T
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*».
SODIUM
SODIUM BROMIDE
-------
00
Ul
$87 HCGUH
Msx/r
ey/w/ee
-------
Table 5-11 . Hazardous Wastes Destined for Land Disposal from the
SIC 28197 Potassium and Sodium Compounds Manu-
facture (metric tons per year, dry basis)
IV Alabama
X Alaska
IX Arizona
VI Arkansas
IX California
VIII Colorado
I Connecticut
III Delaware
IV Florida
TV Georgia
IX Hawaii
X Idaho
V Illinois
V Indiana
VII Iowa
VII Kansas
IV Kentucky
VI Louisiana
I Maine
III Maryland
I Massachusetts
V Michigan
V Minnesota
IV Mississippi -
VII Missouri
yill Montana
VII Nebraska
IX Nevada
I New Hampshire
II New Jersev
VI New Mexico
II New York
IV North Carolina
VIII North Dakota
V Ohio
VI Oklahoma
X Oregon
III Pennsylvania
I Rhode Island
IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII Utah
I Vermont
III Virginia
X Kashinoton •
III West Virqir.ia
V Wisconsin
VIII VK'oming
TOTAL
Region I
II
III
IV
V
VI
VII
VIII
IX
X
Current
Total
Hazardous
Wastes
2r900
200
600
200
500
4,400
200
3r100
Ann
500
Fluoride
Content
1r400
100
300
100
270
2.200
100
1,500
.inn
270
1977
Total
Hazardous
Wastes
3,300
300
600
300
600
5,100
300
3.600
Ann
600
Fluoride
Content
MQO
100
34t)
100
30u
2.400
100.
1.700
340
300
1983
Total
Hazardous
Wastes
3,700
400
700
400
800
6,000
400
4.100
700
800
Fluoride
Content
1,800
200
380
200
370
3,000
200
2tQOO
3fi0
370
5-136
-------
Current 1977 1983
dry basis 4,400 5,100 6,000
(4,800) (5,600) (6,600)
moisture 280,000 320,000 300,000
included (310,000) (350,000) (420,000)
The large estimated water content of these wastes is due to
the use of deep-welling (at one plant) which requires a very
dilute slurry for pumping.
5.5^6 Cata.ly.sts (SIC 2,8198L
There are a large number of materials falling into this
category. Generally, most of the industrial catalysts are
prepared in one of two'ways:
(a) the support material (silica, alumina, carbon,
silica alumina or zeolite) is first impregnated
with a solution of the desired metal or metals
salts (Pt, Pd, Rh, Ni, Co, Mo, Cu, V). If the salt
used is thermally unstable, this material is then
merely calcined in air to yield a supported oxide
catalyst.
(b) if the impregnating salt is thermally stable, a
second impregnation with either aqueous ammonia or
caustic soda effects formation of a supported
hydroxide which is then washed and calcined. This
material is then generally packaged and shipped as
is to the user. If the user desires the metal and
not the oxide, hydrogen reduction is normally
carried out at the user's facility.
The exception to the above rule is with the noble metal
systems (Pt, Pd, Rh). These are generally reduced with
hydrogen at the manufacturers plant. In these cases, also,
the impregnating salt is generally not first converted to
the oxide, but, rather, is directly reduced to the metal.
Contacts with a number of manufacturers of these materials
have revealed that most of the off-batches and spilled
materials are collected and sold for scrap value. Only
small amounts of oxide materials arising from spillages are
wastes, and these are generally insoluble and nonhazardous.
Flow diagrams for supported metal and metal oxide catalysts
are given in Figures 5-73 and 5-74.
5-137
-------
METAL
, V,
AS A SALT IN
MATERIAL
AMD
v&vr
^ REDUCTION (—"H PACK A QIUQ
SILICA
CARBOfi
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SPILLAGE S0LID5
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WATER 45 SUPP&
OR
"-(
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LIQUID
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OR 5£LL
OATALY
PRODUCT
(5-IS*> ACTl\
MATERIAL
PRODUCT
AMD VACUUM
. \ METAL (A^
MISC.
LAUOFILL
MANUFACTURE OF SUPPORTED METAL
CATALYST MATERIALS
-------
AS A
9*?-/<&%? -
, SUPPORT
w i MATE/&AL:
£ ALUMIMA
.«- , SILICA
CAA8QU
ZEOLITE
CAVST/C SQOA
KAM&KXJIOM
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PRECIPITATION
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MISC. TXASH 45
DISPOSAL:
DISCHARGE
OK 5£LL S&L/DS
LANDFILL
OK
MANUFACTURE OF SUPPORTED METAL
OXIDE CATALYST MATERIALS
-------
5^5^..! Aggregate of Hazardous Wastes from SIC 28198
Destined for Land Disposal
No problems of hazardous wastes destined for land disposal
were found from the manufacture of inorganic catalyst
materials. The practice of reclaim of metals is followed
throughout this industry.
5^.5^6^2 Projection of Hazardous Wastes from SIC28198
Destined for Land Disposal
No process changes are anticipated in this industrial
segment that would generate land-destined hazardous wastes,
nor are air and water regulations expected to do so.
5_i5±2 Other Industrial Inorganic Chemicals^ Not Elsewhere
Classified (SIC 28199)
5jLJLt2_..i Activated Carbon
As shown in Figure 5-75, activated carbon and charcoal are
prepared by calcination of material products (coconut
shells, etc.). The by-product gases from these operations
are normally combusted. All wastes are waterborne, none are
land disposed.
5_.i5_2.2.r2 Ammonium Compounds
Ammonium hydroxide is made by dissolution of ammonia in
water under pressure. There are no solid wastes generated,
and other wastes consist only of spills or bottle breakage
of ammonia solution. A flow diagram is shown in
Figure 5-76.
Ammonium chloride is recovered as a by-product from Solvay
process soda ash manufacture. There are no hazardous wastes
generated. The flow diagram is given in Figure 5-77.
SiS-.I.iJ Arsenic Oxides (As2Q3)
This material is produced as shown in Figure 5-78. Flue
dusts from copper smelter operations are collected by bag
filtrations and electrostatic precipitators from smelter
vent gases. These dusts are then roasted to sublimate
arsenic oxide, which is then collected in cooled chambers.
All vent gases from this process are subjected to bag
filtration and electrostatic precipitation systems and all
dusts collected are recycled to the process. No hazardous
wastes are generated.
5-140
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ILi.sLsJ.di S§riujn
Barium salts are made directly or indirectly from barite
ores which are first reduced to sulfide. The sulfide is
then converted to other salts by chemical reaction. For
example, reaction with either soda ash or CO2 under pressure
is used to produce the carbonate. The flow diagram for this
is shown in Figure 5-79. Reaction with sodium sulfate is
used to make purified BaSOU.
Most of the wastes from all of these processes are water-
borne and barium is removed from them by precipitation as
the sulfate. Sulfide wastes from these processes are also
largely waterborne and are treated either by aeration or
chemical precipitation with iron salts. The iron sulfide
(formed in the latter case) is insoluble and not hazardous.
Treatment by oxidation produces thiosulfates and sulfates in
solution, which are not hazardous. Small amounts of
residual sulfide remain after treatment.
The solid wastes generated by these processes are barium
sulfate (which sometimes is reused) and, in some cases,
insoluble iron sulfide. These are not hazardous and
Appendix A discusses these constituents.
5.5.7.5 Beryllium compounds
There are three beryllium compounds produced commercially:
the hydroxide, the oxide, and the metal. Only two U.S.
facilities are involved. Beryl ore (beryllium
aluminosilicate) is leached with sulfuric acid to dissolve
the aluminum and beryllium contents. A solid waste of inert
silica results here, but this waste is non-hazardous. Next,
the solution of aluminum and beryllium sulfates is partially
evaporated causing the aluminum sulfate to crystallize out.
This material is then collected, slurried with water, and
discharged as a waterborne waste. The beryllium sulfate
solution is reacted with caustic to precipitate Be(OH)2A
which is then recovered as product. The sodium sulfate
formed is discarded as a waterborne waste. The flow diagram
is given in Figure 5-80.
To produce the oxide, the hydroxide is redissolved in
sulfuric acid, treated with purification agents to remove
iron salts as a solid waste (FeS) , reconverted to the
hydroxide, and calcined. The remainder of the wastes are
water-borne. The flow diagram is shown in Figure 5-81.
In the production of beryllium metal, the hydroxide is first
converted to ammonium beryllium fluoride, which is pumped,
and decomposed to BeF2. The fluoride is then recovered as a
5-145
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(DRY BASIS)
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3,140 ALUM
(TO LAGOON)
WASTE LIQUOR
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(TO LAGOON)
FIGURE 5-80
BERYLLIUM HYDROXIDE MANUFACTURE
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solid and reacted in a furnace with magnesium. The product
metal is then separated from the magnesium fluoride co-
product which is discarded as a solid waste. This
operation, however, is non-ferrous metallurgy—not included
in SIC 281.
Current practice in the industry (based on plant visits)
appears to involve lagooning of all of the wastes listed
above. Lagoon effluent waters are lime treated to minimize
discharge of fluorides. There is no "significant11 amount of
beryllium compounds in the water-borne effluent. The
properties of beryllium, beryllium oxide, and beryllium
hydroxide are discussed in Appendix A. There are only two
plants involved, and the hazardous wastes are the fluoride
associated with beryllium metal production, which is not
SIC 281 product operation.
JL±.5.s_7.. 6 Boron Halides
Boron trichloride is produced by reaction of chlorine, coke
and boric oxide. The product emerges from the reactors as a
gas, is purified, compressed, and packaged. The only wastes
generated are a small amount of boric oxide from the reactor
cleanout and from the scrubbing of vent gases. The latter
are waterborne and the former are not hazardous.
Figure 5-82 is a flow diagram for the chloride manufacture.
Currently there is only one producer of boron trifluoride.
The details of the process in use are therefore proprietary.
Hence no flow diagram is furnished. This process in general
is the reaction of fluosulfonic acid and boric acid. The
by-product is 99-100% sulfuric acid. All wastes associated
with the process are in liquid form. This information was
furnished by the manufacturer. Based on this it is judged
that all wastes are discharged to water, and none are land
disposed.
5.5.7.7 Bromine and Iodine
These chemicals are extracted from natural brines. In both
cases chlorine gas is added to natural brines and this
effects oxidation from iodide and bromide ions to free
iodine and bromine. These are then air stripped from the
chlorinated brine. There are no associated wastes as the
spent brines are returned to their sources as shown in
Figures 5-83 and 5-84. This constitutes effective recycle
of wastes.
1 5-149
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5.5.7A8 Calcium Compounds
Calcium carbide is produced by thermal reaction of lime and
coke in one of two varieties of furnace. In the case of the
closed furnace, wastes arise from the use of wet dust
collection equipment on the vent gases. The materials
collected by dry collection equipment consist of lime and
coke and are recycled. In the case of open furnaces, wet
scrubbing or dry collection can be employed for the vent
gases. This is shown in Figure 5-85. None of these wastes
are hazardous.
As shown in Figure 5-86, calcium carbonate is prepared by
reaction of calcium chloride with soda ash. The process
wastes include significant amounts of unrecovered product
which are settled out of wastewaters in lagoons. These
wastes are not hazardous.
As shown in Figure 5-87, calcium carbonate is also produced.
by reaction of slaked lime with carbon dioxide under
pressure. No significant wastes arise from this process.
Lime (calcium oxide) is made by calcination of limestone in
a continuous verticle or rotary kiln. After calcination,
the calcium oxide is cooled and then packaged or crushed and
screened to yield a pulverized product. It may be slaked by
reaction with water to yield calcium hydroxide. The only
solid wastes produced by either operation arise from the
scrubbing of vent gases to remove particulates. In cases
where dry bag collection is used, some, if not all of the
recovered materials can be recycled to the process. Where
wet collection methods are utilized, solids are frequently
removed from scrubber waters in settling lagoons. These
wastes are not hazardous. The operations are shown in
Figures 5-88 and 5-89.
Calcium chloride is produced either by extraction from
natural brines or recovered as a co-product from Solvay soda
ash manufacture. In the manufacturing of calcium chloride
from brine, the salts are solution mined and the resulting
brines are first concentrated to remove sodium chloride by
precipitation and then purified by the addition of other
materials to precipitate sodium, potassium, and magnesium
salts. The purified calcium chloride brine is then
evaporated to yield a wet wolid which is flaked and calcined
to a dry solid product. Extensive recycling of partially
purified brine is used to recover most of the sodium
chloride values. There are no solid wastes generated by
either process, and the waterborne wastes are not hazardous.
The recovery from natural brines is shown in Figure 5-90.
5-153
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The principal SIC 281 calcium phosphate products are food-
grade and animal-feed-grade materials. The processes are
shown in Figures 5-91 and 5-92. With food-grade calcium
phosphate, high purity phosphoric acid is used and no
hazardous wastes are produced. The only solid waste is
calcium phosphate, an edible material in pure form. In
feed-grade preparation, land disposed wastes in small
amounts containing calcium fluoride are generated. This
material is "moderately hazardous" (see Appendix A for
calcium fluoride) , but the amounts in this waste stream are
BO small that the waste stream is not judged to be
hazardous.
Most commercially produced soluble cadmium salts (chloride,
nitrate, sulfate) are produced by dissolution of the metal
in the appropriate mineral acid, followed by evaporation of
the solution to recover the desired products, ordinarily
there are no solid wastes generated as pure cadmium is the
starting material.
cadmium oxide is produced in a two step process from the
sulfate. First, an aqueous solution of the sulfate is
reacted with caustic and the insoluble hydroxide formed is
recovered by filtration. The hydroxide is then calcined to
the oxide. There are two sources of wastes from this
process:
(a) Spent aqueous solutions from the precipitation
traces of unrecovered cadmium. Treatment of these
will generate minor amounts of cadmium sludges
which exhibit properties described for cadmium
hydroxide in Appendix A. This is a hazardous waste
and requires stringent safeguards to permanently
isolate the material.
(b) Dusts from the calcination process are normally
collected by bag filtration methods and recycled.
If not recycled, cadmium oxide dust is a potential
candidate for land disposal and would require a
secure landfill. The properties of cadmium oxide
are detailed in Appendix A. The wastes mentioned
here are very small and occur only in a few
facilities.
Cadmium sulfide is produced as shown in Figure 5-93. By
reacting a soluble cadmium salt in solution with sodium
sulfide, the product is recovered by filtration. All of the
wastes are initially water-borne, and treatment of these
generates very small amounts of solids (primarily cadmium
hydroxide). Cd(OH)2 is a hazardous material; its properties
5-160
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MANUFACTURE OF ANIMAL-TEED
CALCIUM PHOSPHATE
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CADMIUM SULFIDE MANUFACTURE
-------
are detailed in Appendix A.- • However, the amounts of
material discarded from this industry are so small as to be
insignificant.
JLsJ>&J.s.IO Chromates
This group of materials includes sodium and potassium
chrornate and dichromate and chromic acid, chromic acid is
included because it is made from dichromates in dichromate
plants, although it is in SIC 28194.
As shown in Figure 5-91, sodium dichromate is prepared by
calcining a mixture of chrome ore, soda ash and lime,
followed by water leaching and acidification of the soluble
chromates. The insoluble residue from the leaching
operation is recycled to leach out additional material prior
to being discarded.
During the first acidification step, the chromate solution
pH is adjusted to precipitate calcium salts. Further
acidification converts it to the dichromate and a subsequent
evaporation step crystallizes sodium sulfate (salt cake) out
of the liquor. The sulfate is then dried and sold. The
solutions remaining after sulfate removal are further
evaporated to recover sodium dichromate. chromic acid is
produced from sodium dichromate by reaction with sulfuric
acid. Sodium bisulfate is a by-product.
The bulk of the waste originates from the undigested
portions of the ores used. These materials are mostly solid
wastes contaminated with chromate. The wastes arising from
spills and washdowns contain most of the hexavalent
chromium. The wastes from water treatment and boiler
blowdowns are principally dissolved sulfates and chlorides.
The manufacture of chromic acid contributes no additional
wastes.
The ore residues are contaminated with chromates. There are
chromium-containing sludges from the wastewater treatment
which constitute significantly hazardous waste streams. The
properties of chromates are given in Appendix A.
Chromic acid plants are normally attached to dichromate
facilities. The dichromate is reacted with sulfuric acid to
precipitate chromic acid, which is then recovered by
filtration. The sodium bisulfate by-product is usually
reused in the dichromate plant. This process does not
generate significant amounts of solid waste.
5-164
-------
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FIGURE 5-94
SODIUM DICHROMATE AND CHROMATE MANUFACTURE
-------
As shown in Figure 5-95, potassium dichromate is made by the
reaction in solution of potassium chloride and sodium
dichromate. The solution is then pH adjusted, saturated,
filtered and vacuum cooled to precipitate crystalline
potassium dichromate which is recovered by centrifuging,
dried„ sized and packaged. The mother liquor from the
product centrifuge xs then concentrated to precipitate
sodium chloride which is removed as a solid waste from a
salt centrifuge. The resulting potassium dichromate
solution is then evaporated to recover the product. The
waste solid sodium chloride is contaminated with chromate
saltsf and is considered hazardous.
Chromic Salts
Chromic salts are produced by reaction of chromic oxide
(Cr203) or hydroxide (Cr(OH)3) with the appropriate mineral
acids, followed by evaporation to recover the solid
products. There are no wastes generated by these processes.
5.2.5^7^1.2 Cobalt Cgmgounds
As shown in Figure 5-96, most of these compounds are
produced by reaction of cobalt oxide with the appropriate
acids. Except for small amounts of purification sludges,
v;h:lch are reprocessed to reclaim cobalt values, all of the
waaten are water-borne. There are small amounts of cobalt
in those. No hazardous wastes destined for land disposal
were ;:ound.
Compounds
As shown in Figure 5-97, copper sulfate :is made by reaction
of air,/ copper, and sulfuric acid. Either concentrated or
dilute acid may be used. In general, the resulting solution
is exposed to evaporation and a series of crystallization
steps to obtain copper sulfate crystals, which are then
ceutrifuged, air-dried, screened, and packaged for sale.
The only solid wastes directly generated by the process are
normally recycled to recover their copper values. A small
amount of solid waste does arise in some cases due to
treatment of wastewater from spills and leakages. This
waste consists of small amounts of copper oxide but is
insignificant in amount. Copper oxide properties are
dincussed in Appendix A.
Cuprous oxide is made by reaction of copper with air in a
furnace or series of furnaces to form cupric oxide. The
cupric oxide is then reduced in another furnace to cuprous
oxide. Solid wastes are generally collected by bag
filtration of vent gases and are recycled to the process. A
5-166
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second method of production involves the anodic oxidation of
copper in saline solutions. No solid wastes are generated
in this case. Small amounts of water-borne wastes occur.
The flow diagram is shown in Figure 5-98.
Siltlili Fluorine
Most of the U.S. production of fluorine is produced in
security classified amounts for the AEC. As shown in
Figure 5-9 9 , fluorine is produced by either electrolysis of
molten potassium acid fluoride or liquid HF. Solid wastes
may result from treatment of water-borne wastes , but no
significant instances were found. Waterborne wastes are
discharged or recovered. Future changes in process waste
treatment involve the manufacture of HF solution for sale
with the waste fluorides. Where caustic potash is used to
scrub fluoride gases, the resultant potassium fluoride is
recovered. This industrial segment was therefore not found
to be a generator of hazardous wastes for land disposal.
5...5..7.S..15 SYdrogerj Peroxide
Hydrogen peroxide is manufactured at six locations in the
U.S. and a plant is on stand-by at a seventh. The principal
method of manufacture (5 of the 6 producing plants) uses a
cyclic organic process involving hydroquinone derivatives,
as shown in Figure 5-100, called the "Reidl-Pfleiderer
Process". No hazardous wastes are land disposed from this
process.
The electrolytic process for hydrogen peroxide manufacture
is based on sulfuric acid and ammonium sulfate raw
materials. This process is operated at only one U.S.
location, in the state of Washington, contacts with
industry have indicated that no new plants of this type are
likely to be built. The plant brought off-stream in recent
years to stand-by in Michigan is of this type. So far as is
known there are no plans to remove the remaining operating
electrolytic plant from production, but as its equipment
becomes obsolete at some time in the future there is high
likelihood that it would be. The process steps are shown in
Figure 5-101. The sole land disposed hazardous waste is
small quantities of iron cyanide compounds as sludges. It
is estimated that less than 1.5 metric tons per year of
these sludges are so disposed at this sole location. See
Appendix A for properties of iron cyanides.
5-170
-------
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CUPROUS OX IOC MANUFACTURE.
-------
ELECTROLYSIS OF LIQUID HYDROGEN
FLUORINE
CAUSTIC VENT
SOLUTION 53 HYDROGEN
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HF RECYCLE
1053 LIQUID HYDROGEN FLUORIDE
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FIGURE 5-99
FLUORINE MANUFACTURE
-------
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HYDROGEN PEROXIDE MANUFACTURE
BY THE RIEDL-PFLEIDERER PROCESS
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1L.5.J7..J6 Hypo phosphates
Hypophosphorous acid and its salts are derived from
treatment of elemental phosphorous with a boiling slurry of
lime. In addition to calcium hypophosphite (which remains
in solution) insoluble calcium phosphate is formed along
with phosphine (PH3) and hydrogen. The reactions which
occur are highly complex. The excess calcium hydroxide is
precipitated as carbonate and filtered from the solution.
The solutions are evaporated to give a calcium hypophosphite
intermediate product which is generally redissolved in water
and reacted with sodium sulfate to yield a solution of the
desired sodium salt. This solution is filtered to remove
the calcium sulfate co-product and evaporated. According to
the manufacturers contacted, the wastes from these processes
consist of the following:
(a) Calcium sulfate from the conversion of the calcium salt.
This is non-hazardous.
(b) Calcium carbonate from the lime removal step. This also
is non-hazardous.
(c) A calcium phosphite mud consisting of about 92 percent
(dry basis) CaHP03.2H20, with lesser amounts of other
phosphite salts present. This mud is the principal
waste-being generated in amounts of about 2.5-3 tons per
ton of product. This waste is not considered to be
hazardous.
(d) A gaseous waste containing hydrogen and phosphine.
Combustion of this gas stream yields a gas containing
phosphoric acid vapors which must be removed by wet
scrubbing prior to venting to the atmosphere. Chemical
treatment of this water-borne waste with lime yields
calcium phosphate as another non-hazardous solid waste.
S^S-J..!? Iron Compounds
Ferric chloride is made by the reaction of iron, spent
pickle liquor and chlorine. For technical solution grade
product there are no wastes. For higher product grades,
there are sludges produced from filtrations. However, these
consist of iron and iron oxide and are not hazardous. The
flow diagram is shown in Figure 5-102.
As shown in Figure 5-103, ferrous sulfate is recovered as a
co-product of sulfate process titanium dioxide production.
All wastes are associated with the TiO2 production, which
was discussed with SIC 2816.
5-175
-------
10
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SiS^Iil § Lead Compounds (Other Than Pigments)
The manufacture of lead oxides was described earlier in the
pigments section. Lead silicate is produced by two methods:
(a) Reaction of sodium silicate in excess in aqueous
solution with soluble lead salts. Here, the product is
recovered by filtration and all wastes are water-borne.
Due to the extreme insolubility of lead silicate, water-
borne wastes contain only trace amounts of lead.
(b) Thermal reaction of lead oxide and silica in a furnace
process. Here all wastes are air-borne and consist of
dusts which are recycled to the process.
Lead nitrate is manufactured principally from scrap lead
battery plates as shown in Figure 5-101. Lead and antimony
residues are disposed of as a by-product. No hazardous
wastes destined for land disposal are generated by this
process due to recovery of residues and by-products.
^a.5.,7^19 Lithium Compounds
Lithium compounds are produced by two methods:
(a) Extraction from brines. A number of materials are
recovered from Searles Lake brines by a series of
evaporation and recovery processes. Among these are a
lithium phosphate which is converted to LiCO3 for sale.
All of the wastes from these operations (consisting
largely of unrecovered salts) are returned to the brine
source. There are no hazardous wastes; all wastes are
recycled.
(b) By recovery from Spodumene Ore as shown in Figure 5-105
and 5-106. The ore is first roasted and then leached
with sulfuric acid to recover lithium sulfate. This is
then converted to LiC03 by reaction with soda ash.
Sodium sulfate is recovered as a co-product. The LiCO3
is then converted to other lithium salts by reaction
with the appropriate mineral acids. The wastes from
these processes consist of ore gangues (which are non-
hazardous) and water-borne wastes containing alkali and
alkaline earth sulfates. These also are not hazardous.
SiSiTj-JO Magnesium Compounds
Magnesium carbonate is produced from dolomitic limestone by
the following process: dolomite is calcined to yield a mix-
ture of lime and MgO. This mixed material is then reacted
with water and CO2 to yield an aqueous solution of magnesium
bicarbonate and a solid calcium carbonate phase. The
calcium carbonate is then removed by filtration and dis-
'5-178
-------
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carded as a non-hazardous solid wastei The magnesium
bicarbonate solutions are then boiled to convert the
bicarbonate to carbonate which is then recovered by
filtration.
Magnesium oxide is produced by calcination of the pure
carbonate. No hazardous solid wastes are produced here.
As shown in Figure 5-107r magnesium sulfate is produced by
reaction of the oxide or carbonate with sulfuric acid. The
product is then recovered by evaporation.
Magnesium chloride is produced by two methods:
(a) As a cc-product of K2S04 manufacture from langbeinite
ore or from K^SOjj recovery operations at Great Salt
Lake. In these cases, no hazardous wastes are produced.
(b) By recovery from sea water. Here, sea water is first
treated with lime to effect precipitation of magnesium
hydroxide. This material is recovered by filtration and
then reacted with HC1 to yield a hydrated magnesium
chloride. The hydrated material is then heated in an
HC1 atmosphere to yield an anhydrous product. From
these operations all wastes are water-borne and non-
hazardous after treatment.
1&JL2.&2.1 MlDa§DJ§e Compounds
As shown in Figure 5-108, manganese sulfate is produced as a
co- product in hydroquinine manufacture which involves the
oxidation of aniline with manganese dioxide (present as
pyrolucite manganese ore) and sulfuric acid. All of the
wastes from the process are water-borne and, while
wastewater treatment does generate some solids, these are
not hazardous. In addition, they are principally
attributable to hydroquinone manufacture which is not an
SIC 281 product operation.
Manganese dioxide is produced by oxidation of manga nous
salts. The product is separated by filtration and there are
no hazardous wastes produced.
5_r5i2i22 Mercury (Redistilled)
Redistilled mercury is obtained by the redistillation of
mercury initially produced by retorting cinnabar ore. In
this process, there 'are small amounts of solid waste (metal
impurities in the crude mercury) which are recovered from
the stills. These materials are generally recovered and
reprocessed for their precious metal values.
5-182
-------
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Ls.5i2.t23 Mercury compounds
Mercury oxides are made by three processes- , each of which
generate some mercury bearing wastes that are recycled.
These processes are shown in Figures 5-109 and 5-110. The
mercury sulfide from waste water treatment is relatively
pure and it is recovered for the mercury present and not
disposed of as a waste.
The first process involves reaction of mercuric chloride
with caustic soda in aqueous solution. The product yellow
mercury oxide, is recovered by filtration, washed, calcined
and dried. Treatment of the wastewaters with sulfide
produces some mercury sulfide as a solid waste, which is
recycled.
The latter two processes produce the red oxide of mercury.
In the second, mercurous nitrate is calcined to give the
oxide. Nitrogen dioxide gas is formed as the co-product.
Scrubbing of vent gases with alkaline solutions generates a
wastewater stream which contains minor amounts of mercury
compounds. Sulfide treatment of this stream will also
produce minor amounts of HgS, which is recycled.
In the third process, mercuric chloride and soda ash are
reacted in hot aqueous solution. The product precipitates
and CO2 is liberated as a gaseous co-product. The mercury
oxide is then recovered by filtration, washed, and dried.
The wastewater here is also treated to remove mercury as the
sulfide, which is recycled.
Calomel (mercurous chloride) is produced by reaction of
mercury with chlorine, as shown in Figure 5-111. The
product is thoroughly washed to dissolve any bichloride
formed along with the calomel, and is then dried and
packaged. There are two sources of waste:
(a) Scrubbing of the vent gases from the reactor produces a
water-borne waste which may contain mercury salts.
Treatment of this waste stream will effect precipitation
of a very small amount of mercury sulfide which will be
a solid waste that is recycled.
(b) The washwaters used to remove bichloride of mercury from
the product contain considerable amounts of this
material. These are not wasted but are evaporated to
recover a co-product, as is shown.
Bichloride of mercury (HgCl2) is produced by reaction of
mercury with excess chlorine. The product is recovered as a
solid and packaged. The only wastes arise from scrubbing of
5-185
-------
370
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the gaseous effluent. This yiilda ft wastewater from Which a
very small amount of mercury 40 removed by eulfide
precipitation, which is recycled.
The major constituent of solid traates from ail these process
wastewaters is HgS, The concentration is such that the
overall properties of the Wants ate the same as those
described for pure Hgfl (Appehdia A) . Stringent safeguards
to protect against environmental contamination are required*
No instance was found in which these wastes were hot
recycled rather than land disposed.
Nickel sulfate is made by teaction of nickel oxide with sUi-
furic acid as shown in Figure 9-*1l2. In some cases* the
oxide is generated on^ site by treatment of spent nickel
plating solutions* Solid wastes ate produced ftoiH
filtration of product solutions prior to evaporation* the
amounts of these solids are small and they ate Usually te-
processed to reclaim nickel Valued. There ate also small
amounts of solids generated by waatewater treatments*
However, these materials (nickel oxides) are generated itt
Very small quantities at only a few locations 4
Nickel hydroxide and nickel hydroxide wastes are not ae
severely hazardous as cadmium, mercury, chromium* etc* |
however, it is not an inert material (e.g. • eilioaj or a
generally non-hazardous material (e.g., calcium sUlfate or
sodium chloride). Ni(oH)2 is a borderline material between
severely hazardous and moderately hazardous materials* Its
properties are described in Appendix Aj and safeguards to
prevent migration of the waste ftom land disposal sites ate
required.
Nickel ammonium sulfate id prepared by evaporation of
aqueous solutions to which the two sulfates have been added*
There are no land destined wastes produced here*
Nickel carbonate is produced by reaction of a soluble nickel
salt (i.e. NiSO4) in water with soda ash. The insoluble
product is recovered by filtration. No land destined wastes
are produced.
5^5. 7 « 25 Phosphorus
This material is produced ad shown in Figure 5-113 with
minor variations by thermal reaction of coke, silica, and
phosphate rock. The product PU distills from the mixture
and is collected in water. There are several possibly
hazardous wastes involved:
5-189
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(a) The furnace slag and dusts collected from the process
are usually wasted. These contain considerable amounts
of fluorides as well as radioactive material such as
uranium oxide. Leaching data from industry shows that
the ceramic nature of phosphorQa production furnace
slag effectively binds the potentially hazardous
constituents (fluorides and uranium oxide) so that
migration of hazardous constituents from the waste does
not occur upon land disposal, hence this is not hazardous,
(b) Waters containing unrecovered colloidal phosphorus are
frequently treated to recover this material, some of
which may not be suitable for use as product.
The properties of colloidal phosphorus are discussed in
Appendix A. Phosphorus containing wastewaters are
hazardous to both plants and animals.
(c) Scrubber water treatment produces pond sediments
containing calcium fluoride, other calcium salts
including calcium phosphate, silicates, and variable
amounts of colloidal phosphorus. Colloidal phosphorus
and calcium fluoride are the potentially hazardous
constituents. Calcium fluoride comprises roughly 10
percent of the total wastes (w/w dry basis) and
colloidal phosphorus comprises 8 percent (w/w basis) or
higher in some instances. The properties of both waste
constituents are described in Appendix A. The
concentration of these constituents in the waste is
sufficient to require stringent safeguards upon land
disposal.
5.5.7.26 Phosphorus Oxides. Sulfides. and Chlorides
As shown in Figure 5-114, phosphorus pentoxide is made by
burning of phosphorus with oxygen followed by condensation
of the formed product. Small amounts of calcium phosphate
(which is not severely hazardous) are formed from wastewater
treatment. Periodically there are minor amounts of
phosphoric acid-contaminated brick to be disposed of.
As shown in Figure 5-115, phosphorus pentasulfide is made
by reaction of phosphorus and sulfur. The wastes from
reactor water seals, still residues, and dust collection
equipment are arsenic sulfide, phosphorus, phosphorus
trisulfude, phosphorus pentasulfide dust, glassy
phosphates, iron sulfide, and carbon disulfide. This
constitutes a hazardous waste stream. The properties are
described in Appendix A. In addition to the potential
environmental hazards, the reactivity of this waste
necessitates special handling. The P2S5 waste constituent
results from equipment cleanout.
5-192
-------
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PHOSPHORIC
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PHOSPHORUS PENTOXIDE MANUFACTURE
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As shown in Figure 5-116, phosphorus trichloride is made by
reaction of phosphorus with chlorine. For the normal
process there is no solid waste, but in the case of a high
purity product, purification is achieved by fractional
distillation which leaves behind small amounts of the
hazardous waste, arsenic trichloride. Its properties are
detailed in Appendix A.
As shown in Figure 5-117, phosphorus oxychloride is
produced by reaction of PCI3, P2O5, and chlorine, followed
by fractional distillation to recover the desired product.
No hazardous wastes are generated.
5.5.7^27 Potassium Permanganate
As shown in Figure 5-118, this compound is produced from
manganese ore (MnO2) by a rather complicated process
involving oxidation of the manganese in the ore to manganate
followed by electrochemical conversion to the permanganate.
There are solid wastes generated in the form of ore
residues, but these consist largely of insolubles such as
silica and are non-hazardous.
5.5.7.28 Radioactive Chemicals
There are small amounts of a wide variety of isotope
labelled compounds produced in the U. S. by a few
manufacturers. The processes involved in these cases are
the normal ones, except that isotopically pure starting
materials are used. In cases where the isotopes in question
are radioactive, regulations established by the AEC are
followed in disposal of wastes. The amounts of these wastes
are very minor.
5^5.7.29 Selenium and Tellurium
These products, along with tellurium dioxide are recovered
from copper smelter flue dusts. The dusts are processed to
recover copper and precious metal values and are then
leached with alkaline solutions to dissolve the selenium and
tellurium salts present. These solutions are then
reacidified. Tellurium dioxide precipitates, with part
being recovered for sale and the remainder treated with SO2
to form selenium, which is recovered by filtration as a
product.
The majority of the wastes from this process are
water-borne. Most of the solids removed by the various
filtration steps are reprocessed to recover metal values.
The only hazardous materials which are not recycled are
various wash and process waters which may contain traces of
5-195
-------
773 CHLORINE
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selenium, chemical treatment of these with iron salts
removes selenium as the insoluble selenide. Only four
plants are involved* and the amounts of selenium-bearing
wastes are very small and economically insignificant* The
properties of selenium and selenides are discussed in
Appendix A.
{LSJL&2&1S Silver. Compounds
Silver nitrate, the only large volume silver compound
production , is made by the reaction of silver with nitric
acid. The process is shown in Figure 5-119. The only solid
wastes generated are heavy metal-containing sludges from
filtration steps and solids recovered from wastewater treat-
ment which contain the following hazardous constituents}
silver, mercury, cadmium, and lead. The properties of these
are discussed in Appendix A. Due to the high cost of silver
most of these materials are reprocessed and not discarded.
5^5.7.31 Strontium Compounds
Strontium compounds are made in a manner similar to that for
barium compounds (discussed earlier) and in the same
facilities. The flow diagram for strontium carbonate is
shown in Figure 5-120. The barium sulfate and strontium
sulfate containing wastes that are land disposed are not
hazardous.
Lt5j.7j.32 Sulfur Dioxide
This product is made by the burning of sulfur in air as
shown in Figure 5-121. The combustion products are cooled*
dried, and filtered, then compressed and cooled to liquefy
the gas. No hazardous wastes are generated, and no wastes
are disposed of on land.
S...5..7...33 Sulf ur Chlorides ISCl^ and S2C121
As shown in Figure 5-122, these compounds are produced by
reaction of sulfur and chlorine under controlled conditions*
All of the wastes are due to the scrubbing of tail gases
with alkaline waters and are non-hazardous.
Sulfur Oxychl grides
Thionyl chloride (SOC12) is made by two producers, each of
which employs their own patented process. In the first,
sulfur monochloride (S2C12) is reacted with chlorine and
sulfur trioxide in the liquid phase in the presence of an
antimony trichloride catalyst under pressure. The thionyl
chloride is then separated by distillation from the catalyst
5-199
-------
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and the 802 co-product. The only potentially hazardous
solid wastes produced are spent catalyst (Sbcl3)
contaminated with products and react ants* This material
requires considerable care in handling, but, as the
production of thionyl chloride by this process is limited to
one plant, the quantities involved are very small. The
properties of sbcljf are discussed in Appendix A. In the
second process, phosgene (COG 12) and SOJ are reacted in the
gas phase over a charcoal activated carbon catalyst. The
product, thionyl chloride, is then condensed from the gas
phase, collected, and packaged. The only wastes are spent
activated carbon contaminated with the gases and wastes from
scrubbing the tail gases.
This latter is a water-borne waste, while the former is
generated in very small amounts at only one site and is not
judged to be present in hazardous amounts.
Bu.lfuryl ££!Q£ide (302C12.1
Sulfuryl chloride (SO2C12) is produced by gas phase reaction
of so 2 with chlorine. The product is separated from the gas
phase of condensation. The only wastes arise from tail gas
scrubbing operations and from the catalysts used. Hone of
these are judged to be hazardous* Flow diagrams for these
sulfur compounds are given in Figure 5-123.
5i5.sJ.tlll Thallium Co
These items are produced at only one facility in the 0. 8.
using lead and zinc smelter flue dusts as a starting
material. Specifically, the dusts are first dissolved in
sulfuric acid and the lead and zinc values are collected and
reused. The purified solutions are then electrolyzed to
recover a cadmium- thallium alloy, from which the thallium is
selectively leached. The leachate is then converted to
thallic sulfate solutions, part of which is used to recover
a solid salt product and the remainder being electrolyzed to
recover the metal (a non-ferrous metallurgical process not
in sic 281).
The only heavy-metal-salt-corttaining wastes, which are not
reprocessed internally, consist of the very dilute spent
electrolysis solutions, a waste not attributable to SIC 281.
These are generally given chemical treatment to remove the
small amounts of heavy metal salts, and then landfilled.
The heavy metals involved in this small waste are the oxides
and hydroxides of such metals as cadmium and lead. Their
properties are detailed in Appendix A.
5-204
-------
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For the production of thallium compounds, other than the
sulfate, the sulfate is first converted to the carbonate as
shown in Figure 5-124 and the carbonate is then recovered
and reacted with the appropriate mineral acid to generate
the desired compound. There are no solid wastes generated
by any of these processes. The total production of thallium
compounds in the U. S. is less than eight tons per year.
5.5.?.35 Tin Compounds
As shown in Figure 5-125, stannous chloride is made by
reaction of tin with hydrogen chloride followed by
crystallization. No wastes are produced.
Stannic oxide is generated by either a dry or a wet process.
The dry process involves calcination of the hydroxide as
shown in Figure 5-126. All dusts are collected from vent
gases via dry collection methods and returned to the
process. The wet process (used by only one company which
considers it proprietary) involves recovery of tin values
from such waste materials as sodium stannate. This material
is then converted to the dioxide. In this second process,
all of the wastes are water-borne. The sludges from
treatment of these wastes are sold for their tin content and
the water-borne waste is discharged. Future plans for this
process call for modification so as to use pure tin instead
of scrap. This will eliminate the need for chemical
pretreatments and, hence, the waste sludge. Thus there are
no present or future hazardous wastes for land disposal.
5^5^.7^36 Thiocyanateg
Alkali metal thiocyanates are produced by reaction in
solution of sulfur with the corresponding metal cyanides.
All of the Wastes generated are water-borne and treated by
either biological or chemical means.
5^5.1.7^37 Zinc Compounds
As shown in Figure 5-127, zinc sulfate is made by reaction
of zinc oxide with sulfuric acid. The zinc oxide is leached
with sulfuric acid and filtered to remove insolubles. This
solution is treated with zinc dust to precipitate metallic
impurities, filtered, evaporated to dryness, and sold as the
monohycrate. Some solid wastes are produced by product
purification steps, but contacts with the industry have
revealed that the wastes are always sold for their lead and
cadmium values and are not discarded.
5-206
-------
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All other zinc salts are prepared by reaction of zinc oxide
or zinc metal with the appropriate mineral acid. The only
wastes are product purification solids which are generally
reprocessed to reclaim lead and cadmium values.
Figure 5-128 shows the typical manufacturing process for
zinc chloride.
5iJL7.._38 Aggregate of Hazardous Wastes From SIC 28199
Destined for Land Disposal
Of the large number of diverse inorganic chemical products
in this industry subcategory, manufacture of the following
products ha 8 been found to generate significant hazardous
waste streams that are disposed of on land:
chromates
iron cyanide compounds
nickel sulfate
phosphorous
phosphorous pentasulfide
phosphorous trichloride
The aggregate hazardous waste streams to land disposal and
the hazardous ingredients contents are given in Table 5-12
on a state-by-state„ regional, and national basis. The iron
cyanide hazardous waste is not given in Table 5-12 because
it is a very small amount (1.5 kkg/yr) at one location
(Washington state, electrolytic hydrogen peroxide manufacture)
5.5.7^.39 Projection of Hazardous Wastes From SIC 28199
Destined for Land Disposal
In both chromates and nickel sulfate manufacture, the impo-
sition of water regulations will bring more chromate-
contaminated solid waste material to land disposal. This
effect together with an estimated 4 percent per year growth
in production through 1983 are the factors on which the
waste projections in these segments were based.
The electrolytic process of manufacture of hydrogen peroxide
will not expand in production volume in years to come since
it is agreed by industry to be an outmoded technology.
Although no plans have been divulged by industry to shut
down the one remaining plant, we estimate that it will be on
standby by 1977 and hence no hazardous iron cyanide wastes
to land are projected from SIC 28199 for 1977 and 1983.
5-211
-------
Ul
I
K)
ro
WATER
A/ 50 CHLORINE GAS »
600 IMPURE
REACTOR
»
REACTOR
^ REACTC
1 1
FILTRATION
— -^ EVAPORATION
)R
-
VENT
-• FILTRATION — * DRYER
,
FILTRATE
1000
PRODUCT
1-10 PURIFICATION SOLIDS FOR
RECLAMATION
(CONTAINS LEAD AND CADMIUM)
FIGURE 5-128
ZINC CHLORIDE MANUFACTURE
-------
Table 5-12. Hazardous Wastes Currently Destined for Land Disposal
From SIC 28199 Other Industrial Inorganic Chemicals,
N.E.C., (metric tons per year, dry basis)
I\f Alabama
X Alaska
IX Arizona
VI Arkansas
IX California
Vill Colorado
I Connecticut
III Delaware
V) Florida
IV Georgia
tt tlawali
X Idaho
V Illinois
V Indiana
VII Iowa
VII Kansas
tV Kentucky
VI Louisiana
I Maine
lli Mary land """ "
I Massachusetts
V Michigan
V Minnesota
IV Mississippi
VII Missouri
VIII Montana
VII Nebraska
IX Nevada
I New Hampshire
II New Jersev
VI New Mexico
II New York
IV North Carolina
VIII North Dakota
V Ohio
VI Oklahoma
X Oregon
III Pennsylvania
I Rhode Island
IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII Utah
I Vermont
III Virginia
X Washington
III West viroinia
V Wisconsin
VIII Wyoming
TOTAL
Region I
II
III
IV
V
VI
VII
VIII
IX
X
Chro mates
Total
Hazardous
Waste
44,000
2.000
3.000
48,000
40.000
160,00?
3.000
/unnn
40,000
2.000 •
Chromium
Content
O.H
0.003
0.007
0.1
0.09
0.34
0.007
0.14
0.1
0,09
0.003
Nickel Sulfate
Total
Hazardous
Waste
O.I
2.0
0.1
0.1
O'.l •"
2.0
0.1
0.3
5.6
0.2
4.6
0.1
0.1
0.3
O.f
Nickel
Content
0.02
0.4
0.02
0.02
0.0} "
0.4
0.02
0.06
0.9 _
0.04
0.8
0.02
0.02
0.06
0.02
Phosphorus and Compounds
Total
Hazardous
Waste
12,600
13.000
81 .OOP
60
13
14,200
10
30
15
]
73,000
7
190.000
40
17
_ 99,000
60
14,200
._ .81,000
Arsenic
Content
0.4
o.«
O.I
0.1
6.5
o.a
0.2
0.1
0.4
3
0.6
0.7
0.8
. 0.9
Fluoride
Content
1,100
1.100
6.900
_
1.200
6,200
16.500
8,400
1.200
6.900
Phosphorus
Content
.140
350
2.200
4.1
1.0
380
0.7
2.1
1.0
2.000
5.300
2.8
1.0
2,700
4.1
380
2.200
26)99
Total
Hazardous
Waste
]?/nn
0.1
13,000
81,000
2
64.000
13
_ 2.000
14.200
.
3.000
30
48.000
2
15
1
73.000
40,000
0.3
2
350.000
3yOOO
64.000
. 150.000
40.000
2.000
14,000
0.1
81.00CL
5-213
-------
Phosphorus and the two phosphorus chemicals, phosphorus
pentasulfide and phosphorus trichloride* were projected on
the basis of a 3.5 percent growth in production through
1033. Air and water regulations will not add to amounts of
land-destined hazardous wastes front phosphorus pentasulfide
and trichloride manufacture*
In phosphorus manufacture, a relatively small amount of
solids will be added to the land-destined hazardous wastes
by the effects of regulations*
The aggregate projections to 1977 are given in Table 5-13
and to 1983 in Table 5-14* The trend in hazardous wastes to
land disposal in SIC 26199 can be summarized in terms of
metric tons per year (short tons per year) as follows:
tsriod SUrjrent 1977 1963
Dry basis 350,000 390,000 (140,000
(390,000) (430,000) (490,000)
Moisture 700,000 800,000 900,000
included (770,000) (880,000) (990,000)
5-214
-------
Table 5-13. Hazardous Wastes Expected to Be Destined for Land Disposal
in 1977 From SIC 28199 Other Industrial Inorganic Chemicals,
N.E.C. (metric tons per year, dry basis)
IV Alabama
X Ala.ika
IX Arizona
VI Arkansas
XX California
VIII Colorado
I Connecticut
III Delaware
IV Florida
IV Georgia
IX Hawaii.
X Idaho
V Illinois
V Indiana
Vil Iowa
VII Kansas
IV Kentucky
VI Louisiana
I Maine
III Maryland
I Massachusetts
V Michigan
V Minnesota
IV Mississipoi
VII Missouri
VIII Montana
VII Nebraska
IX Nevada
I New Hampshire
II Now Jersey
VI New Mex.'.co
II New Yorl;
IV North Carolina
VIII North Dakota
v Ohio
VI Oklahoma
X Oregon
III Pennsylvania
I Rhode Island
IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII Utah
I Vermont
111 Virginia
X Washington
III West Virginia
V Wisconsin
VIII Wyoming
TOTAL
Region I
II
III
IV
V
VI
VII
VIII
IX
X
Chromotes
Total
Hazardous
Waste
72.000
2.000
3.000
54rOOO
45rOOO
180.000
3.0QO
72.000
54,000
45rOOO
2rOOQ •
Chromium
Content
0.15
0.004
0.008
0.11
0.1
0.4
0.018
0.5
b. l
0.1
0.004
Nickel Sulfate
Total
Hazardous
Waste
0.1
2
0.1
0.1
0.1
2
0.1
0.3
6
0.2
4.0
0.1
0.1
0.3
0.1
Nickel
Content
0.02
0.4
0.02
0.02
0.02
0.4
0.02
0.06
0.9
0.04
0.8
0.02
0.02
0.06
0.02
Total
Hazardous
Waste
14,000
15,000
90,000
60
14
16.000
16
30
15
1
81,000
2
220,000
46
17
nn nnn
60
16,000
90rOOO
Phosphorus and Compounds
Arsenic
Content
1.0
0.2
0.1
0.5
0.4
0.2
0.2
0.4
3.0
0,6
0.8
0.6
1.0
Fluoride
Content
1.566 "
1.200
7,700
1,300
6.800
18,000
9 900
1,300
7.700
Phosphorus
Content
370
390
2.200
4.5
1 .1
380
0.8
2.3
1.1
2.000
5,300
3.1
1.1
?,flnn
•4.5
380
2.200
28199
Total
Hazardous
Wastes
14.000
0.1
15.000
90.000
60
2
72.000
14
2.000
!ArOOO
3,000
30
54.000
?
15
1
81.000
45.000
0,3
2
390rOOO
3,000
72.000
.040,000. .
64
45.000
2.000
16,000
0.1
90.000
5-215
-------
Table 5-14. Hazardous Wastes Expected to be Destined for Land Disposal
m 1983 From SIC 28199 Other Industrial Inorganic Chemicals,
N.E.C./ (metric tons per year, dry basis)
IV Alabama
X Alaska
IX Arizona
VI Arkansas
IX California
VIII Colorado
I Connecticut
III Delaware
IV Florida
IV Georgia
iX Hawaii
X Idaho
V Illinois
V Indiana
VII Iowa
VII Kansas
IV Kentucky
VI Louisiana
I Maine
III Maryland
I Massachusetts
V Michigan
V Minnesota
IV Mississipoi
VII Missouri
VIII Montana
VII Nebraska
IX Nevada
I New HainDShire
II New .Terr.pv
VI New Mexico
II New York
IV North Carolina
VIII North Dakota
V Ohio
VI Oklahoma
X Orenon
III Pennsylvania
I Rhode Island
IV South Carolina
VIII South Dakota
IV Tennessee
VI Texas
VIII. Utah
I Vermont
III Virginia
X Washington
III West viroinia
V Wisconsin
VI IT VivomJ.ng
TOTAL
Region I
II
III
IV
V
VI
VII
VIII
IX
X
Chromates
Total
Hazardous
Waste
80,000
3.000
4.000
60.000
Chromium
Content
0.2
0.004
0.009
0.13
1
50.000
200,000
4,060
80,000
60,000
50.000
3.000
0.1
0.4
0.009
0.2
0.13
0.1
0.004
Nickel Sulfate '
total
Hazardous
Waste
0.1
3
0.1
0.)
0.1
3
O.I
0.4
6
0.2
6.0
0.1
0.1
0.4
0.1
Nickel
Content
0.03
b.4
0.03
0.03
0.03
0.4
0.03
0.06
1.1
0.06
0.8
0.03
0.03
0.06
0.03
Phosphorus and Compounds
Total
Hazardous
Waste
' 1 o.OOO
16,000
100,000
80
20
18,000
20
40
20
1
90.000
3
240,000
60
23
120,000
80
isrooo
100rOOO
Arsenic
Content
1.2
Fluoride
Content
1.300
1.400
8,500
Phosphorus
Content
420
440
2,700
5
1
1
0.2
0.1
0.6
0.4
0.3
0.2
0.6
3.6
0.7
1.0
0.7
1.2
i8W •••
Total
Hazardous
Waste
16.000
6.1
16.000
100,000
80
3
80.000
1
1 .4
1,500
470
7.600
20,000
10,000
1.500
8.500
0.9
2.6
1.4
2,400
6.400
3.5
1.4
3.300
5
470
2.700
20
3.000
18.000
4,000
40
60.000
3
20
1
90,000
50,000
0.4
j
440,000
4,000
80.000
180.000
86
50.000
3.000
18,000
0.1
100,000
5-216
-------
6^0 TREATMENT AND DISPOSAL TECHNOLOGY
Land-destined hazardous wastes from the inorganic chemicals
industry, varying from high to low water content, originate
either directly from the manufacturing processes or from air
or water pollution control systems, and are usually in the
form of slurrioa or wet solids. The technology used in
their treatment and disposal depends for the most part on:
(1) The volume of hazardous waste involved. Small volume
wastes can be treated and disposed of by almost any
available technology without major economic impacto
Large volume wastes often are not hazardous, but those
that are can be significant economic impacts upon
treatment and disposal.
(2) The chemical composition of the waste. Both the
hazardous chemicals involved and the concentrations in
which they are found determine the treatment and
disposal technology required,
(3) Geographical location. Both the technology and the
costs for land disposal are more favorable in the dry
portions of western 0.S. than in eastern U.S. Where
rainfall is slight, both liquid and solid hazardous
wastes can be disposed of with less danger of environ-
mental contamination. The numerous isolated, thinly
populated western areas available for hazardous waste
disposal also minimize the effect on the population.
Therefore, treatment and disposal options must be
considered in light of the ambient climate, geology and
population pattern.
(4) Availability of land. Some plants have little or no
on-site disposal space available. This factor
influences both location and methods of treatment and
disposal.
Table 6.0 summarizes the estimates of present distribution
of hazardous wastes currently disposed of on land by the
various segments of the industrial inorganic chemicals in-
dustry. Very small quantities of hazardous materials
originating from atypical plants, (e.g., small volume of
several pounds per year hazardous wastes, residues
containing minuscule heavy metals concentration) are not
included in this table. By their small volume and/or low
potential hazardousness they can usually be disposed of
readily and with small economic impact. These minor
hazardous waste streams are discussed in Section 5.
In the following sections are given brief discussions of the
current treatment and disposal practices in those segments
of the industrial inorganic chemicals industry having
significant hazardous wastes destined for land disposal.
6-1
-------
Table 6-0. Summary of Current Land Disposal
Of Hazardous Wastes
Industry
Subcategory
SIC 28121 Chlorine
total Amount, Dry Basts
. (metric tons per year)
57,000
SIC 28161
SIC 28162
SIC 28163
SIC 28194
SIC 28196
SIC 28197
Titanium
Dioxide
Pigment
White
Pigments
Chrome
Colors
Inorganic
Acids
Aluminum
Compounds
K and Na
Compounds
150,000
240
8,000
1 ,400,000
32,000
4,400
Number and
Type of Plants
Land-Dlspoilng
38 Diaphragm Cell
28 Mercury Cell
5 Down's Cell
8 Chloride Process
1 Antimony Oxide
8 Chrome Pigments
or Chrome Pigments/
Iron Blues Complexes
12 Hydrofluoric Acid
6 Aluminum Fluoride
3 Sodium Silicofluortde
SIC 28199 Others NEC
350,000
3 Chromates
4 Nickel Sulfate
10 Phosphorus
7 Phosphorus Pentasulfide
5 Phosphorus Trichloride
6-2
-------
-------
Nine plants are now using on-site pond storage of sludges
and 7 use on- site landfill. Four plants send wastes to
£niSfrri£$?£iL*0* 2£cure2 landfilling. Several plants employ
combinations of these treatment/disposal technologies ,
chlorinated hydrocarbon wastes from these plants are either
not separated from product streams t separated and used
elsewhere, or drummed for land storage *
fLlil Downls CeJJ, Process
The principal hazardous waste stream from this process that
may go to land disposal is the metallic sludges of sodium
and calcium from the filtration of sodium product* These
materials pose a hazard due td violent reaction with
moisture, producing a possibility of explosion. However at
both plants having this waste to dispose of barging to sea
is used instead of land disposal. The other hazardous Waste
stream that is present at all sodium plants is sodium-
contaminated cell rubble.
It should be pointed out that once this waste material has
been thoroughly reacted with moisture, it is no longer
hazardous in that sense. After reaction with atmospheric
moisture and dissipation of the reaction products, the
rubble waste is no longer hazardous.
6.2 Treatment and Disposal in. Inorganic Pigments Manufacture
1SIC 28J61
Significant amounts of land-disposed hazardous wastes are
generated by several segments of this industry subcategory.
&S.2.2..1 Titanium Dioxide-Chloride Process
Chromium-containing wastes are generated by this process by
solubilizing of ore impurities and subsequent treatments.
Of the nine plants now generating such wastes, one
deep-wells, one disposes at sea by barging, two send the
wastes to contractors for off-site disposal, and U dispose
on land by on-site ponding. The remaining plant is now
discharging these wastes. Prior treatment in some cases
consists of neutralization.
6^.2.^2. Antimony Oxide Manufacture
This SIC 28162 process generates land-disposed hazardous
wastes at only one site. These antimony-rich wastes are
stockpiled on-site at present, waiting for a final use,
presumably by recovery. At present they constitute a waste,
6-4
-------
although in the long run thiti may be partially or completely
eliminated.
6.2.3 ctjroms
The plants and plant complexes manufacturing chrome
pigments, iron blues and cadmium Colors generate land-
disposed hazardous wastes containing lead* chromium, zinc,
cyanide and cadmium hazardous constituents, of the
3 plants land-disposing such wastes, one disposed on-site by
ponding and one by landfill after treatment, which consists
principally of neutralization and precipitation* six other
plants use off-site disposal, one to municipal landfill,
four to secured private landfill, and one to a land dump*
Two remaining chrome pigments plants do hot land dispose,
one claiming to recover all wastes and the other
discharging.
iil Treatment and Disposal jn the Manufacture^ Oj
Miscellaneous Inorganic Chemicals (SIC 28J91
Several segments of this industry subcategory generate
hazardous waste streams that may be disposed of on land.
These wastes are contaminated with one or more of the
following hazardous constituents: arsenic, fluoride,
nickel, and phosphorus (elemental) .
6_-.!il Manvjfacture g£ Inorganic Acids t&tc 2B19U)
Hydrofluoric acid manufacture generates fluoride-containing
hazardous waste streams that are land-disposed. The
principal fluoride constituent is calcium fluoride, which
results from waste treatment by lime neutralization* Of the
12 plants generating such wastes, 6 are known to Use on-site
ponding disposal, 2 to use contractor general purpose
landfills and one to send to a contractor Who uses it for
roadfill. The remainder is unknown.
Boric acid manufacture in only one location Uses a process
that generates wastes that go to land disposal. This waste
is arsenic sulfide from product purification and wastewater
treatment by sulfide precipitation. The Waste is sent to
secured municipal landfill.
6.3.2 Aluminum Fluoride
This SIC 28196 product is manufactured by a process that
generates fluoride wastes. Waste treatment by liming
produces calcium fluoride-containing hazardous waste streams
for land disposal. One plant uses a unique proprietary
6-5
-------
process that generates no wastes of this sort. Of the
remainder, U plants use on-site disposal by ponding or
dumping and one uses a general purpose municipal landfill*
6jJil sodium, silicofiuorid.e
The manufacture of this SIC 28197 product generates
fluoride-containing land-destined Wastes similar to the
foregoing. Of the 3 plants generating such Wastes, one is
known to deep-well the fluoride Waste and one UseS on-site
pond disposal. The other is unknown*
6-s.lil Chrgmates Manufacture
Chromate-contaminated land-destined hazardous wastes ate
generated by the manufacture of these SIC 28199 products in
3 locations. One plant disposes of the chrome ore gangue
off-site to a contractor for land and road construction
purposes. One uses on-site land dumping and another uses
approved private landfill.
liJiS Nickel Sulfate
Nickel-containing hazardous wastes for land disposal in
relatively small amounts are generated by the manufacture of
this SIC 28199 product. They result from the treatment of
wastewaters by raising the pH to precipitate metallic salts.
Two plants in this segment directly sewer their Wastes. One
plant uses on-site landfill for the precipitates, and
another uses contractor landfill (general purpose)*
Furnace Process
Ten plants manufacturing this SIC 28199 product produce
fluoride- and phosphorus-containing hazardous waste streams.
These are universally disposed of on-site. The wastes
result from water treatment. The phosphorus-containing
wastes are settled on the bottom of storage ponds. Most
plants endeavor to recover as much of the phosphorus as
possible, although significant amounts remain. The fluoride
wastes from scrubber water treatment are also settled in
ponds. The fluoride is principally in the form of calcium
fluoride from reaction with lime.
iilil Phosphorus Pentasulfi.de
Several plants making this SIC 28199 product report no land-
destined wastes. Treatment and disposal for these wastes,
which are arsenic sulfide, phosphorus and phosphorus
compounds, are specific to each company and the disposal
technology is in a state of flux. Four plants presently
6-6
-------
landfill these wastes on-sitej the other plants are dttittt
storing their wastes pending further developments.
The arsenic trichloride waste from the purification of this
28199 product is generated in relatively small amounts* one
plant uses on- site drum storage and two Use on- site land
dumping* several plants report no land-destined hazardous
wastes. The treatment and disposal of these wastes are also
in a state of flux, and these latter plants are drum storing
their wastes pending further developments.
iil Treatment and Disposal TechfiQigaX teyels as.
Hazardous Wastes Geji§£ateg fey. tjie Manufacture gf
Spgcific chemicals
The following Tables 6-1 through 6-13 provide information on
three identified levels of technology and disposal of haz-
ardous wastes from the inorganic chemicals industry* These
levels are characterized as follows:
Level I - Technology currently employed by typical facili-
ties; i.e., broad average present treatment and disposal
practice.
Level II - Best technology currently employed. Identified
technology at this level must represent the soundest process
from an environmental and health standpoint, currently in
use in at least one (1) location. Installations must be
commercial scale; pilot and bench scale installations are
not suitable.
Level III - Technology necessary to provide adequate health
and environmental protection. Level 111 Technology may be
more or less sophisticated or may be identical with Level t
or II Technology. At this level, identified technology may
include pilot or bench scale processes providing the exact
stage of development is identified.
The treatment and disposal of hazardous wastes from
industries such as chlor-alkali. Sodium, chrome pigments,
iron blue, nickel sulfate, Kind chloride, sodium sulfides,
titanium dioxide, and phosphorus chlorides and sulfides are
currently in a state of flux and will change in the near
future.
The large volume land-destined wastes that are no
particular hazard and are presently land dumped and land-
filled on- site will probably Will continue being disposed of
in much the same fashion.
6-7
-------
Table 6-1 . Chlor-AI kali-Diaphragm Cell Process
i
GO
Factor
Physical and Chemical
Properties of
Residual Wastes
Amount of Residual Wastes
(kg/ltkg product)
Factors Affecting
Hazordousness
Treafment/Di sposal
Technology
Estimate of Number and
% of Plants Now Using
Technology
Level I, Prevalent Technology
Solids - Lead hydroxide or sulfide •
Asbestos fibers as slurry
Liquids - Chlorinated hydrocarbons,
where separated
Approx. 1
Solubility of lead compounds changes with
pH. Burning of hydrocarbons con result in
explosions and air pollution if not properly
done.
1. Pond storage of lead precipitateSjOsbestos;
burning of hydrocarbons.
2. Landfill lead precipitates and asbestos
hydrocarbons not separated from product.
Approx. 19 plants (50%)
Adequacy of Technology Not adequate for future
Level II, Bast Available Technology
Some as Le /el I
Approx. 0.1
Same as Le 'el I
1. For trios • with carbon anodes: landfilling
2. For thos t with coated metal anodes: lead
waste eliminated by in-process change;
landfill! ig of asbestos; burning or recov-
ery of c- ilorinoted hydrocarbons(if any).
Approx. IS plants (50%)*
Not adequ ite
Level III, Adequate Health and Environmental Protection
Same as Level I
Same as Level II
Same as Level I
Same as Level II, except use approved landfill for
asbestos and secured landfill for lead wastes.
None
Not proven
Non-land Environmental
Impact
Problems and Comments
Compatibility with
Existing Facilities
Monitoring and Sur-
veillance Techniques
Installation Time for
New Facility
Energy Requirements
Possible ground and surface water contami- Same as L ivel I
nation from lead and asbestos
Lead and asbestos wastes should be reduced Same as Le- -el I
as new process technology of coated metal
anodes and plastic cell membranes advance. \
No process changes envisioned Same as Le' pel I
None practiced Some as Le -el I
Installed Installed
Slight - trucks and bulldozers for landfill. Same as Le' 'el I
None
Same as Level I
Same as Level I
Surface and groundwater monitoring for
landfllllng leachate. A1r pollution
monitoring for burning chlorinated
hydrocarbons.
One year
Some as Level I
*No further breakdown available since plants are presently converting fron carbon anodes to coated anodes.
-------
Table 6-2. Chlor-Alkali-Mercury Cell Process
factor
Physical and Chemical
Properties of Residual
Wastes
Amount of Residual Wastes
(kg/kkg product)
Factors Affecting
Hazard ousness
Treatment/Disposal
Technology
Estimate of Number and
% of Plants Now Using
Technology
Adequacy of Technology
Non-land Environmental
Impact
Problems and Comments
Compatability with
Existing Facilities
Level I, Prevalent Technology
Mercury-containing »!udges from various
brine and water treatment sources. May
contain elemental soluble or insoluble
sulfides.
40-200 (wet slurry basis)
Containment plus isolation performance of
ponds, drums, and landfills. Leaching and
pH control are factors for ponds and landfills
On-lite storage and/or disposal ui'ng ponds,
drums, landfills
20 plants (711)
Inadequate - storage in ponds and drums
will decrease as improved technologies are
utilized.
Possible ground and/or surface water con-
tamination through leaks and leachates.
Industry is in flux concerning the most
economical and reliable ultimate disposal
method.
No process modifications required.
Level II, I est Available Technology
Mercury-c 5.itcining sludges plus dry solids
of low resi iuol mercury content (retorting)
Mercury-* ontaining sludges, 40-200 (wet
basis); dry solids 15-20
Contcinmi nt end isolation performance of
secured Ic.idfill. Mercury content of
retorted dry solIds.
A. Secured landfill, or
B. Chemical extraction and secured landfill,
or
C. Retort ng sludges, landfill residues.
D. Combi -rations of the above.
A & E - ' plants (14%); C - 9 plants (32%)
8 retort h gh mercury sludge only.
Adequate
Retorting releases some mercury vapor and
sulfur ox;Jes to the air. Adequate conden-
sation an i gas scrubbing is needed.
Both sect red landfilling and retorting are
relativel • expensive operations.
Varies; r Porting is usually on add-on to the
end of bi ine and water treatment processes.
level III, Adequate Health and Environmental Protection
Dry solids of low (approx. 1-5 ppm) residual mercury
content
15-20
Mercury content of dry solids.
A. Monltoredretorting of all mercury-containing
sludges plus landfilling of residues
B. Secured landfill
A. At least one plant is currently approaching this
level.
B. Secured landfill - 4 plants (14*)
Adequate.
Same as Level II
Some producers may find it more economical to
contract for their sludge disposal.
Same as Level II only with improved monitoring and
control of operations.
Monitoring and Sur-
veillance Techniques
Installation Time for
New Facility
Energy Requirements
Visual inspection of stored drums. Monitoring
of ponds and landfill with wells.
Installed
Small - mainly trucks, bulldozers, pumps,
and filter operations.
A and B jse monitoring wells and ambient
surface i 'ater analysis.
C rnonitjrs mercury content in
air and i sh, SOa content in air.
Extraction and secured landfills - 1 year;
Retortini facilities for all sludges - 2 years.
A and B - small, trucks and bulldozers;
C - con iderable fuel required for furance.
A. Monitoring of mercury content in retort ash
and SOs and mercury in the air
B. Monitoring used to maintain low mercury
content
Some as Level I!
Considerable for retorting. This is a furnace roasting
operation.
-------
Table 6-3. Chior-Alkali-Down's Cell Process
factor
Physical and C!>emical
Properties of Residual
Wastes
Amount of Residual Waste
(kgAkg product)
Factors Affecting
Hazardousness
Treatment/Disposal
Technology
Level i. Prevalent Technology
(1) Sodium calcium alloy sludge - reacts
strongly with water to form caustic
(2) Sodium contaminated rubble - same
reaction
(1)0-13
(2)50-80
Exposure of material to water under uncon-
trolled conditions.
Land dumping and spreading of residues (item
2), barging and disposal at sea of item (1),
where they are present.
level II, Bi st Available Technology
Sense as Le> cl I
Same as Le1 el I
Same as Le1 el I
Same as Le- e! I except some plants practice
recovery of sodium, calcium wastes, an in-
process chai ge.
Lcval ill. Adequate Health and Environmental Protection
Same as Level I
Same cs Level I
Same as Level I
Off-site contract disposal with controlled
neutralization
I
M
O
Estimate of Number and
% of Plants now using
Technology
Sea disposal 2 plants (40%), rest only have
contaminated rubble.
Adequacy of Technology Environmental adequacy of sea disposal in
drums is controversial.
Same as Le> el I
Same in filling. Land dump disposal requite*
proper handling to avoid hazards, until re-
oclive materials are dissipaied. Sea burial
requires specie! dispose! procedures in accord-
ance with Coast Guard regulations.
Compatible
...':, :-jtf.;..s- v:u..v'..~-.:i- !i :i:-^io(.iss recc.-
cry from cu rer.f ocian dumping w''' require-
technology development and installations.
Tcrsporaiy i n-sitc drum storage may be neces-
sary until rt ehnclogy dcvelopirwrit and inrta!-
lations are :ompleted.
Sett above c ornments
A. Land durrf leacficfe and ctaincgi mu;; be
pH monitored.
B. Sea disposal - special Coast Guard observa-
tion required.
None
Same cu Lev
Small
Conversion 'ram ocean dumping to recovery
2-3 yean, I ut this Is not a treatment dispasaJ
option, it i! an in—proccn cnanaje.
Same as Lev si I
Ttiti option is conccpiuOi>zed and nc contractor
prcssr.tly offers rhi; service. This option has not
been demonstrated
Compatible
Same as Level I
2-2 years, if contractors are willing.
Small
-------
Table 6-4. Titaniunri^oxide - Chloride Process
Foctor
Phyvcol ond Chemical
Properties of Residual
Wastes
Level I, Prevalent Technology
Level II, B -st Avoiloble Technology
A. Ore gangues are inert solids (i.e., silica) Same as Le »el t
B. Waste treatment colids are mixed heavy
metal oxides (mostly Fe)
C. In some cases heavy metal salt solutions
Amount of Residual Waste (Varies wide!/ with ore). Inerts (ore gongue. Same as Le 'el I
(kg/kkg product)
Factors Affecting
Hazardousness
Treatment/Disposal
Technology
Estimate of Number and
% of Plants Now Using
Technology
Adequacy of Technology
Non-land Environmental
Impact
Problems and Comments
Comparability with
Existing Facilities
Monitoring and Sur-
veillance Techniques
Installation Time for
New Facility
Energy Requirements
i.e., SiOs + coke 160 ovg) TiO3 18 - >0
Other metal salts 130-1100* (as oxide)
A. For deep well disposal, the geology of
the area determines seepage hazards
B. Solubility of heavy metal salts vary - pH
dependent.
A. Land storage of ore gangue waste plus
land storage of oxide wastes from waste-
water treatment.
B. Contract disposal of heavy metal salt
solutions plus oxides generated by their
treatment (Probably finally by landfill).
C. Deep well disposal of concentrated pro-
cess wastewaters.
D. Ocean disposal**
A. On-site land storage - 4 plants (50%)
8. Contract disposal - 1 plant (12%)
C. Deep well - 1 plant (12%)
D. Ocean disposal - 2 plants (25%)
A. Burial of inerts is adequate.
B. Deep well disposal is limited to areas hav-
ing proper geology.
C. Land storage of oxides may lead to leachate
problems.
Burial of oxides or deep well disposal serves
to abate surface water pollution problems.
Burial sites ond well sites should be closely
monitored to eliminate sub-surface problems.
Landfill is reliable under conditions where
leaching can be avoided. Deep welling is
limited by geological considerations.
Deep well disposal, where geologically
acceptable is an add-on operation not requir-
ing additional land. Burial of oxide wastes
may require use of an out of the plant disposal
site.
A. Deep well are not monitored for
seepage (analysis for heavy metals).
B. Burial sites also require similar monitoring.
Installed
Same as Le /el I
Landfil ing of ore plus landfilling of oxides
genera ed by wastewater treatment in
approv rd landfill
Deep well disposal - minor, for pumping of
liquids only. Landfilling - minor for water
pumping, pond dredging, trucking ond burial.
1 plan. (13*)
Adequale
SameasLivel I for burial sites
Someaslevell for landfilling
Same os level I fcr burial
Monltorl ig wells around landfill
1 -2 year ;
Minor
Level III, Adequate Health and Environmer.tcl Protection
Same as Level I
Some os Level I
Same as Level I
Some as Level II
Same as Level II
Same as Level II
Same as Level II
Same as Level II
Same os Level 11
Same as Level 11
Same as Level II
Same os Level ''
•Note: These numbers are based on amounts of heavy (i.e., Fe, V. etc.) oxides thai would be generated by wastewater treatment. Points having higher amounts of heavy
metal salts, deep well disposed such solutions in lieu of neutralization and Ic idfilling.
"Since ocean barainq is not an on-land disposal method, it Is not costed in Section 7.
-------
Table 6-5. Chrome Pigments and Iron Blue Manufacture
Factor
Physical and Chemical
Properties of Residua!
Wastes
Amount of Residual Waste
(Itg/kkg product)
Factors Affecting
Hazardousness
Treatment/Disposal
Technology
level I, Prevalent Technology
Level II, test Available Technology
Sludges of chromates, lead, zir.c, cycrvdes, Some as L- *vel I
iron, chronium end ether hazardous f«o*erial*
depending on product mix.
150-250 (dry basis)* includes filter aids and Recovery educes wastes by approx. 25%
calcium sulfate and woter treatment
precipitates.
Treatment and containment efficiency, product Depends c ily on containment efficiency of
mix, pH lev«l landfill ana.
Off-site landfill
A. Secure i landfill off-site
Level III, Adequate Health and Environmental Protection
Same as Level I
Recovery by several plants will reduce wastes by
approximately 50%.
Efficiency and containment of landRMing and chemical
fixation operations.
Same as Level li; or chemical fixation and landfilling
(not proven).
Ni
Estimate of Number and
% of Plants Now Using
Technology
6 plants (BOX)
Adequacy of Technology Major improvements needed.
Non-land Environmental
Impact
Problems and Comments
Compatability with
Existing Facilities
Both surface and ground water may be com-
promised.
This is one of the major problem areas in
inorganic chemicals hazardous wastes. Large
amounts of money hove beer, spent in the post
few years. Primarily on water quality. More
attention is still needed.
These are existing facilities.
4 plants (40S)
Adequate
A. Planning secured landfill - 2 plants.
B . Chemical fixation pilot stage.
All can be adequate
None, ex :ept from failure of landfill integrity None, except from failure of landfill, recovery or
and possitle water contamination. chemical fixation process.
Distinct p ogress has been made within the past Chrome pigments and iron blue arehighed-valued
2 years in upgrading technology utilities. chemicals worthy of recovery. Chemical
fixation not proven.
Off-site f icilities for land disposal may be re- When facilities ore cramped or secured landfill areas
quired dui to geology of available land not available, recovery and/or chemical fixation may
considerations. be desirable alternatives.
Monitoring and Sur-
beillance Technique*
Installation Time for
New Facility
Energy Requirements
Sofi^jtiny OHO nwMiiiorirtg of su/vacc: w-Iar
and ground water around ponds and land
disposals.
Installed
Small - mainly pumping and transporting
Maniforir. i wells used around landfill and
! each ale control.
Monitoring installation time - 1 year.
Small - mi inly pumping, transporting and
landfillinf .
Same as Level !l
Chemical fixation and recovery will take 2-3 years
to evaluate and install.
Small - chemical fixation is a chemical reaction process
rather than thermal or electrical.
'Depends on product mix produced.
-------
Table 6-6. Hydrofluoric Acid
CTi
i
t->
U)
Factor
Phyiical and Chemical-
Properties of Residual
Wastes
Level I, Prevalent Technology
Solids formed from waste treatment are a
mixture of silica, CoFa , and gypsum.
Amount of Residual Waste 2700-4325 Co SO., (3700 ovg)
of product) 45-100 Cof? (75 ovg)
1-27 silica (13 avg)
Factors Affecting
Hozardousness
Treotment/Oi sposal
Technology
Estimate of Number and
% of Plants Now Using
Technology
Solubility of CoFa limits degree to which
fluoride con be reduced in waters, possibility
of leachate problems.
Lime treatment; pond storage or on-site
landfill.
9 plants (75%)
Level II, B ?st Available Technology
Same as Le /e! I
Same as Le /el I
Same as Le /el I
Level III, Adequate Health and Environmental Protection
Some as Level I
Same as Level I
Same as Level I
Pond st mage (water treatment needs) and/ Secured on-site landfill, leachate
or cent act disposal (general). monitoring, rainwater diversion.
2 plant (22%)
Adequacy of Technology Inadequate without pM and leachate control Adequate i f approved land site
Non-land Environmental
Impact
Problems and Comments
Comparability with
Existing Facilities
Monitoring and Sur-
veillance Techniques
Installation Time for
New Facility
Energy Requirements
Leaching and runoff problems due to either
runoff or improper pond pH control ore
possible, leading to water problems with
dissolved fluorides.
Wastes are a mixture of co-product gypsum
(CaSO«) and Cari along with minor amounts
of silica. Plants producing HF frequently also
produce sulfuric ocid on-site and may also
manufacture other fluorides.
Ponds and land available for disposal are
present in all HF plants.
None
Installed
Smoll - for slurry pumping, dredging and
piling of wastes.
Negligible with runoff collection and treat-
ment and £ xxl pond pH control.
Same as Le vel I
Same as Le /el I
None
Installed
Same as Le /el I
None
Not proven
Same as Level II
Same as Level I
Same as Level I
Need to monitor runoff waters for fluoride
and pH
On-site facilities for approved land
storage - 1 year.
Some as Level I
-------
Table 6-7. Boric Acid
Foclor
Leve! !, Prevalent Technology
Leve! !!, !;;T Available Technology
Level III, Adequate Health and Environmental Protect Jon
Physical and Chemical
Properties of Residual
Wastes
Amount of Residua! Waste
(kg/kkg of product)
Factors Affectir-i,
Hczardousness
Treatment/Disposal
Technology
Estimate of Number and
% of Plants Now Using
CTi Technology
1
r— ' Adequacy of Technology
Non-land Environmental
Impact
Problems and Comments
Comparability with
Existing Facilities
Monitoring and Sur-
veillance Techniques
Installation Time for
New Facility
Energy Requirements
Sludge containing AsuSe
Approximately 6
pH of ground wcrsr affects solubility of
arsenic salt. Prepared secured Icndf!!!:
must be used .
Burial off-site in secured Iarsdf!!!s.
1 plant (100%)
Satisfactory
None
None
No problems.
Monitoring wells.
None
Minims! - trucking and boric! c=Jh cr.iy
Same as Le rel !
Same as Lc vel 1
Same as L< ve! 1
Same as Lc vel !
Same as Li vel 1
Same as L< vel I
Some as L. vel 1
Same as L vel 1
Same as L ive! 1
Same as L ivel 1
Same as L rvel 1
Some as Isvc! !
Same as Level I
Same as Level 1
Same as Level 1
Same as Level 1
Same as Level 1
Same as Level 1
Same as Level 1
Same as Level 1
Same as Level 1
Same as Level 1
Same as Level 1
Scale as Level !
-------
Table 6-8. Aluminum Fluoride
Factor
Level I, Prevalent Technology
Lave I II, Be:t Available Technology
level III, Adequote Heolth ond Environmental Protection
Physical and Chemical
Properties of Residual
Wastes
Amount of Residual Waste
(kg/lckg product)
Factors Affecting
Hazardous ness
Treatment/Disposa 1
Technology
Estimate of Number and
Ot % of Plants Now Using
1 Technology
Adequacy of Technology
Non-land Environmental
Impact
Problems and Comments
Comparability with
Existing Facilities
Monitoring and Sur-
veillance Techniques
Installation Time for
New Facility
Energy Requirements
Mixture of alumina, gypsum, CoFP, other
Inert* (silica, etc.) recovered from waste-
water treatment
Alumina 12-24*; gypsum 63-1 26; CaF,30-
42; other inerts 4-6
A . pH of pond water
B. Presence of other materials in waste piles
which may farm soluble fluorides
C. Leachate problems
A. Precipitation of fluorides, storage or on-
site landfill
B. Municipal landfill
A. 4 plants (67%)
B. 1 plant (15X)
Land storage alone is at best a temporary
disposal method.
Storage of fluoride containing wastes, if
not done properly can lead to leachate
problems.
Ability to avoid leochate problem is
limited by the solubility of CaF,
Ponding and land storage foci lities are
already in existence at the plants.
None
Installed
Minimal water pumping, dredging solids
from pond and piling.
Same as Low -1 1
Same as Lev. .1 1 •
Same as Lev >l J
Same as Lev >l 1 (A)
Same as Lev il 1 (A)
Same as Lev >l 1
Same as Lev >l 1
Same as Levil 1
Same as Lev il 1
Same as Lex el 1
Same as Let el 1
Same as Let el 1
Same as Level 1
Same as Level 1
Same as Level 1
A. Level 1 plus leachate monitoring and rain water
diversion.
B. Recycle and reuse of waterborne wastes (limited
to certain types of complexes).
A. None
B. 1 plant (15%)
Adequate
Same as Level 1
Same as Level 1
Same as Level 1
Runoff needs monitoring for fluoride
Monitoring and leachate control, 1-2 years
Same as Level 1, for recycling, only minor
requirements.
pumping
'These numbers are based on amounts of final products after wastewoter treatment.
-------
Table 6-9. Sodium Si I Fcofluoride
Factor
Physical and Che mi;-!
Properties of Residual
Wastes
Level I, Prevalent Technology
rEuoriJss (CaFa recovered with wostewafer
along with such larger amounts of gypsum)
Amount of Residual Waste 30-61 (as F~)
(kg/kkg product)
Factors Affecting
Hazordousness
Treatment/Disposal
Technology
Estimate of Number ana'
% of Plar.fs Now Using
Technology
Adequacy of Technology
Non-land Environmental
Impact
Problems and Comments
Compatab! lity with
Existing Facilities
Monitoring and Sur~
veil lance Techniques
Installation Time for
Now Facility
En
pH of pond water (higher pH increases
CaFa solubility)
A. Common ^eotmenl of process wostewoiers
with those from cdiacent HbPO* production
facilities; landfill
B. Deep well disposal of all wastes
A. 1 plant (33%)
u. 1 plant (33%)
level II, E-st Available Technology
Same as U »el I
Same as U/el I
Same as U *el I
Same as U vei i (A)
Same as U
-------
Table 6—1Q. Cttramates Manufacture — Ore ft
fuutai
Wiywcd are* Chemical
FTOpBf TI6X fl* KC3X0UB*
Amoam-of ReriAial Wmt»
(kg/lckg of product)
Factors Affecting
HazardotJBncss
Tr«u liiciU/Dispoaat
leret l> ftevntent Technology
Slurry-of ore reshtoes.. Catcf
U
T4I^^ fl**tf I FOR
II, Bat Available Technology
a*.te-«U
LCT»J Bt,
Heojfband
30O-35QQ (dry bnris). Imlmkt me aaitlua^
Sastmcf la-mil
Effectiveness of cliroiluil treatment- to comert- San»ai; Lo-fd I
Cr^ to Cr^s ana pH t miliol otncttngtaof^'
EstiTOtB of N j.-iter and
% of Plants N«. Uiing
Technology
Adequoqrof Tedaofogy
On or off -site Tamtftlt
J l»T»it an-stte f 33$
* plant off ^tt* C33J»
Itot adequate. LantffTT TeadrfraF
possible.
Cheiracn treuftnicnt
off -site TandftlT
I (rtmt t:3«
Sane as
; IS t»el E
-axlemei tt wttb secure
Nun 'lufuJ EIWI i oronHntnt
\tcfoct
FVablerm and Commend
Campotiblllty with
Existing Fodliticr
Monitoring and Sur—
veil lance Techniquet
usuuui^* into grennn or surfoctf watBfcaff SCBBVOX L9'vi' r
occur.
Maaive quontrtiet of Juumimii-miiluimiiij Sonror L»'«l I
IIUAU or sluuyGf constitute potentioily MQBXVI^^
fflIT luiU. UBSllflBa WOStBS*-
Plonts need large apt* uvej landfill ana*. Sanaa leal I
far waste disposal . Not all plants hove
rime foci (trie* -or places ta develop them
nearby.
Surface vniter analysis and ground water Soms-cs Le«i I
njarrttaHmf by mrans of Mel Is.'
Inrtallorian Time far
New Facility
Energy Reoujrementi
ImfnHed
tastzrtTedr
Italerate. Due ta the large quontirtei of Sane at La rel I
miilra rhot hnv^tobft exacavated
Biul turtiuf sat
I -year
Same ss. Letel
-------
Table 6-11. Nickel Sulfate
Factor
Level III, Adequate Health and Environmental Protection
Physical and Chemical
Properties of Residual
Wastes
Amount of Residual Waste
(kg/kkg product)
Factors Affecting
Hazardousness
Treatment/Disposal
Technology
Esti mate of Number and
% of Plants Now Using
Technology
(TV
1 Adequacy of Technology
r-1
00
Non-land Environmental
Impact
Problems and Comments
Compatability with
Existing Facilities
Monitoring and Sur-
veillance Techniques
Installation Time far
New Facility
Energy Requirements
Sludges containing nickel oxides and sulfides
0-250
pH of waters in contact with the solids
(soluble at low pH)
A . Land disposal
B. Sewer disposal
A. 1 plant (25%)
B. 2 plants (50%)
Pond and land storage is inadequate due to
leachate problems
Leachate problems passible with land or
uuju storage
Leachate problems
No problems
None
Installed
Small, only far trucking and pumping
Same as U vel 1
Same as U vel 1
Same as Uvel 1
Same as Level 1 (A)
Same as U vel 1 (A)
Same as Level 1
Same as Le/el 1
Same as Le /el 1
Same as Le/el 1
Same as Le /el 1
Same as LB /el 1
Same as Le /el 1
Same as Level 1
Same as Laval 1
Same as Level 1
A. Off-site secured landfill in lined drun.
B. Chemical fixation by coBtracrar (nor t»imin)
None
Not proven
None
Problems only as related to economic roco»eiy of
nickel values from impure «*»»*j"«
Same as Level 1
Need to monitor around secured landfill
No installation required
Trucking far landfilling, some energy requirements
far reprocessing
-------
Table 6-12. Phosphorus Manufacture
I
M
VO
Factor
Physical and Chemical
Properties of Residual
Wastes
Amount of Residual Waste
(IcgAkg of product)
Factors Affecting
riozordousness
Lave! I, Prevolent Technology
Aqyeous suspensions and slurries of colloidal
phosphorus stable except in presence of air.
Scrubber wastes are fluoride,lime
-------
Table 6-13. Phosphorus Trichloride and Phosphorus
Pentasulfide
i
to
o
Factor
Physical and Chemical
Properties of Residua)
Wastes
Amount of Residual Waste
(kg/lckg of product)
Factors Affecting
Hazardousness
Treatment/Disposal
Technology
Estimate of Number and
% of Plants Now Using
Technology
Adequacy of Technology
Non-land Environmental
Impact
Problems and Comments
Comparability with
Existing; Facilities
Monitoring and Sur-
veillance Technique*
Level I, Prevalent Technology
Phosphorus plus P
Arsenic trichloride
1-2 fJ^Ss); 0.3 (PCfe )
Phosphorus and P^SB are bath flammable, ft
and AsCI3 ore toxic volatile material. For
later use, there is high solubility. Treat-
ment is required prior to disposal.
Level II, Btst-Available Technology
Son* ox Lev el I
Some ox Level I
Some as Lei at I
A. PCI3 -arsenic heavy wastes are collected, Same-ax Le^el I
treated, Jimmied, and buried. P-£F
wastes (Pt & PtS3) are typically drummed
and buried.
PCI, -5 plants (100%)
P,,SS -8 plants (100%)
Inadequate
Problems will exist-only if leaching occurs
Same as Le -et I
Same as
Sorre ox
There tsnewoy to remove- rise taxi city from Same-at ta*«£f
arsorrc heuvy muter tots* The best that can
off oxiliufVGu tf to bury the ncrtwiat i n such
A nvimer~tnir IT" connot escopv to1 Hwr otntos^
Same ex Lr el I
leiuujMfa; Of tmrtnvnT uzim
Compatinw
None
Level III, Adequate Hea)rhatBtCmai"""—^Tt Pcarectrarr
Same ax Level I
Same as Level I
Same at Level I
Sam* as Level II, eacept bsrfet cites.
should be secured TareifTTTs
None
Not
tL*Ml I
leretl
-
Toctrate (arssric conpoorotsi) ^
Installation Time for
New Facility
Energy RequlieinBfitT
InstalUd
Miiiliml far-
gnrf nurlql orrfy »
Sane as Leref I
Someo* Le-«J I
BurtaT
- T
-------
Although there ate exceptions, most phosphorus, fluoride
chemical, boron chemical arid zinc oxide plants are located
on large blocks of land in tairly isolated areas. For these
general relatively large volumes of rather dilute hazardous
wastes:, increased monitoring, rainwater control and leachate
control and treatment will be needed for many of the
existing facilities, but except in exceptional cases, should
not change the present on-site disposal pattern. There will
also be increased utilization of preserit calcium smlfate and
ore residue wastes for purposes of construction and raw
material reclamation. The extent and timing for these
developments can not be accurately forecast at this time.
Treatment and disposal of wastes may be expected to follow
one or more of the following paths:
(1) More use of approved or secured landfill operations both
on-site and by off-site contracting;
(2) Less dependence on ocean barging and deep well disposal;
(3) More recovery of valuable components such as mercury,
chromates» nickel, zinc, sodium, chromium and vanadium;
(U) Conversion of present wastes to saleable products;
(5) More dependence on both on-site and off-site contractors
who will assume total responsibility for hazardous waste
treatment and disposal technology.
6.1.5 General Description of Present Treatment Technologies
The following describes existing treatment and disposal
technology appropriate to the inorganic chemical industry:
iilJii Chemical Detoxification
Toxic or hazardous wastes are often treated chemically to
reduce or destroy their hazardous nature. These treatments
most often are included in water quality maintenance, but
can be utilized for land-destined wastes as well,
particularly by off-site contractors. The chemical
reduction of hexavalent chromium wastes to trivalent is an
example of chemical detoxification carried out in this
industry category.
SilLs-l Neutralization
Acids and caustic wastes are reacted either with each other
or with additional acid or caustic to form neutral salts.
The resulting salts are usually less hazardous than either
of the reactants. Also, the resultant salt may be insoluble
and precipitate from the solution. Calcium salts derived
from low cost limestone or lime are particular examples of
limited solubility.
6-21
-------
lilsJ.s.2 p_H Control
The control of pH may be equivalent to neutralization if the
control point is at or close to pH 7. Chemical addition to
waste streams may be designed, however, to maintain a pH
level on either the acidic or basic side for purposes of
controlling desired reactions or solubility as shown by
Figure 6-1 (12).
f
Examples of pH control being used for precipitating
undesired pollutants are:
(1) Cr+3 + 3OH- = Cr(OH)3
(2) Fe+3 4 30H- = Fe(OH)3
(3) Mn+2 + 20H- = Mn02 +~2H+ + He-
(U) Zn+2 + 20H- =Zn(OH)2
(5) Ni+3 + 30H- = Ni(OH)"3
(6) CU+2 + 20H- = CU(OH)2
Reactions (1) and (2) are used for removal of chromium and
iron contaminants involved with chromate reductions.
Reaction (3) is used for removing manganese from perman-
ganate and manganese sulfate water-borne wastes. Reactions
(4) , (5) , and (6) are used on wastewater from nickel
sulfate, copper salts and zinc salts of this study. It is
estimated that approximately 1 percent of the 250,000 metric
tons of concentrated hazardous wastes is treated in this
manner.
6.5.1.3 oxidation-Reduction Reactions
The modification or destruction of many hazardous wastes is
accomplished by chemical oxidation or reduction reactions.
Cyanides can be oxidized with chlorine or ozone to less
hazardous cyanates or to final destruction to innocuous
material. Hexavalent chromium is reduced to the less
hazardous trivalent form with sulfur dioxide or bisulfites.
Sulfites, with large COD values, can be oxidized with air to
inert sulfates. These examples and many others are basic to
the modification of inorganic chemicals water-borne wastes
to make them less troublesome.
Cyanides
The two most common methods of treating cyanides are:
(1) single or two-stage alkaline chlorination and
(2) hypochlorite oxidation.
6-22
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1.6
i
AOl
6
I I
a
-i
SOLUBILITY OF C&PPZtf.
AMD ^/A/C AS A
or SOLUTION
6-23
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Alkaline chlorination:
Stage 1 - 11.5 pH NaCN + Cl2 * 2NaOH = NaCNO + 2NaCl + H2O
(fast)
Stage 2 - 7.5 to 9.0 pH 2NaCNO + 3Cl2 * 4NaOH =
N2 + 2C02 * 6Nad + 2H2O (slow)
The stage 1 cyanates are stable and less toxic than cyanides
(23). Stage 2 completes the destruction to nitrogen and
carbon dioxide, but considerably more chlorine and caustic
are required for the overall 2-stage process than for the
single-stage oxidation to cyanate. The reaction is also
slower.
Hypochlorite Oxidation
2NaCN * Ca(OCl)2 = 2NaCNO + CaCl2
2NaCN + 2NaOCl = 2NaCNO + 2NaCl
Either calcium or sodium hypochlorite can be used depending
on economics and availability. For small plants or small
cyanide wastewater loads, the recently developed electrical
hypochlorite generators may be useful.
Both alkaline chlorination and hypochlorite treatments
normally reduce oxidizable cyanide to essentially zero
concentration. Complex cyanides are not usually affected.
Ozone has also been used for oxidation of cyanides (55).
Other methods include boiling and peroxide decomposition
(57).
Complex cyanides are much more resistant to oxidation or
removal than simple cyanides. Soluble complex cyanides may
often be removed by chemical precipitation with iron salts
(such as ferrous sulfate) or other heavy metal ions (zinc or
cadmium).
Ferro- and ferricyanides as well as other complex cyanides
may be destroyed by either ozone or chlorine oxidation in
acid solution. Ozone appears to be the best choice (15).
complex cyanides are less toxic than oxidizable cyanides and
are stable except to ultraviolet light (sunlight).
The proposed mechanism is:
UFe(CN)6<-*> + 02 + 2H20 = UFe(CN)6(-3) +
6-24
-------
12H20 « We(OH) + 12HCN
Reported rate of oxidation of ferrocyanide in the presence
of sunlight leaves about 25 percent of the original concen-
tration in five days — the ferrocyanide disappearing
completely in 10-12 days.
Chrotttates are reduced to less toxic ct+* compounds by such
chemicals as sulfur dioxide (reaction 1) » sodium
metabisulf ide (reaction 2) , sodium bisulfite (reaction 3) ,
sodium suifite (reaction 4) » ferrous sulfate (reaction 5),
and f erroua chloride (pickle liquor) (reaction 6) 4
(1)
(2) HH2drOJi * 3Na382.0Ji + 3tt^SOJi * 2Cr^(8OJl) 3 * 3NaJSOj| * 7H2.0
(3) 4M2Cr04 + 6NaHSO| * 3H2SOJJ * 2Cr2(80a)3 * 3Na2,Soa * 10H2O
(U) 2H^Croa * 3N32SOJ * 3H^flOJi * Cr^(SO4)J * 3NaJSoa + 5H^O
(5) 2H2Cro4 * 6fe60li«7tt20 + BM^jflOJi * Cr2(Soa)J * 3Fe^(SO«)3 * 5oH2O
(6) 2M2c«>a + 6feCl2 * 12HC1 - Ci^2lj * 6teCl^ * 8H2O
These reactions go to virtual completion with limits of
approximately 0.01 mg/liter residual chr ornate. Removal of
the less toxic but still undesirable cr*3 compounds is
accomplished with pH control or precipitation on the basic
side*
(7) Cr*s + 30M- « C
Total chromium is a mixture of suspended cr(OH)3 plus
residual dissolved chromate. Total chromium levels of 0.1
to 0.3 mg/liter can usually be attained since the suspended
chromium hydroxide usually settles readily. Suspended
chromium in the cr+* category may also be present from
insolubles such as lead chromate or other chroma tes such as
particulates of chrome pigments*
Inorganic suifur compounds
Inorganic sulfur compounds range generally with degree of
oxidation from the very harmful hydrogen sulfide to the
relatively innocuous sulfate salts such as sodium sulfate*
Intermediate oxidation steps include sul fides, thiosulfates»
hydroBulfites* sulfites and finally sulfates*
6-25
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Oxidation is accomplished with airr hydrogen peroxide,
chlorine and other oxidizing agents.
(1) Sulfides (58)
Sulfides are readily oxidizable with air up to the
thiosulfate level. Thiosulfates are less harmful than
sulfides (of the order 1000 to 1) and approach the
innocuousness of sulfates: US- * 302 = 2S2O3-*. Reaction
level is 90-95 percent complete.
(2) Thiosulfates
Thiosulfates are difficult to oxidize further With air (51) .
They can, however, be oxidized to sulfates with powerful
oxidizing agents such as chlorine and peroxides: S2O3~Z +
C12 = 2SO4-2; S2O3-2 + H2O2 = 2SOU-2. Reaction level~should
be 95-99 percent complete.
(3) Hydrosulfites
Hydrosulfites can also be oxidized by oxidizing agents such
as C12 and peroxide, and perhaps with catalyzed air
oxidation: S2OU-2 + C12 = 2SOU-2;s2O4-2 + H202 = 2SO4-2.
Reaction level should be 90-99 percent complete.
(4) Sulfites
Sulfites are readily oxidized with air to sulfates at a 90-
99 percent completion level. Chlorine and peroxides would
be expected to perform similar oxidation: 2SO3-2 •»• o2 =
2S04-2.
e^j^l^a Precipitations
This reaction of two soluble chemicals to produce insoluble
or precipitated products is the basis for removing many
undesired water-borne wastes. The use of this technique
varies from lime treatments in order to precipitate
sulfates, fluorides, hydroxides and carbonates to sodium or
ferrous sulfide precipitations of copper, lead and other
toxic heavy metals. Precipitation reactions are
particularly responsible for heavy suspended solids loads.
Removal of these suspended solids is accomplished by means
of settling ponds, clarifiers and thickeners, filters, and
centrifuges.
The following are examples of precipitation reactions used
for waste-water treatment:
(1) S04-2 + Ca(OH)2 = CaS04 + 20H-
6-26
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(2) 2F- * Ca(OH)2 = CaF2 + 20H~
(3) Na2SiF6 * 3Ca(OH)2 = 3CaF2 + Si02 + 2NaOH + 4H20
(U) BaS + FeSOU = BaSOa + FeS
(5) Zn+2 * Na2C03 = ZnC03 * 2Na+
(6) CrOU-2 = + pb+2 = PbCrOU
(7) Cu+2 + Na2S = CuS * 2Na+
6iJL..2 Recovery and Reuse
Many toxic or hazardous inorganic chemicals wastes contain
valuable materials. Whenever this is the case, recovery and
reuse is one of the most desirable methods of hazardous
waste avoidance. Silver, selenium, thallium, mercury,
copper, lead, chromium, zinc and other heavy metals, once
they are removed from water or air streams, are often
recovered rather than land disposed. It is uneconomical to
reclaim these metals only when they are very minor
constituents of the waste or when the quality of the product
is adversely affected as in chrome pigments manufacture.
There are also private contractors that specialize in
hazardous waste reclamation (1) (33) (36) . In view of the
fact that recovered and recycled materials are not land-
destined, these do not appear in the earlier hazardous
waste allocations in Section 5.0.
£..5^3 Disposal Ponds or Lagoons
Approximately ninety percent of the hazardous waste in the
United States is in liquid or sludge form (47). It is
likely that a similar percentage of close to ninety percent
non-dry-solid hazardous waste exists for the inorganic
chemicals industry as well.
Whenever feasible, pond or lagoon disposal of hazardous
wastes is one of the simplest and most economical of
approaches. It suffers from a number of restrictions,
however:
(1) The pond needs to provide protection from both surface
and groundwater contamination. With the exception of
some pit.s in naturally impervious soil or in some very
dry climates this means a lined pond. Liners include
clay, plastic sheeting, asphalt, concrete, epoxy and
other impervious materials, all of which are relatively
expensive.
(2) Except for dry climates such as found in the western
U.S., the ponds without discharge will eventually
overflow from rainfall accumulation.
(3) Ponds are prone to be "flushed out" whenever massive
rainfall and floods inundate the pond area. Here again.
6-27
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it is difficult and expensive to provide flood
protection, particularly in wet climates.
In view of these restrictions, disposal ponds and lagoons
are usually feasible only in the western U.S. where
evaporation disposal of a large volume per year of liquid
waste is carried ouc. Ponds, in other regions,must be
considered as storage ponds which will eventually need
drainage cleaning or treatment and disposal action. Pond
storage and disposal probably accounts for 20-30 percent of
the total land-destined hazardous wastes. Pond storage of
wastes occur, for example, in the manufacture of borax (SIC
2819), sodium silicofluoride (SIC 2819}„ dichromates
(SIC 2819), boric acid (SIC 2819), and chlorine (SIC 2812).
6^.5^/4 Burning and Incineration
Since inorganic chemicals are generally non-combustible and
their wastes are mainly found as sludges and liquids,
burning or incineration is rarely used for treatment and
disposal of inorganic hazardous wastes. A few small organic
wastes are the exception. These account for less than 1
percent of the total wastes. An example from these
industries is the incineration of chlorinated hydrocarbon
wastes from the chlor-alkali industry (SIC 28121).
£-.5^5 High Temgerature Processing
Although not flammable, inorganic hazardous wastes in some
cases can be decomposed, smelted, roasted, volatilized
and/or distilled in fashion similar to recovery of metals
from ores. Mercury can be driven from wastes by heating in
furnaces and retorts, condensed in chilled heat exchangers
and recovered. This is one of the more promising approaches
to treatment of mercury sludges from the mercury cell
chloralkali industry (23) (33). Smelting operations are
also widely used for hazardous metallic wastes (35) (43).
High temperature processing accounts for an estimated 1-2
percent of the total hazardous wastes-
JLs.-l.sJJ QE^Q Dumping
Open dumping of hazardous inorganic chemicals wastes into
gravel pits, dumps and other uncontrolled disposal areas is
still a disposal practice in a few isolated instances in
these industires. Most of the companies producing inorganic
chemicals contacted during both this study and previous
water quality studies, however, have demonstrated increasing
awareness and responsibility for treatment, control and
disposal of hazardous wastes. According to information from
both private contractors and interviewed inorganic chemicals
6-28
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producers, most chemical companies want no "surprises" from
disposal and are checking closely on both their own and
contract disposal sites and procedures.
Massive processing wastes such as ore residues and
unsaleable by-products contribute a major portion (estimated
95 percent) of the potentially hazardous land-destined total
waste volume for the inorganic chemicals industry. These
large volume wastes, containing relatively small amounts of
hazardous components, are currently land dumped or
landfilled usually on-site. Examples of such wastes are ore
and water treatment residues from the ore processing in
chromates manufacture, calcium sulfate contaminated with
calcium fluoride from the production of hydrogen fluoride,
and ore residues fron the production of lead and zinc
compounds. The large volume and the obviously high economic
impact of more costly treatment and disposal technology make
it necessary to consider each of these situations very
carefully.
lls.5^! Municipal Sewers
Hazardous wastes from a number of inorganic chemicals
manfacturers currently go into municipal sewer systems.
These materials wind up in sewage sludge, some of which is
destined for land disposal. Percentage of total volume of
inorganic chemicals industry wastes being disposed of in
this fashion is judged to be small (less than 1 percent) .
6,5.8 Burial
Some quantities of inorganic chemicals industry hazardous
wastes are disposed of by burial. These wastes include dry
solids, sludges and liquids. Burial locations include
specialized disposal sites such as abandoned mines,
quarries, and government facilities, as well as public and
private landfills.
Details are given later in Section 6.6.
6^5^ Deep Well Injection
The deep well injection of hazardous inorganic chemicals
includes acids, cyanides, heavy metal compounds, chromates
and arsenates as well as a number of relatively innocuous
inorganic salts.
Deep welling is a specialized form of land disposal of
hazardous wastes. It is normally restricted to liquids only
since suspended solids or sludges tend to clog the porous
6-29
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rock shale or sand structure into which the injection
occurs.
bisposai of inorganic chemicals industry hazardous wastes by
deep wells is done both on-site by the plants and off-site
by contractors. Most of the contract disposal wells
encountered were in southern locations such as Texas,
Oklahoma, and Louisiana, disposal wells are located in
Florida and Tennessee and account for 11 percent of the
total waste volume, beep well injection of Wastes is used,
for example, at some plants manufacturing titanium dioxide
pigment by the chloride process (QIC 28161).
O ocean Bargina
Currently a number of hazardous wastes generated by the
inorganic chemicals industry are disposed of by ocean
barging* Some of these wastes will in the future be
destined for land disposal. Sodium sludges * titanium
dioxide wastes and small quantities of miscellaneous
hazardous chemicals are among the materials currently
involved.
Examples of current use of barging and disposal at sod in
these industries occur in the manufacture of sodium
(Sic 28121) and titanium dioxide pigment (Sic 28161),
6-6 Qn-0it§ x&± Qff±aiJ:g BJBpQBaj
Of a total of 179 plant sites, an estimated 29 percent (35*
t|5 plant sites) hire contractors for off-site disposal of at
least a portion of their hazardous wastes* The remaining 75
percent treat and dispose of their own wastes. In general,
contractors are used for small volume wastes, particularly
In congested areas where treatment and disposal land is at a
premium. Contractors account for 10-15 percent of the total
volume disposed.
&.sl.l Sgeqializecj Mafiosal gi£§S
In the disposal of hazardous wastes, advantage is often
taken of existing mines, quarries, abandoned government
property and other facilities which have fortuitous
geological and environmental isolation, for example,
abandoned missile silos in Idaho are Utilized by a private
contractor for disposal of hazardous wastes (37). clay
pits in Ohio and California provide impervious liquid waste
disposal sites (27) .
6-30
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In general, however, specialized disposal sites are not
utilized to any significant degree by the inorganic
chemicals industry (less than 0.2 percent).
6.6^2 EUblic and Private Landfills
Definitions of landfills that pertain to this means of
disposal are:
General landfill: A site which is limited to disposal of
inert solid wastes which should not pose
a threat to water quality. The site may
contain water (e.g., marshy areas, gravel
pits, or periodically flooded areas) with
no threat to water quality from the
wastes.
Approved landfill: A site which is suitable for the disposal
of inert solid wastes and decomposable
organic materials. The site must provide
separation of the wastes from underlying
or adjacent usable water because of
leachate possibilities.
Secured landfill: A site suitable for disposal of all
wastes, including liquid and/or solid
hazardous wastes. The site must allow no
discharge of these materials or their by-
products to usable ground or surface
waters by leaching, percolation or any
other means. Another feature which may
be included is inventory control on the
wastes buried in the secured landfill.
The prime requisite for such disposal is
that the hazardous contents of the
landfill be isolated from the surrounding
environment. Water quality of surface
and ground water must not be compromised.
Air quality must also be maintained.
Landfills may be classified as:
(1) General purpose landfills;
(2) General purpose approved landfills for small volume
hazardous wastes;
(3) Approved landfills for large volume hazardous wastes;
(
-------
It should be noted that this classification of landfills is
not that of the Environmental Protection Agency,
£iJL2±l General Purpose La.ndf.iiig
It is estimated that 55 percent of concentrated hazardous
wastes of the land-destined hazardous Waste from the
inorganic chemicals industry currently finds its way into
general purpose landfill sites. General purpose landfills
are characterized by their acceptance of a wide variety of
wastes, including garbage and other organic materials, and
by the usual absence of special containment, monitoring, and
leachate treatment provisions for hazardous wastes.
The potential for environmental damage by landfilled
hazardous wastes differs depending on both the composition
and quantity of that waste. Many general purpose landfills
will accept small quantities of hazardous Wastes,
particularly if they are in drums or plastic containers, but
refuse large amounts. Cyanides, arsenic compounds and some
heavy metal compounds are examples of such materials. On
the other hand general purpose landfills are usually wary of
even small amounts of beryllium and mercury compounds.
when the hazardous level is relatively low» due either to
the inherent characteristic of the compound or its low
concentration in the overall waste mass* even large
quantities of hazardous wastes may be accepted.
6.6,2.2 General Purgose Aggroyed Landfills
Each general purpose landfill has its own ambience -
geologically, hydrologically, and environmentally. Ideally,
a general purpose landfill would be located in an isolated,
dry part of the country with a thick layer of impermeable
soil between the waste and the water table, such areas are
plentiful in the western U.S., but not in the east.
However, many existing and future landfill sites throughout
the U.S. can approach ideal conditions.
The degree of approach is differentiated in this report as
approved landfills and secured landfills. Secured landfills
are defined and discussed in a following section.
Approved general purpose landfills are defined to meet the
following criteria:
(1) The composition and volume of each hazardous waste is
known and approved for site disposal by pertinent
regulatory agencies.
6-32
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(2) The site should be environmentally suitable for hazardous
wastes.
(3) Provision is made for monitoring wells and leachate
control and treatment if required.
The advantages of approved landfill sites include:
(1) Many hazardous wastes may be disposed of in a controlled
and environmentally safe fashion.
(2) Selection of landfill sites and disposal technology for
environmental suitability still leaves a great number of
available landfill sites.
(3) Disposal costs, for both transporting the waste to the
site and the landfilling itself, are kept to levels
close to those for general purpose sites and still much
lower than for secured landfill.
From a practical standpoint many local regulatory agencies
and landfill site owners are informally practicing much of
this discrimination by selective acceptance of waste
materials. Sites with known high potential for surface and
groundwater contamination are thereby avoided.
*LdLi2..3 Apjgrgved Landfill fgr Large Volume Hazardous Wastes
Whenever the volume of a potentially hazardous waste is
large, general purpose landfill operations are no longer
appropriate. These wastes warrant, and because of their
small number can be given, special attention. In the
inorganic chemicals industry these large volume wastes
usually come from ore residues and process by-products.
Examples are chrome ore residues from sodium dichromate
production and calcium fluoride-calcium sulfate residues
from hydrofluoric acid production. Hazardousness for these
wastes is generally of a lower level than for more
concentrated and/or toxic compounds. On the basis of this
selection, a rough estimate is that 5 percent of the total
wastes are disposed of in this fashion. Large volume
hazardous wastes normally have their own landfill site so
that interaction with other wastes is not a factor. Also,
since transportation costs are high, disposal is usually
either on-site or within a few miles of the plant.
In view of their small number, large size, and
transportation restrictions, each of these wastes can be
given in-depth disposal analysis for environmental safety.
6-33
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1L.6.I.2..J General Purgoge Secured Landfills
The inorganic chemicals industry has a number of small
volume wastes of extremely hazardous potential. For these
wastes landfilling involves additional safeguards beyond
those described for approved landfills. Criteria for these
secured landfills include*
(1) The composition and volume of each extremely hazardous
waste is known and approved for site disposal by
pertinent regulatory agencies.
(2) The site should be geologically and hydrologically
approved for extremely hazardous wastes. Included in
the criteria would be a soil or soil-liner permeation
rate of less than 10-* cm./sec, a water table well below
the lowest level of the landfill and adequate provision
for diversion and control of surface water.
(3) Monitoring wells are provided.
(4) Leachate control and treatment (if required).
(5) Records of burial coordinates to avoid any chemical
interactions.
(6) Registration of the landfill site for a permanent record
of its location once filled.
A number of landfills which meet the physical requirements
(if not all the regulatory criteria) are located around the
country. California has a number of Class I impermeable
landfills which accept extremely hazardous materials (51).
Texas has similar sites (41). A number of low level
radioactive waste landfill sites accept industrial hazardous
wastes (<42) . In addition to the radioactive waste sites,
various other private secured landfills also take extremely
hazardous wastes (1) (31) (34) (37). At the present time
secured landfills are scattered and not fully utilized.
Part of the lack of utilization stems from the fact that the
majority of the sites are in isolated western areas away
from inorganic chemicals industrial centers. Another reason
for the lack of utilization is the high cost as compared to
other available disposal methods. The present utilization
of secured landfills is estimated at 5 percent.
Relatively isolated impermeable soil conditions exist in
many areas of the country. If impermeable soil is not
available then clay, special concrete, asphalt, plastic and
other liners and covers are available to accomplish similar
containment and isolation of wastes.
Once a landfill area has been isolated fron surface and
groundwater contact and leachates are being handled
satisfactorily, almost any non-flammable, non-explosive and
non-air polluting hazardous waste can theoretically be
6-34
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disposed of safely. There are a number of practical
restrictions, however, to this approach:
(1) In wet climates the impervious landfills are flooded
with heavy rainfall. Dumping of liquids or sludges into
the landfill only accentuates the problem.
(2) Some inorganic hazardous wastes create hazards for
landfill personnel and/or give air pollution problems.
(3) Chemical interactions with both other materials and the
liner can cause undesirable side effects.
Li.li.2^5 Factors Affecting the yse of Landfills
6.6.2.5.1 Rainfall
In southwestern U.S. the annual rainfall is significantly
less than the evaporation. In the San Francisco area a net
evaporation rainfall differential of four feet exists.
Therefore, in these dry climates, liquid and sludge
hazardous wastes can be mixed into either refuse or fill
dirt without having the landfill area flooded. California
private and public Class I landfill areas accept liquid
hazardous wastes as allowed under State requirements.
Eastern U.S. on the other hand tends to handle these liquid
wastes by treatment, ponding and final discharge to surface
water.
6..6._2._5.2 Personnel and Air Pollution Hazards
Some hazardous chemicals, particularly liquids and sludges,
are not usually landfilled even in dry climates because of
danger to landfill personnel and/or air pollution. Strong
acids and caustic solutions, reactive sulfides, volatile
solvents and '.nercaptans are examples of such materials. One
hazardous waste handling company is so concerned with
hydrofluoric acid exposure that it has issued special
treatment cards to its waste handling personnel specific to
this chemical (32).
6.6.2^5.3 Chemical Interaction
Indiscriminate dumping of hazardous chemicals into landfills
leads to serious interactions. The dumping of acid sludges
on top of cyanides is a classic example which has actually
occurred in California and perhaps other places. Acid
similarly attacks metallic sulfides and changes the
solubility of heavy metal precipitates. Dumping of liquids
into landfill areas is particularly prone to give such
interactions because of the relative mobility of liquids in
seeping throughout the wastes.
6-35
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In addition to the chemical interactions between landfill
components, liners can also be attacked. Many plastic
materials used in liners are attacked by organic solvents,
oxidizing agents and other waste components, clay liners
are attacked by a variety of chemicals and become more
porous. An old construction practice is to mix clay with
lime to give a sand-like soil. There have been instances in
California where clay liners have failed to stop seepage of
hazardous wastes such as chromates into ground water (28).
It is believed that chemical impairment of the clay liner
was responsible.
6A7 Safeguards used in Disposal
Most land-destined hazardous wastes from the inorganic
chemicals industry are company land stored (dumped on the
land, stored in steel drums or containers or on the bottom
of settling ponds) or in company on-site landfills.
Safeguards to avoid environmental contamination include clay
or plastic pond linings, the aforementioned steel drums and
chemical fixation to change hazardous sludges and liquids
into solids with low leaching rates.
Off-site safeguards on the remaining estimated 10-15 percent
of the hazardous wastes include a number of approaches.
HsJEii Pif§S£ £i
-------
storage and transportation. A rough estimate of 10-20
percent of the off-site waste is handled in drums.
£i2il Clay or A.sj>halt Encapsulation ig Bulk
In wet climates, sections of or entire landfill areas are
encapsulated by adding clay or asphalt "caps" or "covers" to
impervious isolation cells or landfill liners (4). The
impervious cover is necessary to protect the hazardous waste
from rainfall flooding. Neutralizing or pH control
ingredients such as lime may also be used to encase or
surround the hazardous waste to avoid solubility,
decomposition or other change in the character of the waste
to increase its environmental damage (30) (39).
In dry climate, there is no need to encapsulate the entire
landfill since rainfall and water buildup is not a problem.
Isolation cells may still be constructed, however, for
specific hazardous waste containment. Perhaps 10 percent of
the off-site wastes are handled this way.
ILI-iii Lea.c.hate collection and Treatment
In wet climates particularly, both private and public
landfills are paying increasing attention to leachate
collection, monitoring and treatment. Landfill areas in the
State of Pennsylvania are representative of those in a wet
climate and leaching treatment has been initiated in some
public landfill areas (40). Leachate monitoring and
treatment is also practiced in an on-site inorganic
chemicals plant landfill. The vast majority of the landfill
operations handling hazardous wastes, however, do not have
any leachate control and treatment provisions.
6.7.5 Chemical Fixation
Except for the western U.S. where many aqueous hazardous
wastes are being directly landfilled or evaporated, aqueous
liquids are usually handled by chemical treatment as
described in this section. Hazardous sludges on the other
hand are being increasingly treated either on-site (2) (9)
or in collection areas (55) (56) by mixing them with
inorganic chemicals and catalysts to set up the entire mass
into solid structures with low leachability and good land
storage or landfill characteristics. There are a number of
such processes which produce solids ranging from crumbly
soil-like materials to concrete to ceramic slags. There has
been no reported instance of chemical fixation being used on
inorganic chemicals industry wastes. These processes have
been used in other industries, however, to treat inorganic
6-37
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chemical type wastes and will most likely be used in the
inorganic chemicals industry in the near future*
Landfilling of hazardous wastes as discussed earlier in this
section can lead to undesirable (Chemical interactions. A
few public and private landfill operations keep records of
all hazardous waste burials by location and composition. By
means of this record undesirable interactions may be avoided
and potentially reactive chemicals isolated from each other*
one necessary corollary to coordinate record keeping is
prior knowledge of hazardous wastes coming to the landfill
area so that a satisfactory disposal section may be
selected, prior written requests for the specific hazardous
waste disposal are already required for some public! and
private landfill areas.
Organisations
Off 'Site treatment and disposal of land-destined hazardous
Wastes from the inorganic chemicals industry are most often
handled by private contractors and waste service
organizations, the contractors may provide both hauling and
disposal services or the hauling and disposal services may
be provided by two different firms. In Borne eases the
inorganic chemical companies supply their own hauling
service. A list pf private treatment and disposal
contractors and waste service Organisation is given in
Appendix B. Thie list is not intended to toe complete but
does give a good oross~sectioh of facilities* including most
of the largest and most active, involved with treatment and
disposal of inorganic chemical wastes.
&t2
The costs for contractor handling of hazardous wastes from
the inorganic chemical industry may be broken down into two
basic components - the coot oil getting the waste to the
treatment and disposal facilities and the treatment and
disposal costa themselves. Depending on circumstances,
either cost may dominate.
£.9,1 transportation CssfcS
Transportation or hauling costs depend on many factors,
individualistic with each contractor and waste situation.
The most important of these factors includes
(1) Distance
(2) Type of transportation used
6-38
-------
(3) Amount of wastes
(4) Region of the country
A constant density factor has been used for all cost calcu-
lations since almost all wastes are relatively dense
materials.
Almost all hazardous wastes taken from inorganic chemicals
plants are transported by trucks. This transportation may
be broken down into local hauling and long distance hauling.
Local hauling is defined as 75 miles (one way) or less.
Hauling
When distances are short more then one load may be made per
day. Loading and unloading times become a major factor.
Fast loading by power shovels and loaders and fast unloading
by simple dumping, for example, makes it possible to haul
several loads per day. On the other hand, short hauls are
often made with small trucks and partial loads. The effects
of these variables on transportation costs for wastes are
shown in Figure 6-2. Location factors given in the
following section for long distance hauling can be used for
geographic adjustments. Short distance (0-2 miles) railway
rates for large volume bulk wastes such as ore wastes are
similar to local truck rates or approximately $1.10/metric
ton ($1.00/ton) .
6ilili2 Long Distance Hauling
Motor transportation rates obtained from Interstate Commerce
Commission information (10) are given in Figure 6-3 as a
function of geographic location and distance hauled. Table
6-14 summarizes the mathematical equations and adjustment
factors needed to calculate motor transportation costs
directly. Rail shipping costs as a function of distance and
geographic location are also shown in Figure 6-3.
The present scattered locations of hazardous waste treatment
and disposal facilities make it necessary to haul perhaps 1
percent of the inorganic chemicals industry wastes distances
of 100 to 500 miles. Costs for hauling distances such as
these range from $11 to $44 per metric ton ($10 to $40 per
ton) of waste, a major portion of the overall disposal
costs. The percentage of wastes requiring long distance
hauling may be expected to increase as regulations become
more stringent.
6-39
-------
6
1
8O MO 'ZO
0.3. L3&9L
6-40
-------
- UYC- WASH. ffT I
PACIFIC
MI&-ATIMJTI?
R0CXY
x>l 1 J. , i I' j
Q 56O I6O6 150*
1973 MOTOR
-------
Table 6-14. 1973 U.S. Motor Rate Transportation Rates
Est. From 1971 I.C.C, Information (Ref 10)
Terms of" Equation
y » $/ton
x = ml l«s
Equation
y =6.0+ (0.0545X) (Region Factor) (Density Factor)
(load factor)
Density Factor = 0.9
Load Factor:
1. 40,000 Ibs = 1.00
2. 20m-30m Ibs. = 1.42
3. 10m-20m= 1.51
4. Im-I0m=1.74
Regional Factor:
1. New England-N.Y.C. - Wash Route 1.41
2. Pacific-1.34
3. Central (OH, IND, IL, Ml) -1.19
4. Mid-Atlantic (NY, NJ, PA, MD, WV, DE) - 1.07
5. Rocky Mountain - 1.02
6. New England - 1.00
7. Mid-West (Wl, MN, IO, MO, ND, SD, NB, KS) - 0.98
8. Southern (VA, KY, NC, SC, GA, FL, MS, AL, TN) - 0.94
9. Southwest (TX, AR, OK, LA) - 0.70
6-42
-------
Treatment and Disposal Costs
With the exceptions of a few reclamation and recovery opera-
tions and a small number of chemical destructions, solid
inorganic chemicals hazardous wastes are usually land
stored, dumped, landfilled, or buried without treatment.
Liquid and sludge wastes on the other hand are quite fre-
quently filtered, concentrated, settled, chemically detoxi-
fied, separated and solidified before final disposal. A
relatively small number of contractors are capable of
carrying out these operations in any general fashion on the
wide variety of liquids and sludges encountered. A number
of these contractors are listed in Appendix B. Some other
contractors treat and dispose of special segments of these
liquid and sludge hazardous materials. Quite often solid
hazardous wastes are developed in the course of liquid and
sludge treatment.
6.9.2.1 Costs of Liquid and Sludge Treatments
Due to the great variety of hazardous liquid and sludge
wastes from the inorganic chemicals industry, and more
importantly from the inorganic chemicals users, no precise
treatment and disposal costs may be developed for general
situations. The competitive nature of the contract
treatment and disposal business also results in a natural
reluctance for contractors to pass on confidential
information.
Therefore, the values given in Figure 6-4 have to be taken
as ranges and approximations for any specific case.
However, all the values were taken directly from major
liquid waste treatment company or industrial customer
numbers or literature numbers directly attributed to
specific companies.
6.9.2^2 Costs for Direct Land Disposal
The lowest cost land disposal of hazardous inorganic
chemicals wastes is simple dumping.
6.9.2.2.1 pumeiaa costs
Dumping costs may be estimated to range from nothing to less
than $1/metric ton. Zinc and chrome sludges are now being
dumped in a gravel pit in quantities of several tank trucks
per week at no dumping charge. Some municipal or county
dumps or landfills take local wastes gratis, some of which
is undoubtedly hazardous. The bulk of potentially hazardous
land dumped wastes from the inorganic chemicals industry,
6-43
-------
10
?o°o0oc
?o°o°oc
DOOC
opo
&AJ &&I/3/TY
ooooo
'o0o0o0o°o'
or casrs
IOOOOOOO
§8,0o0o0o°o0
-------
however, arise from ore residues and process by-products
that contain low concentrations of hazardous components.
£os&fi
Bulk Solids
Landfill costs for refuse were collected from California
(several locations) , New Jersey (several locations) ,
Michigan, Illinois (several locations) , New York, South
Carolina and Pennsylvania. These costs range from $0-6/kkg
($0-6 /ton) . Hazardous inorganic chemicals wastes are
undoubtedly coming in to landfills under this category.
When properly identified, and disposed of according to local
regulations, the average costs for easy to handle bulk
materials are approximately the same, ranging from $1 to
$6/metric ton ($1 to $6/ton) with an average value of
approximately $2.20/metric ton ($2/ton) .
Liquids
Disposal of liquids and sludges in landfills is permitted in
some states and not in others. Where liquids are permitted,
the disposal costs are usually higher than for bulk solids
as shown in Table 6-15.
Drums
Drums of liquids, sludges, and solids, including hazardous
materials, are accepted in many landfills. Table 6-16 shows
some of the charges.
Segregated Burial or Secured Landfill Costs
For very hazardous materials there are a number of secured
landfill or burial sites, some of which were initially
established for handling radioactive wastes, which provide
environmental protection above general landfill operations.
These sites cost considerably more than the landfills as
shown by Table 6-17 and are used only where other disposal
methods are not adequate.
6.9.2.3 Ocean Disposal Contractor Costs
For inorganic chemical plants located close to the coast
ocean disposal is an alternative for hazardous wastes.
Table 6-18 summarizes contract costs for liquids and sludges
and for small quantities of solid wastes.
6-45
-------
Table 6-15. Bulk Liquid and Sludge Disposal Costs*,
Landfill Areas
State <;/Uter fa/gallon) I/metric ton (I/ton)
California, Los Angeles 0.4(1.5) 3.30(3)
California, Ventura 0.8 (3) 6.60 (6)
Illinois (general) 0.8 (3) 6.60 (6)
Illinois (several sites) 0.8 (3) 6.60 (6)
New Jersey 0.7-0.9 5.50-7.70
(2.5-3.5) (5-7)
Oklahoma 0.5 (2.0) 4.40 (4)
'Based on 1.2 kg/liter (10 Ibs/gallon)
6-46
-------
Table 6-16. Drum Disposal Costs - Landfill Areas
State Waste
Illinois General
Illinois Heavy metals
Illinois Arsenic
Oklahoma Arsenic
Oklahoma Cyanide
*Drum size is 208 liters (55 gallons).
COST
$/drum*
3
3-5
5
5
5
COST
$/metric ton
(S/ton)
16:50(15)
lfc.50-27-50
(15^25)
27'.50(25)
27.50(25)
27.50 (25)
6-47
-------
Table 6-17, Segregated Burial of Secured Ldhdftll Costs
(1) Bulk Materials
Location
Illinois
Texas
New York
Idaho
(2) Bulk Liquids
Idaho
(3) Drums (Solid of Liquid)
Large
Illinois
Nevada
Texas
New York
Appro*, Cost
1/co in ($/cu ft)
46-54 (1.30-1.50)
46-54(1.30-1.50)
54(1.50)
36(1.00)
C/llter (c/gallon)
6.6-7.9 (25-30)
Number of Drums
10-20
10-20
10-20
10
Approx. Cost
t/kkg ($/ton
39-44 (35-40)
39-44 (35-40)
44(40)
30(27)
$Akg «/ton)
55-65 (50-60)
$/kkg (lAon)**
55-110(50-100)
55-110(50-100)
55-100(50-100)
55 (50)
*Based on 1.2 kkg/ co m (1 ton/ cU yd)
"Based on 182 kg/drum (400 Ib/drum)
NOTE: Single drums may cost as much as $50.
6-48
-------
film tifiUiftfl
HaeatdoUB liquid waste§ are disposed of by several deep well
contractors in Texas and Oklahoma*
Wastes that aan be injected without treatment ate handled at
a oustomet cost of 16 to 09 per ton (based on 10
Although many contractora in the liquid and solid waste
field do Bonta reclamation* at least one company takes this
approach for almost all wastes that they r«c«iv«« Ptiots
for disposal of these wastes through reclamation arei
BUlk Solids - $2.20 - $6,60/kkg ($2-6/tOh)
Bulk liquids - 0,5* - 3.2*/lit«r (2**12*!/q
Drums - 209 liters (93 gallons) - $10 eacm
j.l Cpntracfrgt: £on^ fi40figfi§l Costa
One dontraotor encountered in this program stores and
disposes of industrial sludge in an impervious base settling
pond, cost for this service , subtracting transportation is
$1.10-1.65 per metric ton ($1.00-1. SO pet ton) or 0.9*-0.8rf
per liter (2* -It per gallon) of eiudge.
6-50
-------
ZiP. COST ANALYSIS
Cost information contained in this report was assembled
directly from industry, from waste treatment and disposal
contractors, engineering firms, equipment suppliers,
government sources, and published literature. Whenever
possible, costs are based on actual installations,
engineering estimates for projected facilities as supplied
by contributing companies, or from waste treatment and
disposal contractors quoted prices. In the absence of such
information, costs estimates have been developed insofar as
possible from pi ant- supplied costs for similar waste
treatments and disposal for other plants or industries.
Most of the treatment/disposal technology levels and costs
developed have been submitted for comment to the specific
companies and plants producing the involved chemicals.
Adjustments have then been made incorporating these inputs.
Numerous cross-checks have also been made, whenever
information has been available, for treatment/disposal costs
from different sources, such as contract disposal companies.
The estimates presented were prepared on an engineering
basis, using accepted engineering format. No attempt was
made to prepare estimates which would reflect impact on
individual companies financial statements. Inclusion of tax
considerations, product pricing, and other such factors
would entail practices unique to each company, and should be
recognized as beyond the scope of this report.
ls.1 COST REFERENCES AND
l Interest Cost§ a.nd Equity Financing charges
Capital investments involve the expenditure of money which
must be financed either on borrowed money or from internal
equity. Estimates for this study have been based on 10
percent cost of capital, representing a composite number for
interest paid or return on investment required. This value
has been established as reasonable by discussions with
industry and are compatible with a recent EPA publi-
cation. <»i>
Ltl^2 Time Ifidex For gosts
All cost estimates are based on mid- 1973 prices and when
necessary have been adjusted to this basis using the
chemical engineering plant cost index. The inflationary
nature of the past year makes it particularly important that
this 1973 constant dollar basis be cited for any cost
estimation purposes. Appendix C presents published indices
which may be used to convert mid- 1973 costs to December
7-1
-------
1973. In general, costs presented herein are low by
approximately 4% in terms of December 1973 dollars.
7. 1.3 Useful Service Life
The useful service life of treatment and disposal equipment
varies depending on the nature of the equipment and process
involved, its usage pattern, maintenance care and numerous
other factors. Individual companies have their own service
life values based on actual experience and use these values
for internal amortization. A second source of such
information which , however, is based on other factors less
relevant than company experience, is the Internal Revenue
Service guidelines. <62>
Based on discussions with industry and condensed IRS guide-
line information, the following useful service life values
have been used:
Facility Estimated Useful
Service
(1) General Process Equipment 10
(2) Incineration, Distilling and 5
Retorting Equipment
(3) Ponds, Lined and Unlined 20
(4) Trucks, Bulldozers, Loaders 5
and other such materials
handling and transporting
equipment
7.1. 4
As the useful life of the treatment and disposal equipment
and facilities progresses, their economic value decreases,
or depreciates. At the end of their useful life, it is
usually assumed that the salvage or recovery value becomes
zero. IRS tax allowances, or depreciation charges, provide
capital cost recovery based on either service life or
accelerated write-off schedules. In effect, the straight
line depreciation approach used herein is similar to a
conservative depreciation approach which some companies
might actually use for income tax purposes. Using a
different depreciation rate would have the impact of
changing the cash flow companies would actually experience
based on reported expenses.
7-2
-------
Capital costs.
Capital costs are defined for the purposes of this report as
all frontrend loaded, out-of-pocket expenditures for the
provision of treatment/disposal facilities. These costs
include any money for research and development necessary to
establish the process, land costs when applicable,
equipment, construction and installation, buildings,
services, engineering, special start-up costs and contractor
profits and contingencies.
When capital costs are known for a specific plant using a
given treatment/disposal technology, cost adjustment to the
typical plant size was made using experimental factors.
Exponent values of 0.6 for process equipment, 0.8 for situa-
tions involving scale-up by use of multiple units and/or
partial process equipment and partial non-volume oriented
operations, and 1.0 for treatment/disposal operations that
are independent of volume, at least in the range covered,
were applied.
Zilili Annualized Capital Costs
Almost all capital costs for treatment and disposal
facilities are front-end loaded; i.e., most if not all of
the money is spent during the first year or two of the
useful life. This present worth sum can be converted to
equipment uniform annual disbursements by utilizing the
Capital Recovery Factor Method:
Uniform Annual Disbursement = P i(1+i} nth power
(1+i)nth power - 1
Where P = present value (capital expenditureV/i =
interest rate, X/100,n = useful life in years
The capital recovery factor equation above may be
rewritten as:
Uniform Annual Disbursement = P(CR - i% - n)
Where (CR - i% - n) is the capital Recovery Factor
for i% interest taken over "n" years useful life.
The capital recovery factor method is used for all
annualized capital costs on this report, which, in effect,
would be similar to constant annual payments on principal
and interest were the capital facilities paid for through a
constant payment mortgage.
7-3
-------
Land-destined hazardous wastes require removal of land from
other economic use. The amount of land so tied up will
depend on the treatment/disposal method employed and the
amount of wastes involved. Although land is non-depreciable
according to IRS regulations, there are instances where the
market value of the land for land-destined wastes has been
significantly reduced permanently, or actually become
unsuitable for future use due to the nature of the stored
waste. Therefore, costs estimates have assumed land values
and capital recovery on the following basis:
(1) If land requirements for on-site treatment/disposal are
not significant, then no cost allowance has been made.
(2) where on-site land requirements are significant and the
storage or disposal of wastes does not affect the
ultimate market value of the land, cost estimates
include only interest on invested money.
(3) For significant on-site land requirements where the
ultimate market value and/or availability of the land
has been seriously reduced, cost estimates include both
capital depreciation and interest on invested money.
(t») off-site treatment/disposal land requirements and costs
are not considered directly. It is assumed that land
costs are included in the overall contractor's fees
along with its other expenses and profit.
In view of the extreme variability in land costs, no attempt
has been made to set different land values for each plant,
industry or location. Instead, a constant value of
$12,350/hectare ($5000/acre) has been used throughout.
Where land costs are a major portion of on-site
storage/disposal costs discussions and figures have been
used to demonstrate the sensitivity of costs to land value.
liJii Qeerating Expenses
Annual costs of operating the treatment/disposal facilities
include labor, supervision, materials, maintenance, taxes,
insurance and power and energy. Operating costs combined
with annualized capital costs give the total costs for
treatment and disposal operations. No interest cost was
included for operating (working) capital. Since working
capital might be assumed to be one sixth to one third of
annual operating costs (excluding depreciation) , about 1-236'
of total operating costs might be involved. This is
considered to be well within the accuracy of the estimates.
7-U
-------
a. Labor a.rjd Supervision Cpstg
Based on discussions with inorganic chemicals indus-
try plant management personnel, the following costs
are used for labor and supervisory needs.
Category
Process operators, $7.50
Plant laborers
Truck driver, 8.50
Equipment operators
Supervision 10.00
The above figures include wages, fringe benefits, and
plant overhead.
b. Taxes and Insurance
Taxes and insurance are taken as 2 percent of
invested capital, excluding research and develop*
ment.
c . Other Operating ^Costs
Operating costs for maintenance, materials and
power and energy are variable for each individual
case.
Rationale for ^Tyjoical Plants"
All plant costs are estimated for "typical plants" rather
than for any actual plant. "Typical plants" are defined for
purpose of these cost estimates as:
the arithmetic average of production size and age for ,
all plants, or the size and age agreed upon by a
substantial fraction of the manufacturers in the
subcategory producing the given chemical.
Locations are treated somewhat differently. Where
pertinent, geographical descriptions of typical plants are
given. In those cases where production is widely
distributed, it is not given. Otherwise site location
descriptions such as "industrial complex", "rural" or
"urban" solitary location are given. The exclusive use of
"typical plants" also allows us to maintain confidentiality
of supplied information.
7-5
-------
It should be noted here that the costs to treat and dispose
of hazardous wastes at any one given plant may be
considerably higher than the typical plant on a visit basis
because of individual circumstances.
lil DEFINITION OF TECHNOLOGY LEVELS
Costs are developed for three levels of technology
consistent with those defined in Phase III. These
definitions redefined, with pertinent comments, are:
Level I
Technology currently employed by typical facilities^ i.e.
broad average present treatment and disposal practice. For
most large volumed wastes two or three options are required
to cover the .different technologies utilized.
Level II
!§§£ technology currently employed. Identified technology at
this level must represent the soundest process from an
environmental and health standpoint, currently in use in at
least one (1) location. Installations must be commercial
scale; pilot plant and bench scale installations are not
suitable . For inorganic chemicals land-destined hazardous
wastes this level may in a number of instances be similar to
Level I .
Level III
Technology necessary to groyide adeguate health and envi-
ronmental protection^ Level III may be more or less
sophisticated or may be identical with Level I or II
Technology. At this level, identified technology may
include pilot or bench scale processes providing the exact
stage of development is identified. One pertinent
difference between Level III Technology and Levels I and II
Technology is that it is not necessary that at least one (1)
location be using this technology. Technology transfers
from other industries is also included.
I:.! COSTS FOR TREATMENT AND DISPOSAL OF LAND DESTINED
WASTES
Treatment and disposal costs are presented below for the
hazardous wastes involved in the production of individual
inorganic chemicals.
7-6
-------
7^3.1 Alkalies and Chlorine (SIC 2812)
liJ-Jj-Ji Chlorine - Diaphragm Gel,!, P£ocgss
Hazardous wastes from the diaphragm cell process for pro-
duction of chlorine are relatively small in volume but
varied in nature. These hazardous wastes include lead
compounds, asbestos, and chlorinated hydrocarbons.
Because of the several approaches to handling hazardous
wastes in this industry, costs have been developed for
various options of treatment/disposal technology. Both lead
and chlorinated hydrocarbons are rapidly diminishing in
quantity and importance as the change to coated metal anodes
progresses. At least 75 percent of the plants contacted are
either now using coated metal anodes or plan to make the
conversion in the near future. This conversion is taking
place not so much for environmental reasons as for operating
costs and energy savings. Asbestos will also be replaced
with plastic membranes but the timing of this possible
transition is uncertain.
The treatment/disposal technology situation for hazardous
wastes from diaphragm cell plants is dominated by two
factors:
(a) the continuing conversion to coated metal anodes is re-
ducing the total amount of hazardous waste being
generated, and,
(b) the size of the hazardous waste streams are relatively
small. The brine purification sludges, which comprise
the major portion of the solid wastes, are not
contaminated with asbestos, lead or chlorinated
hydrocarbons .
The costs for all treatment/disposal options are up to
$0.30 /metric ton of chlorine produced.
All indications are that the diaphragm cell chlor-alkali
industry is moving in the direction of diminishing amounts
of land-destined hazardous waste and that even if total
elimination of these hazardous wastes is not achieved
through use of plastic membranes or other process
modifications the level of residual wastes will be small
enough that they can be disposed of safely without any
significant economic impact to the industry. Table 7-1
summarizes costs for various levels of disposal technology.
The costs for the landfill and secured landfill disposals
have been given as contractor disposal costs. These should
be considered as bounding values.
7-7
-------
Table 7-1. Costs For Treatment/Disposal, Diaphragm Cell Process,
Alkalies and Chlorine, SIC 2812
Plant Description
450 metric tons of chlorine per day
28 /ears old
located in industrial complex
uses carbon anodes and asbestos separators
Hazardous Waste Stream
Form:
Hazardous components:
Non-hazardous compo-
ents:
Total Hazardous stream:
Sludges
0.09 kkg/day lead as metal and carbonates
0.18 kkg/day asbestos
0.2 kkg/day chlorinated hydrocarbons
water
carbon
rubble
salt
1.7 kkg/day (dry basis)
5.7 kkg/day (moisture included)
Level:
Option:
Investment Costs
Land
Other
Total
Annual Costs
Capital
Operating
Energy & Power
Contractor
Total
Cost per Metric Ton Chlorine
Overall Cost per Metric Ton
of Hazardous Waste (Wet)
1
4,000
40,000
44,000
500
4,000
TOO
3,700
8,300
0.06
4.0
2
0
0
0
0
0
0
7,500
7,500
0.05
3.6
II and III
3
0
0
0
0
0
0
50,000
50,000
0.3
24.
Description of Treatment/Disposal Technical Options
(1) Pond storage of lead precipitates and asbestos, contractor burning of chlorinated hydrocarbons
(2) Landfill (off-site) for asbestos and lead sludge and burning of chlorincated hydrocarbons by
contractors.
(3) Secured landfill (off-site) for asbestos, lead sludges and chlorinated hydrocarbons
7-8
-------
Chj,grj,ne-tyercury Cell Process
Although there are small amounts of chlorinated hydrocarbons
present in the hazardous wastes from this process the pre-
dominant contaminant is mercury. Wastes come from three
general sources:
(a) brine purification muds containing low concentrations of
mercury but often rather large in volume,
(b) process wastes - often rich in mercury content but
rather low in volume. These wastes include filter
sludges, vessel cleanouts, leaks and spills,
(c) water treatment precipitates - again small but conce-
trated in mercury content, usually as the sulfide.
Costs have been developed for several options of
treatment/disposal technology for mercury-containing sludges
(see Table 7-2). In addition to technology options, factors
which have paramount influence on costs, the purity of the
salt used and availability of secured landfill facilities,
have also been costed and are shown in summary Figures 7-1 •
The treatment/disposal technology costs range greatly
depending on the treatment/disposal option, amount of brine
impurities and availability of secured landfill facilities.
For purposes of these calculations it has been assumed that
secured landfill is not available on-site and has to be
contracted.
Conclusions that may be drawn from the cost calculations
are:
(a) For all treatment/disposal technologies it is important
that the water of the mercury-containing sludges be
minimized. Distillation of water in retorting
operations significantly increases the fuel
requirements. Contract disposal of water in secured
landfill is also not desirable. Whenever possible solid
contents of sludges should be at least 40-50 percent.
(b) On-site secured landfill facilities may be the most
economically attractive approach. Cost calculations
indicate approximately $8/ton (of waste) for on-site
landfill as contrasted with $50/ton or more for contract
secured landfill disposal.
(c) Off-site contracted secured landfill costs are lower or
similar to retorting or extraction costs when the waste
load is 40 Ibs/ton or less, and the transportation
distance is less than 100 miles. For long distance
hauling the transportation costs become prohibitive.
7-9
-------
Table 7-2. Costs For Treatment/Disposal, Mercury Cell Process,
Alkalies and Chlorine, SIC 2812
Plant Description
250 metric tons of chlorine per day
12 year* old
eastern state, in industrial complex
Hazardous Waste Stream
form:
hazardous components:
non-hazardous
components:
total hazardous waste
stream:
sludges, muds and filter cake
0.08 kkg/day chlorinated hydrocarbons
0.015 kkg/day mercury as metal, chloride and sulfide
calcium carbonate
magnesium hydroxide
barium sulfafe
salt
graphite
filter aid
water
4.8 kkg/day (dry basis)
12 kkg/day (moisture included)
Level:
Option:
Investment Costs
Land
Other
Total
Annual Costs
Capital
Operating
Energy & Power
Contractor
Total
Cost per Metric Ton Chlorine
Overall Cost per Metric Ton
of Hazardous Waste (Wet)
1
1
0
15,000
15,000
4,000
294,400
negligible
0
298,400
3.3
68.7
2
50,000
350,000
447,500
52,500
39,000
130
0
91,600
1.0
20.8
3
10,000
30,000
40,000
10,000
41 ,000
2,700
0
53,700
0.6
12.5
II
4
10,000
470,000
580,000
94,500
122,000
6,500
.0
222,700
3.0
62.
II and III
5
0
0
0
0
0
0
306,000
306,000
3.4
70..
6
10,000
500,000
510,000
135,000
130,000
20,000
0
285,000
2.9
59.
Description of Treatment/Disposal Technical Options:
(1) On-site drum storage
(2) On-site pond storage
(3) On-site landfill
(4) Chemical extraction of brine purification sludge and on-site secured landfilllng of
process sludges
(5) Off-site secured landfill (50 miles)
(6) Retorting of sludges and on-site landfill of residues
7-10
-------
Ul
HI
3.00r
2.00 •
O
z
OT
E
t
U.
3
200
400
600
800
TRANSPORTATION DISTANCE TO NEAREST
SECURED LANDFILL(KILOMETERS)
6.oor
4.00 -
O
fc
2.00|-
jjj
s
d
O
2OO
4OO
6OO
8OO
TRANSPORTATION DISTANCE TO NEAREST
SECURED LANDFILU KILOMETERS)
12.00
Q
g
o.
Ul
£
3
5
fe
S
£
d
8.00-
4.OO •
200
400
600
800
TRANSPORTATION DISTANCE TO NEAREST
SECURED LANDFILU KILOMETERS)
20 POUNDS (DRY BASIS)/TON CHLORINE
40 POUNDS (DRY BASIS)/TON CHLORINE
100 POUNDS (DRY BASIS)/TON CHLORINE
O-RETORTING AND LANDFILL, Q - SECURED LANDFILL BULK HANDLING, Q- SECURED LANDFILL DRUM CONTAINERS, A- EXTRACTION AND LANDFILL
FIGURE 7-1
DISPOSAL COSTS FOR MERCURY-CONTAINING SLUDGES
-------
(d) Contract secured landfilling is not economical at any
hauling distance for waste loads greater than 75
Ibs/ton. 0
(e) Retorting and extraction treatments which involve
residues are particularly attractive for heavy waste
loads, but may also be competitive at lower Values.
A number of plants now follow a combination of
treatment/disposal options for their wastes.. One often used
is to retort the high mercury content process and water
treatment sludges and landstore or landfill brine sludges*
Only one company is currently retorting the entire waste
load. Other plants are considering this option, however,
and are watching the current full waste retorting operation
carefully.C23>
Brine sludge constitutes the major volume (but not amount of
mercury) of hazardous wastes. If regulatory actions force
brine sludge treatment or disposal in secured landfill
areas, plants with large amounts of brine sludge have the
options of finding new sources of salt, purifying their salt
prior to possible mercury contamination, or converting to a
diaphragm cell process.
liJiliJ Chlorine - DownJ^s Cell Process
The only remaining land-destined hazardous wastes after
treatment from the the manufacture of chlorine with co-
product sodium consist of calcium-sodium sludges filtered
from the product for purification purposes. Two of the five
plants located near saltwater ocean barge their wastes. The
other three for reasons of process confidentiality gave only
sketchy descriptions of their in-process treatment
technologies and the wastes involved, but recovery
techniques are practiced by all three. Some report land-
destined residues from the recovery process, others do hot.
They state that the residues are non-hazardous. The reacted
cell tear-down rubble is also non-hazardous.
Table 7-3 summarizes the cost estimates for two
treatment/disposal technologies. Although the economic
value of the sodium product of these plants exceeds that of
the chlorine product by 3-fold, for consistency with the
other SIC 28121 processes, the costs per unit product have
been given on a chlorine-only basis.
The Level III off-site contract treatment/disposal of the
sodium-calcium sludge assumes $320/metric ton of sludge
disposal costs. Safe and controlled destruction should be
feasible on land, but as yet there is likely to be little
demand for this service.
7-12
-------
Table 7-3. Costs For Treatment/Disposal, Down's Cell Process,
Alkalies and Chlorine, SIC 2812
Plant Description
140 metric tons of chlorine per day
sodium metal co-product
25 years old
estern state, industrial complex
Hazardous Waste Stream
form:
hazardous components:
non-hazardous components:
total hazardous stream:
metallic sludge (no water)
cell tear-down rubble
0.9 kkg/day sodium plus calcium (elemental)-
principal waste load in sludge
< 0.1 kkg/day sodium for residues left from cell
tear-down
negligible in sludge
carbon and cell construction materials
approx. 8-10 kkg/day contaminated rubble
0.9 kkg/day sodium-calcium sludge, where wasted
Level
Option
Investment Costs
Land
Other
Total
Annual Costs
Capital
Operating
Energy & Power
Contractor
Total
Cost per Metric Ton Chlorine
Cost per Metric Ton of
Hazardous Waste
1 and II
1A*
5,000
5,000
10,000
1,000
4,000
nil
0
5,000
0.1
1.4
IB*
5,000
5,000
10,000
1,000
34,000
nil
20,000
55,000
1.1
15.
Ill
2
5,000
5,000
10,000
1,000
34,000
nil
90,000
125,000
2.4
35.
Description of Treatment/Cost Options:
(1) On-site dumping and spreading of rubble contaminated with small amounts of sodium.
Drumming and disposal at sea of sodium-calcium sludges by those plants having such wastes.
(2) Off-site contract land disposal of sludges. This option is a conceptualized one since no
contractor presently offers this service. This estimate is based on the principal waste load
of 0.9 kkg/day of sludge to cover the possibility that those disposing at sea may resort to
land disposal in the future. The contaminated rubble wastes treated and disposed'of as at
present.
*(1A) Option (1) for those plants without sludges to waste, only contaminated rubble.
i (IB) Those plants with both wastes.
7-13
-------
lilil Inorganic Pigments JSIC 2816)
2iJi2il 2iianium Dioxide-Chloride Process
The ores from which titanium dioxide is produced contain
chromium, vanadium and iron. These components are largely
removed from the titanium dioxide and therefore concentrated
in the Wastes. Ores (and wastes) differ widely in both
amount of non-titanium dioxide wastes and the composition of
those wastes.
Most wastes from the chloride process are currently land
disposed, common disposal methods are on-site land dumping,
off-site contract land-dumping or landfilling and deep
welling. Some is ocean barged.
Approved landfills or land dumping should suffice for
neutralized wastes, which are largely ore gangue and iron
compounds, and small amounts of hazardous metals which are
present.
In view of the vast difference in waste quantities involved
with ore composition, cost estimates have been made for
rutile ore (approximately 95 percent titanium dioxide) and
ilmenite ore (approximately 60 percent titanium dioxide) as
representative of each end of the waste load spectrum.
Table 7-4 and 7-5 summarize the costs developed for wastes
for each ore.
2ili2i2 Chrome Pigments and Iron Blue
The manufacture of chrome pigments such as zinc yellow,
chrome yellow, molybdate orange, chrome green, and chrome
oxide green produces relatively large volumes of
land-destined wastes containing lead, zinc, and chromates.
Iron blue contributes complex cyanide wastes.
Chrome pigments are usually made in integrated facilities
flexible to shift from one product or combination of
products to another. Since iron blue is needed for
manufacture of chrome green, the inclusion of iron blue
manufacture with the chrome pigments is a logical one and
Wastes are combined.
Zinc yellow being somewhat soluble in water differs from the
other chrome pigments, which are relatively insoluble, and
has to be treated differently.
Some waste sludges are not now being treated prior to
disposal. Attention is being paid to minimizing the amount
of these sludges through at least two mechanisms:
7-14
-------
Table 7-4. Costs For Treatment/Disposal, Chloride Process,
Titanium Dioxide Pigment, SIC 2816
Plant Description
100 metric tons of pigment per day
rutlle ore raw material
12 years old
located In Industrial area, eastern state
Hazardous Waste Stream
for IK
hazardous components:
non-hazardous compo-
nents:
total hazardous stream:
waste treatment sludges
0.13 kkg/day chromium as Cr(OH>3
ore residues
coke
silica
misc. metal hydroxides
water
27 kkg/day (dry basis)
110 kkg/day (moisture included)
Level
Option
Investment Costs
Lan3
Other
Total
Annual Costs
Capital
Operating
Energy & Power
Contractor
Total
Colt per Metric Ton
Pigment
Cott per Metric Ton
of Hazardous Waste
Wet)
1
1
5,000/yr.
nil
nil
5,000
32,000
nil
0
37,000
1
0.9
2
0
0
0
0
0
0
110,000
110,000
3
2.7
3
10,000
90,000
100,000
10,000
134,000
20,000
0
164,000
4.5
4.1
II and III
4
5,000/yr
nil
nil
5,000
47,000
nil
0
53,000
1.4
1.3
5
0
0
0
0
0
0
131,000
131,000
3.6
3.3
Description of Treatment/Disposal Options;
(1) neutralization; precipitation of wastes and on-site storage
(2) as above, except off-site contract disposal
(3) deep-welling without treatment
(4) as (1), except approved land storage on-site
(5) as (4), except off-site
7-15
-------
Table 7-5. Costs For Treatment/Disposal, Chloride Process,
Titanium Dioxide Pigment, SIC 2816
Plant Description
100 metric tons of pigment per day
Hmenite ore raw material
12 years old
located in industrial area, eastern state
Hazardous Waste Stream
form: waste treatment sludge
Hazardous components: 0.13 kkg/day chromium as Cr(OH)g
non-hazardous components: ore residues
coke
silica
misc. metal hydroxides
water
total hazardous stream: 140 kkg/day (dry basis)
560 kkg/day (moisture included)
Level
Option
Investment Costs
Land
Otter
Total
Annual Cosh
Capital
Operating
Unergy & Power
Contractor
Total
Cost per Metric Ton
Pigment
Cost per Metric Ton
of Hazardous Waste
(We*)
1
1
25,000/yr
nil
nil
25,000
140,000
1,000
0
166,000
4.5
0.8
2
0
0
0
0
0
0
550,000
550,000
15
2.7
3
10,000
110,000
120,000
12,000
160,000
24,000
0
196,000
5.4
1.0
II and III
4
25,000/yr
nil
nil
25,000
154,000
1,000
0
180,000
4.9
0.9
5
0
0
0
0
0
0
660,000
660,000
IB
3.2
Description of Treatment/Disposal Options:
(1) reutrallzation; precipitation of wastes and on-site storage
(2) us above> except off-site contract disposal
(3) deep welling without treatment
(4) as (1), except approved land storage on-site
(5) as (4), except off-site
7-16
-------
(a) Recovery during an early stage of processing so that the
materials can be reused. Heavy metals and chromates are
expensive and these provide some economic advantage to
this approach. Two plants are now recovering these
wastes completely.
(b) Maximizing the solids content of the sludges through
filtration or centrifuging.
The treatment/disposal technology costs, aside from
recovery, are primarily based on the availability of
suitable land for disposal. This in turn depends primarily
on land disposal regulations. Presently no unified set of
land disposal guidelines are in existence. There are
distinct movements at the state level in this direction.
California, Pennsylvania, Texas and a number of other states
have, are preparing, or are modifying such regulations.
Table 7-6 summarizes the costs for land disposal of sludges
from the chrome pigments and iron blue industry. Land
dumping is clearly the most economical. In fact, some
actual land dumping disposal costs are significantly lower
than the average cost estimated for the typical plant.
Simple landfilling is the next most economical disposal
practice.
Secured landfill, either by off-site contract or on-site
disposal is definitely more expensive. Some plants have
geologically suited disposal areas on-site, most do not. In
the cases where off-site contract disposal is necessary, a
significant additional cost for transportation may be added.
Transportation for 500 miles would approximately double the
disposal costs.
Costs for secured landfill facilities vary over a wide spec-
trum:
Potential Costs For Secured Landfill Facilities
Type of Secured Cost Range
$/ton
Public Facilities 1.50-6.00*
(California, Pennsylvania etc.)
Private 4.00-50.00**
(Scattered - Oklahoma, Washington,
Nevada, New York, Texas, Illinois)
7-17
-------
Table 7-6. Cosh For Treatment/Disposal, Chrome Pigments
and Iron Blues, SIC 2816
Plant Description
23 metric tons of pigment per day
46 yean old
northeastern state, Industrial area
Hazardous Waste Stream:
form:
hazardous components:
sludge from waste treatment
0.2 kkg/day chromic hydroxide
0.6 kkg/day lead chror,nte
0.06 kkg/day lead hydroxide
0.1 kkg/day zinc as oxide
0.06 kkg/day Iron complex cyanides
non-hazardous components: water
iron oxides and hydroxides
calcium sulfate
total hazardous stream:
2.3 kkg/day (dry basis)
3 kkg/day (moisture included)
Level
Option
Investment Costs
Land
Other
Total
Annual Costs
Capital
Operating
Energy & Power
Contractor
Total
Cost per Metric Ton
hgment
Cost per Metric Ton
of Hazardous Waste
(Wet)
1
1
0
0
0
0
0
0
15,000
15,000
1.7
14.
2
0
0
0
0
0
0
16,000
16,000
1.9
15.
II and III
3
0
0
0
0
0
0
62,000
62,000
7.5
57.
4
10,000
155,000
165,000
28,000
28,000
1,000
0
57,000
6.9
52.
Ill
5
0
0
0
0
0
0
62,000
62,000
7.5
57.
Description of Treatment/Disposal Options:
(1) pond storage and off-site land dumping
(2) simple landfilling (contractor)
(3) secured landfilling (contractor)
(4) on-site secured landfilling
(5) contractor chemical fixation and land disposal (not proven)
7-18
-------
* - Facilities need some modification to meet secured land-
fill definition but have basic potential with minor
modifications.
**- Low values are usually found where favorable geological
or climate conditions or fortuitous disposal facilities
are available and more disposal business is needed.
High values are found for specialized facilities such as
radioactive materials disposal sites and where disposal
conditions are difficult.
Itlil Industrial Inorganic Chemicals (SIC 2819)
liltlil Hydrofluoric Acid
Hydrofluoric acid is the basic chemical for the production
of most fluoride chemicals.
Fluoride-containing hazardous wastes from the production of
fluoride chemicals such as hydrofluoric acid, sodium sili-
cofluoride and aluminum fluoride, and including the
fluorides from phosphorus manufacture, constitute the
largest volumed single category of hazardous wastes within
the inorganic chemicals industry. As much as 60 percent of
the total hazardous wastes from the inorganic chemicals
industry contain fluorides, usually in the form of the
calcium salt.
It should be pointed out, however, that calcium fluoride is
only sparingly soluble in water (approximately 18 mg/liter)
and that most of the calcium fluoride is present in slags or
as a low percentage in major wastes such as calcium sulfate.
Nevertheless, fluoride-containing wastes require attention
as to both their storage and disposal. Leaching and
rainwater runoff from land-destined piles of such wastes is
of particular concern.
The process wastes from the manufacture of hydrofluoric acid
consist of approximately 3700 kgs of calcium sulfate,
calcium fluoride mixture per metric ton of acid produced.
Calcium fluoride content of the waste is approximately 2 to
3 percent by weight. Although some of this waste is used in
road beds, the great majority is land-dumped or landfilled.
Pond storage prior to final disposal is common. Table 7-7
summarizes technology and cost levels.
Waste loads are largely determined by the process and do not
vary in any significant fashion from plant to plant. The
waste load is also insensitive to plant age or size.
7-19
-------
Table 7-7. Costs For Treatment/Disposal, Hydrofluoric Acid
Manufacture, SIC 2819
Plant Description
64 metric tons of hydrofluoric acid per day
18 years old
eastern state, industrial complex
Hazardous Waste Stream
form: waste treatment sludge
hazardous components: 7 kkg/day calcium fluoride
non-hazardous components: water
calcium sulfate
silica
total hazardous stream: 240 kkg/day (dry basis)
300 kkg/day (moisture included)
Level
Option
Investment Costs
Land
Other
Total
Annual Costs
Ca pi ta 1
Operating
Energy & Power
Contractor
Total
Cost per Metric Ton HF
Cost per Metric Ton
of Hazardous Waste
(Wet)
1
1
(5,000/yr)
300,000
300,000
79,000
91,000
30,000
0
200,000
8.6
1.8
II
2
0
0
0
0
0
0
109,000
109,000
4.7
1.0
III
3
(5,000/yr)
500,000
500,000
133,000
101,000
30,000
0
264,000
11.3
2.4
4
(10,000/yr)
825,000
825,000
218,000
106,000
30,000
0
354,000
15.2
3.2
Description of Treatment/Disposal Options:
(1) on-site land dumping, transport by truck
(2) pond storage (ponds for water treatment needs) and contractor disposal (general)
(3) approved land dumping on-site, rainwater diversion and leachate monitoring
(4) as in (3), except secured landfill
7-20
-------
Plant location is an important factor for several reasons:
(a) Large amounts of disposal space are required;
availability and cost of land are major factors;
(b) Since leaching and rainfall runoff are major potential
sources of environmental contamination from disposed
wastes, a dry climate such as found in the western U. S.
would be desirable.
(c) Future use of the wastes for road beds, parking lots,
and other useful structural purposes depends on
proximity to the market. This is not a major factor
today but could be for the future.
7.3.3.2 Boric Acid
Residues from boric acid production are buried in secured
landfills and at a cost of $0.03 per metric ton of boric
acid processed ($6 per metric ton of waste stream). Since
there is only one boric acid manufacturer having a hazardous
waste situation, the details of the cost breakdown are not
divulged.
7.3.3.3 Aluminum Fluoride
Land-destined hazardous wastes from the manufacture of alu-
minum fluoride consist of aluminum fluoride, calcium
fluoride, calcium sulfate and lime. Since the fluorides
have only limited solubility in water they are considered to
be suitable for approved landfill operations. Also, since
aluminum fluoride is often produced in complexes producing
other fluoride chemicals the wastes are likely to be
combined with much larger quantities of similar wastes from
other processes.
Low per ton costs combined with a relatively low volume of
waste per ton of aluminum fluoride production gives disposal
values of $0.2 to $0.6 per metric'ton depending on the level
of technology employed. These costs are summarized in Table
7-8.
ZilsJjJi Sodiujn Silicofluoride
There are three plants in the United States producing this
chemical. Each uses a different waste treatment and
disposal process:
Plant 1 - Has no attributable land-destined wastes since
it recycles unused portions of its raw
material supply back to the parent
process.
Plant 2 - Deep wells all wastes.
7-21
-------
Table 7-8. Costs For Treatment/Disposal, Aluminum Fluoride
Manufacture, SIC 2819
Plant Description
145 metric tons of aluminum fluoride per day
25 years old
southeastern stare, industrial complex
Hazardous Waste Stream
form: waste treatment sludge
hazardous components! 12 klcg/day calcium fluoride
non-hazardous components: calcium sulfate
hydra ted lime
water
total hazardous stream: 26 kkg/day (dry basis)
33 kkg/day (moisture Included)
Level
Option
Investment Costs
Land
Other
Total
Annual Costs
Capitol
Operating
Energy & Power
Contractor
Total
Cost per Metric Ton AlF-^
Cosf per Metric Ton
of Hazardous Waste (Wet)
1 and II
1
(1,000/yr)
30,000
30,000
4,000
8,000
small
0
12,000
0.2
1.0
2
0
0
0
0
0
0
12,000
12,000
0.2
1.0
III
3
(1,000/yr)
120,000
120,000
J4,000
18,000
small
0
32,000
0.6
2.7
Description of Treatment/Disposal Options:
(1) pond storage and on-site dumping
(2) contract landfill
(3) secured landfill on-site, rainwater diversion, leachate monitoring
7-22
-------
Plant 3 - Treats its wastes as a small portion of an
overall waste stream from the chemical
complex.
The small number of plants and the different waste
treatment/ disposal technology used at each reduces the
significance of the "typical plant" for this industry
segment.
Treatment and disposal of the hazardous wastes is similar to
previous fluoride chemicals wastes. Deep welling of the
entire waste stream without treatment costs over $8 per
metric ton but by-passes expensive water treatment costs not
included in the other disposal values. This cost is
misleading because it can be attributed largely or wholly to
waste water discharge control. Table 7-9 summarizes
disposal technology and cost levels.
liliJjJ Chromates Manufacture (Ore Processing^
Chromate ore is the source for the basic chromate chemicals
such as sodium chromate, sodium dichr ornate, potassium di-
chromate, and chromic acid. The ore, which is generally of
low purity produces a large volume of gangue and
land- destined solid waste. Costs for various levels and
options of treatment/disposal technology for land-destined
wastes from the production of chromates through ore
processing are given in Table 7-10.
The basic process consists of reacting chromite ore with
limestone and soda ash in kilns to produce sodium dichromate
and chromate. The ore residues, along with much smaller
quantities of water treatment precipitates and
residual water soluble chromates in the solid wastes, are
large in volume, approximately 1700-3500 kg/kkg of product.
Other chromium chemicals such as chromic acid and potassium
dichromate are produced in secondary operations using the
sodium chromates and dichr omates as raw materials. Chromic
acid processes have negligible hazardous solid wastes which
are handled as part of the ore processing process.
Potassium dichromate process solid wastes consist primarily
of sodium chloride plus a small quantity of water treatment
chrome precipitates and residual water soluble
chromates. Solid waste volumes for the potassium dichromate
process are significantly less than for the primary ore
process, but aside from the sodium chloride have similar
treatment and disposal technology considerations as the
land-destined solid wastes from the ore process.
7-23
-------
Table 7-9. Costs For Treatment/Disposal, Sodium Stltcofluortde
Manufacture, SIC 2819
Plant Description
45 metric tons of sodium stllcofluoride per day
20 years old
Florida or Texas, Industrial complex
Hazardous Waste Stream (lime treatment option)
form: watf* treatment sludge
hazardous components: 2.6-4.5 Wco/day calcium fluoride
non-hazardous components: silica
hydrated lime
water
salt
total waste stream:
7 kkg/day (dry basis)
23 kkg/day (moisture included) — land-dumped
Level
Option
Investment Costs
Land
Other
Total
Annual Costs
Capital
Operating
Energy & Power
Contractor
Total
Cost per Metric Ton
Sodium Silicofluorlde
Cost per Metric Ton of
Total Hazardous Waste
Stream (Wet)
1 and II
deep-
welling
0
650,000
650,000
105,000
35,000
1,000
0
141,000
8.5
17.**
lime treatment,
wastes
land-dumped
(1,000/yr)
34,000
34,000
4,000
5,000
nil
0
9,000
0.6*
1.1
III
lime treatment,
land-dumped
collection
and treatment
of run-off
(1,000/yr)
44,000
44,000
7,000
6,000
500
0
13,500
0.8*
1.6
*Cost for solid waste disposal only. Water treatment costs not Included.
**Thls cost given on the same moisture content basis (70%) as the land-dumped option
for comparison only. It should be realized that a pumpable slurry for deep-welling
would have much more water in it.
7-24
-------
Table 7-10. Costs For Treatment/Disposal, Chromates Manufacture,
SIC 2819
Plant Description
182metric tons of sodium dichromate per day
23 yeors old
North Carolina, Maryland or Texas, industrial area
Hazardous Waste Stream
form: wast* treatment muds and sludges
hazardous components: chromium as chromfc'hyclroxide or chromate
non-hazardous components:
water
or* residues
total waste stream: 150 kkg/day (dry basis)
200 kkg/day (moisture included)
Level
Option
Investment Costs
Land
Other
Total
Annual Coirs
Capital
Ope ret ing
Energy & Power
Contractor
Total
Cost per Metric Ton of
Chromate
Cost per Metric Ton
of Hazardous Wastes
CWet)
1
1
(annualized)
700,000
700,000
82,000
91,000
7,000
0
180,000
2.7
2.5
2
[annualized)
3,200,000
3,200,000
370,000
170,000
7,000
0
550,000
8.4
7,6
3
0
700,000
700,000
82,000
91,000
7,000
250,000
430,000
6.5
6.0
II and III
4
(annualized)
1,020,000
1,020,000
132,000
91,000
7,000
250,000
480,000
7.3
6.7
5
0
500,000
500,000
81,000
158,000
1,000
250,000
490,000
7.4
6.8
Description of Treatment/Disposal Options;
(1) unltned pond storage
(2) lined pond storage
(3) unlined pond storage plus on-site or local contract landfill
(4) chemical treatment plus ponding and approved contract landfill
(5) chemical treatment plus filtration and approved contract landfill
7-25
-------
The primary hazardous wastes from all chromate processes
discussed above are water soluble chromates* To maintain
water quality standards for discharge of aqueous streams the
chromates are usually reduced to the less hazardous chromium
hydroxides by any one of a number of chemical agents such as
sulfides, sulfur dioxide, ferrous sulfate and ferrous
chloride followed by alkaline precipitation. Less commonly,
the soluble chromates are reduced by washing and extraction
operations. The solid precipitates and ore residues are
then separated from the aqueous phase by filtration or pond
settling.
Once the water soluble chromates have been reduced or elim-
inated, the solids are sent without further treatment to
land storage or landfill. These wastes, if free of
appreciable water soluble chromates, contain primarily inert
ore residues, soluble salts such as sodium chloride, and
precipitated chromium hydroxide. As may be seen in Figure
6-1 the solubility of chromium hydroxide is 0.1 mg/liter
or less between pH of 7 and 9, but increases rapidly as the
media becomes more acidic or basic. For this reason land
storage or landfill needs to be restricted to near neutral
environments.
The treatment /disposal costs are primarily due to:
(a) treatment of the aqueous waste streams to reduce all
soluble chromates to very low levels, usually determined
by water quality guidelines.
(b) disposal of large amounts of ore residues from the
primary ore processing process.
If soluble chromates are not removed from the land-destined
solid residues, significant hazardous leachate problems
result, and solid wastes must be disposed of in secured
landfill areas. Removal of chromates allows disposal of the
solid wastes in lower cost and more available approved
landfills.
The heavy load of ore residues for the ore processing
chromates process makes it mandatory that:
(a) the land disposal have low cost per ton,
(b) large disposal sites are available.
* Nickel Sulfate
The only land-destined wastes from the manufacture of nickel
sulfate come from purification muds and water quality
treatment to remove residual nickel salts. Table 7-11
summarizes disposal technology and cost levels. On-site
7-26
-------
Table 7-11. Costs for Treatment/Disposal, Nickel Sulfate
Manufacture (SIC 2819)
Plant Description
9 metric tons of nickel sulfate per day
37 years old
northcentral state, industrial area
uses plating wastes as part of raw material
Hazardous Waste Stream
form: waste treatment sludge
hazardous components: 0.7 kg/day nickel hydroxide
non-hazardous components:
total waste stream:
water
filter aid
0.5 kkg/day (dry basis)
1 kkg/day (moisture included)
Level
Option
Investment Costs
Land
Other
Total
Annual Costs
Capital
Operating
Energy & Power
Contractor
Total
Cost per Metric Ton of
Nickel Sulfate
Cost per Metric Ton
of Hazardous Waste
(Wet)
1 and II
1
(annual! zed)
10,000
10,000
1,200
2,500
0
0
3,700
1.1
10.
Ill
2
0
0
0
0
9,000
0
18,000
27,000
8.3
75.
3
0
0
0
0
0
0
13,000
13,000
3.8
36.
Description of Treatment/Control Options;
(1) on-site landfill
(2) off-site secured landfill in lined drums
(3) chemical fixation by contractor off-site (not proven)
7-27
-------
landfilling cost estimates are approximately $1/metric ton,
off-site secured landfilling SB/metric ton, and chemical
fixation costs $4/metric ton.
Zil.i3.il Phgsghgrus
Hazardous land-destined waste components from phosphorus
manufacture include phosphorus itself and fluorides.
Hazardous phosphorus land-destined wastes come from air and
water treatment operations and process components.
To protect the effluent water quality it is necessary to
reduce or remove the following wastes:
(a) suspended phosphorus from the phossy water,
(b) fluorides, dusts and other air pollutant components
through gas scrubbing from the ore calcining and furnace
vents.
There are a variety of methods used for treating the phossy
water including pond settling, clarifiers, filters and
centrifuges. The latter three treatment methods usually
involve direct return of collected phosphorus to the
process. Phosphorus settled to the bottom of ponds often is
allowed to remain there indefinitely.
The fluorides removed in the scrubbers are treated with lime
and also allowed to settle in ponds. Because of the large
quantities of settled wastes fairly frequent pond cleaning
is practiced.
Phosphorus stored in the bottom of ponds is often recovered
by means of:
(a) direct mining of pure phosphorus,
(b) combinations of isolation, heating (to enable separation
and handling of molten phosphorus) pumping and settling
sequences for gravity separations, and
(c) distillation operations. These recovery techniques are
economically feasible because of the high price for
elemental phosphorus.
The solid calcium fluoride wastes from the scrubbers are
usually land stored or landfilled on-site.
In addition to the phosphorus and calcium fluoride wastes
there is also phosphorus containing dust from electrostatic
precipitators in the process. This dust may be settled in
ponds and returned partially or entirely to the process,
land dumped to let the small amount of phosphorus oxidize or
7-28
-------
burned to remove residual phosphorus. Fumes and air
pollution problems arise from the land dumping and the
burning. Burning operations may, however, be integrated
with furnace fume control facilities. At least one major
producer is using this approach.
The cost for treatment/disposal technology for phosphorus
land- destined wastes are summarized in Table 7-12.
Recovery of phosphorus from phossy water, either as a
process operation or from the settling ponds, is an
economically viable option. The high recovery value of
phosphorus ($300+/ton in 1973 to perhaps twice that in mid
1971) pays for most of the recovery operation costs.
7 ..3.3.81 Phosphorus Pentasulfi.de
Phosphorus is reacted with sulfur to form phosphorus
pentasulfide. Hazardous waste loads are small, both from
the standpoint of production tonnage of the chemical and the
waste generated per unit of product.
The wastes may be either incinerated (with proper air pol-
lution safeguard) or placed in secured landfills. Estimated
costs for either secured landfilling or incineration are
$0. 07/metric ton of phosphorus pentasulfide produced. (See
Table 7-13).
7.3.3.9 Phosp_horus Trichloride
Phosphorus is reacted with chlorine to produce phosphorus
trichloride. Hazardous waste loads are even smaller than
for phosphorus pentasulfide. Costs for secured landfill
after treatment are of the order of $0.4 /me trie ton. (See
Table 7-
7.3..U Samgle Cost Calculation
Mercury Cell Process, Alkalies and Chlorine (SIC 28121)
Basis: (a) 10 pounds (dry) of mercury-containing sludges
per ton of chlorine produced (20 kg/kkg) .
(b) All sludges are combined and stored and
disposed of in the same way (unless otherwise
noted) .
(c) Size of plant is 250 metric ton/day
(275 ton/day) of chlorine.
7-29
-------
Table 7-12. Costs For Treatment/Disposal, Phosphorus Manufacture,
SIC 2819
Plant1 Description
136 metric tons of phosphorus per day
26 years old
Florida, Tennessee, Idaho, or Montana, rural area
Hazardous Waste Stream
form:
waste treatment sludges
hazardous components: 9 kkg/day calcium fluoride
7 kkg/day phosphorus
non-hazardous components:
total waste stream:
silica
hydrated lime
calcium phosphate
calcium sulfate
water
50 kkg/day (dry basis)
100 kkg/day (moisture included)
Level
Option
Investment Costs
Land
Other
Total
Annual Costs
Capital
Operating
Energy & Power
Contractor
Total
Cost per Metric Ton of
Phosphorus
Cost per Metric Ton
of Hazardous Waste
(Wet)
1
(annual ized)
150,000
150,000
19,000
62,000
2,000
0
83,000
1.7
2.3
2
(annualized)
110,000
110,000
27,000
73,600
1,000
0
104,600
2.1
2.8
II and III
3
(annualized)
805,000
805,000
210,000
65,000
4,000
0
280,000
5.6
7.7
Description of Treatment/Control Options:
(1) on-site storage of phossy water in bottom of water-filled settling ponds. Precipttator
dusts land dumped. Calciner and furnace fume scrubber wastes landfilled after
lime treatment.
(2) on-site storage of phossy water in bottom of water-filled unlined settling ponds.
Precipitator dusts recycled. Calciner and furnace fume scrubber wastes landfilled
after lime treatment.
(3) Recovery of phosphorus wastes by distillation. Precipitator dust recycled. Calciner
and furnace fume scrubber wastes put in approved landfill.
7-30
-------
Table 7-13. Costs For Treatment/Disposal, Phosphorus
Pentasulfide Manufacture, SIC 2819
Plant Description
55,000 metric tons of phosphorui pentasulflde per year
18 years old
eastern state, industrial area
Hazardous Waste Stream
form:
dry residues and dusts
hazardous components: 3 kkg/year arsenic sulflde .
8 kkg/year phosphorus and phosphorus sulfldes
non-hazardous components:
total waste stream:
glassy phosphates
iron sulfide
110 kkg per year
Level
Option
Investment Costs
Land
Other
Total
Annual Costs
Capital
Operating
Energy & Power
Contractor
Total
Cost per Metric Ton of
Phosphorus Pentasulfide
Cost per Metric Ton of
Hazardous Waste
1,11, and III
1
0
0
0
0
0
0
3,900
3,900
0.07
35.
2
0
20,000
20,000
2,300
1,000
500
6
3,800
0.07
35.
Description of Treatment/Control Options
(1) contract secured landfill
(2) incineration
7-31
-------
Table 7-14. Costs for Treatment/Disposal, Phosphorus Trichloride
Manufacture (SIC 2819)
Plant Description
58,000 metric tons of phosphorus trichloride per year
10-20 years old
eastern state, industrial area
Hazardous Waste Stream
form: dry residues
hazardous components: 3 kkg/year arsenic chloride
non-hazardous components:
total waste stream:
glassy phosphates
iron chlorides
60 kkg per year
Level
I, II, and III
Option
Secured contract landfill in lined drums
Investment Costs
Land
Other
Total
Annual Costs
Capital
Operating
Energy & Power
Contractor
Total
Cost per Metric Ton of
Phosphorus Trichloride
Cost per Metric Ton
of Hazardous Waste
0
15,000
15,000
1,700
9,000
300
9,600
20,600
0.4
340.
7-32
-------
Option 3: On-site Landfill
Level I Technology
Capital Costs
Land Requirements
Sludge volume at 40% solids (40 #/ton C12 divided
by .40 = 100 S/ton C12)
= 100 #/ton C12 x 275 ton/day x 1 ftV75f x 365 day/yr
= 133,833 ftVyr = 4,957 yd*
27 ftVyd* yr
Use 20 ft. depth and 75% utilization of space
= 15 ft deep
acres - 4.957 vdVvr x 3 ft x 27 acre _
year" 15 ft yd 43,560 yd*
= 0.62 acre/year needed
= 0.62 acre/year x $5,000/acre = $3,000/yr
Equipment
Front end loader $10,000 x 1/2* = $5,000
Dump truck (10 tonj $13,000 x 1/2* = $6,500
Bulldozer (cat-977) $56,000 x 1/2* = $28.000
Total $39,500
*The capital cost for equipment is halved because
it is used only approximately 1/2 time for land-
fill operations.
Assume 5 year life for front end loader, truck,
and bulldozer
Capital recovery factor = 0.2638 (10%, 5 years)
Uniform annual series am't = $39,500 x 0.2638
= $10,420
7-33
-------
Labor 1/2* man each at $8.50/hr on front end
loader, truck, and bulldozer
* $8.50/hr x 8 hr/day x 260 day/yr x 3/2
$26,550/yr
*1/2 man indicates that only approximately 1/2 of
the actual working time is spent in landfill opera-
tions.
Supervision =* 25% of labor costs = $6,630
Materials = none
Maintenance = 10X of capital
= 0.10 x $42,500
$4,250
Insurance and taxes - 2% of capital
0.02 x $42,500
$850
Energy and power
(a) bulldozer Uses 30 gal. diesel fuel per day,
1/2 time or 20 hr/week
(b) truck makes one trip per day using <1 gal/day
(c) front end loader makes one trip per day
using 5 gal/day
This equals 21 gal/day at $0.50/gal
= $10.50/day x 260 day/year
= $2,730/year
Monitoring = negligible
Recovered values = none
Total Operating Costs
Labor $26,520
supervision 6,630
Maintenance 4,250
Insurance and taxes 850
Energy 2,730
Total $40,980
7-34
-------
Total Annual Costs
Capital Costs $10,420
Operating Coats 40.980
Total $51,400
Cost Per^Uni.t_grgduct3,on^of Chlorine Produced:
$51.400/vr - $0.56/metric ton chlorine
250 metric ton/year x 365 days/year
7-35
-------
8^0 REFERENCES
1. Anonymous, "New York Firm Buys Chemical Waste for
Recycling," Ind^^Wastss , Nov. /Dec. 1973, pp. 14, 15, 27.
2. Anonymous, "Truckloads of Landfill from Waste Sludge."
Chemical Week, Jan. 26, 1972. pp. 41-42.
3. Besselievre, Edward B. ,
The Treatment of Industrial Wastes, McGraw-Hill Book
Co., New York, 1968.
4. Black and Veatch, Consulting Engineers, "Process Design
Manual for Phosphorus Removal," U.S. EPA Program 17010
GNP Contract 14-12-936, October 1971.
5. Census of Manufactures (1972), U.S. Department of
Commerce, Bureau of Census, Mc72 (P)-28A-1, Alkalies and
Chlorine, November 1973.
6. Census of Manufactures (1972), U.S. Department of
Commerce, Bureau of the Census, Mc72 (P) -28A-2,
Industrial Gases, March 1974.
7. Census of Manufactures (1972), U.S. Department of
Commerce, Bureau of the Census, Mc72 (P)-28A-3,
Inorganic Pigments, March 1974.
8. Census of Manufactures (1972), U.S. Department of
Commerce, Bureau of the Census, Mc72 (P)-28A-4,
Industrial Inorganic Chemicals, N.E.C. , December 1973.
*
9. Connor, J. R. "Ultimate Liquid Waste Disposal Methods."
Plant Engineering. October 19, 1972.
10. "Cost of Transporting Freight by Class I and Class II
Motor common Carriers of General commodities. " (For the
year 1971) Interstate Commerce Commission, Bureau of
Accounts - Statement No. 2C1-71, Washington, D. C. , July
1973.
11. "Current Industrial Reports - Inorganic Chemicals,
1971," Bureau of the Census, U.S. Department of
Commerce, Series: M28A(71)-14, October 1972.
12. "Development Document for Proposed Effluent Limitations
Guidelines - Copper, Nickel, Chromium and zinc. Segment
of the Electroplating Point Source Category,"
EPA-440/1-73-003, August 1973, EPA, Washington, D. C.
20460.
8-1
-------
13. "Development Document for Proposed Effluent Guidelines
for the significant Inorganic Products Segment of the
Inorganic chemicals Manufacturing Point Source
Category," EPA Contract No. 68-01-1513* December 1973*
Washington, D. c.
11* Encyclopediajpf Chemical^Technology., 3rd ed.* R* Kirk
and D.F. othmer, eds., McGraw-Hill Book company* Mew
York, 1965.
15. Environmental Protection Technology Series, Report No.
EPA-R2-73-269 (June, 1973) "Treatment of Complex Cyanide
Compounds For Reuse or Disposal." Office of Research and
Monitoring, U.S. Environmental protection Agencyt
Washington,, D. c«
16. Fairall* J.M. * Marshall, L.S*, Rhiries, C*E., "Guide for
Conducting an Industrial Waste Survey*" Draft only* U.S.
17. Faith, W.L., Keyes, D.B** and Clark, R.t.* Industrial
Chemicals, 3rd ed., John Wiley and Sons* Inc.* New York,
1965.
18. Gurnham, c. Fred, Industrial Wastewater Control*
Academic Press* New York* 1965.
19. "Industrial Waste Study of Inorganic Chemicals, Alkalies
and chlorine," General Technologies Corp,* Reston* Vat.
EPA Contract No. 68-01-0020, July 1971.
20. Lund, Herbert F. * Industrial Polj.ution Control Handbook*
McGraw-Hill Book Co., New York* N.Y.
21. "Major Inorganic Products Segment of the Inorganic
Chemicals Manufacturing Point Source Category"
EPA-440/1-74-007a, March 1974, Washington* D. C. 20<460.
22. Patterson, J. and Minear* Roger A., "Wastewater
Treatment Technology," 2nd ed., Report to Inst. of
Envir. Cont*, State of Illinois, January 1973.
23. Perry, R.A*, "Mercury Recovery from Process Sludges**1
Chemical,Engineering Progress, Vol. 70, No. 3, March
1974, pp.~73-80.
21. Perry, J.N., Chemical.TEngineer's; Handbook, 4th ed. *
McGraw-Hill Book, Co.,~New York, 1962.
8-2
-------
25. Peters, Max S., and Timmerhaus, Klaus D., Plant; Design
and EconomicsT for^Chemical^Engineers, 2nd ed.,
McGraw-Hlll~Book Co.,, New York, 1968.
26. Popper, H., Modern Cost Engineering Techniques,
McGraw-Hill Book CO., New York, 1970.
27. Private communications with Mr Ray Barbour,
Browning-Ferris Industries,, Houston, Texas.
28. Private communications with Mr. Charles Bourns, Solid
Wastes Management, EPA Region 9, San Francisco,
California.
29. Private communications with Mr. R.E. Dorer, Bureau of
Solid Waste and Vector Control, Department of Health,
State of Virginia.
30. Private communications with Mr. Bert Fowler, Waste
Management, Inc., Palos Heights, Illinois.
31. Private communications with Mr. Hardage, Industrial
Hazardous Waste Disposal Site, Lindsay, Oklahoma.
32. Private communications with Mr. Vic Johnson, Industrial
Tank Company, Martinez, California.
33. Private Communication with Mr. Robert Kasz of Aztec
Mercury Company, Alvin, Texas.
34. Private communication with Mr. John R. Kimberly, Jr.,
Resource Recovery Corporation, Seattle, Washington.
35. Private communication with Mr. Kenneth Nelson, Asarco
Chemical Co., New York, N.Y.
36. Private communication with Mr. G.J. Niewenhuis of
Western Processing Company, Kent, Washington.
37. Private communications with Mr. Gene Rinebold, Wescon,
Inc., Twin Falls, Idaho.
38. Private communications with Mr. John Shea, Safety
Products and Engineering, West Quincy, Massachusetts.
39. Private communications with Mr. John Starr, SCI Services
Inc., Boston, Massachusetts.
40. Private communications with Mr. Carl Stead, Montgomery
County Landfill, Montgomery County, Pennsylvania.
8-3
-------
11. Private communications with Mr. B. Steihgrabber, Texas
Water Quality Board.
12. Private communications with Mr. Stan Williamson, Nuclear
Engineering* Inc., San Ramon, California.
13. private communication with Dr* Rodney Wood,
Sherwin-Williams company, coffeyvilie, Kansas*
41 . •' Program f6r the Management of Hazardous Wastes*'*
Battelle EPA Contract No* 68-01-0762, July 1573.
Pacific Northwest Laboratories, Richiand, Washington,
15. "Rail Carload Cost scales by territories from the
Year 1970'' 4 Statement No. 1C1-70. Bureau of Accounts *
interstate Commerce Commission, Washington, D. C., May
1973.
16* "Recommended Methods of Reduction Neutralization*
Hecovery, or Disposal of Hazardous Waste," TRW systems
Group, Redondo Beach* California, EPA Contract Ndi
68-01-0039, AUgUst 19?3, Vole. 1-16.
17. "Report to Congress on Hazardous Waste Disposal," EPA,
June 30, 1972, p. v.
18. Sawyer, Clair N. , Chemi st rv for Sani tar y ^ Engineers ,
McGraw-Hill Book Co., NevTtfork, 1960*
19. Sax, N. Irving, Dangerous Properties of Industrial
Materials, Van Nostrand* Reinhold CO* » New 1fork, 1S>68»
50. Shreve, R.N. , Ghemical^Ptqces8_lQ4
-------
55. Unpublished Communications, Calgon Corporation,
Pittsburgh, Pennsylvania-Cyanide Treatment.
56. Unpublished communications. Chemical Research
Laboratories, E.I. DuPont Company-Cyanide Treatments.
57. Unpublished Communications. "Cyanide Treatment with
Hydrogen Peroxide." Dr. P.R. Mucenieks, Research
Laboratories, FMC Chemicals, Princeton, New Jersey.
58. Unpublished Communications, "Sulfide Treatment With
Hydrogen Peroxide." Dr. P.R. Mucenieks, Research
Laboratories, FMC Chemicals, Princeton, N.J.
59. Witt, Phillip A., Jr., "Disposal of Solid Wastes,"
Chemical Engineering, October, 1971, pp. 67-77.
60. Federal Register, Vol. 39, No. 164, "Hazardous
Substances, Designation of and Determination of
Removability (EPA)".
61. Annual Report of the Administrator of the EPA, "The Cost
of Clean Air", EPA Publication 230/3-74-003, April 1974.
62. Internal Revenue Service, "Guidelines for Industry,
1973".
63. Stanford Research Institute, Chemical Information
Services, 1974^pi.rectQry of Chemical Producers, Menlo
Park, California.
64. The chlorine Institute, Inc., North American Chlor-
^Alkali Industry Plants and Production Data,Book,
"January 1974, No. 10. ~
65. Kienholz, P.J. "Outlook for Chlorine-Caustic
Production", Chem. Eng. Progress, Vol. 70, No. 3, pp.
59, 63.
66. Davis, John C., "Chlor-Alkali Producers Shift to
Diaphragm Cells", Chem. Eng., Feb. 18, 1974, pp. 84-87.
67. lammartino, N.R., "Chlorine, Caustic Abuilding",
Chem. Enq., Feb. 18, 1974, pp. 80-82.
68. TRW Systems Group, "Recommended Methods of Reduction,
Neutralization, Recovery or Disposal of Hazardous
Waste," Vo. XIV, Aug. 1973, PB-224593.
8-5
-------
69* Environmental Protection Agency, "thermal Processing and
Land Disposal of Solid Waste, Guidelines'1 »
|e3§£§U*egi§t§r» Vol.39* NO* 158, Part 111, Atig* 1U»
197
-------
9.0 GLOSSARY
Adsorption - Condensation of the atoms, ions or molecules of
a gas, liquid or dissolved substance on the surface of a
solid called the adsorbent0 The best known examples are
gas/solid and liquid/solid systems.
Air pollution - The presence in the air of one or more air
contaminants in quantities injurious to human, plant,
animal life, or property
-------
Caustic - Capable of destroying or eating away by chemical
action. Applied to strong bases and characterized by
the presence of hydroxyl ions in solution* Usually
applied as a name for sodium hydroxide.
Centrifuge - A device having a rotating container in which
centrifugal force separates substances of differing
densities.
Chemical oxygen demand, COD - Its determination provides a
measUte of the quantity of oxygen required to oxidize
the organic matter (or othet oxidizable matter) in a
waste Sample t Urtdet specific! conditions of oxidizing
agents^ temperature and time* The general method is
applied to waste samples having an organic carbon
concentration greater than 15 mg/liter.
Coke - Hie carbonaceous residue Of the destructive
distillation (carbonization) of coal or petroleum.
Condensation - Transformation from a gas to a liquid.
Conditioning - A physical and/ot chemical treatment given to
water used in the plant or discharged.
Conductivity, electrical - The ability of a material to
conduct a quantity of electricity transferred across a
unit area, per unit potential gradient per unit time.
in practical terms, it is used for approximating the
salinity or total dissolved solids content of water.
Cooling water - Water which is used to absorb waste heat
generated in the process. Cooling Water can be either
contact or non-contact.
copperas - Ferrous sulfate.
crystallization - The formation of crystalline substances
from solutions or melts*
Cyclone separator - A mechanical device which removes
suspended solids from gas streams.
tie mineralization - The removal from Water of mineral
contaminants usually present in ionized form. The
methods used include ion-exchange techniques, flash
distillation or electrolysis.
Dewater - Remove water from solid material by Wet
classification, cehtrifugation» filttation, or similar
solid-liquid separation techniques.
-------
Digestor - A pressure vessel or autoclave used to effect
dissolution of raw materials into aqueous solutions.
Effluent - The wastewater discharged from a point source to
a waterway or other body of water.
Electrolysis - Decomposition by means of an electric
current; the compound is split into positive and
negative ions which migrate and collect at the negative
and positive electrodes.
Electrostatic precipitator - A gas cleaning device using the
principle of placing an electrical charge on a solid
particle which is then attracted to an oppositely-
charged collector plate.
Filtrate - Liquid after passing through a filter.
Filtration - Removal of solid particles from liquid or
particles from air or gas stream through a permeable
membrane.
Flocculation - The combination of aggregation of suspended
solid particles in such a way that they form small
clumps. The term is used as a synonym for coagulation.
Flotation - A separation method for ore in which a froth
created in water by a variety of reagents floats some
finely crushed minerals, whereas other minerals sink.
Fluidized bed reactor - A reactor in which finely divided
solids are caused to behave like fluids due to their
suspension in a moving gas or liquid stream.
Gas washer (or wet scrubber) - Apparatus used to remove
entrained solids and other substances from a gas stream.
Hammer mill - An impact mill consisting of a rotar, fitted
with movable hammers, that is revolved rapidly in a
vertical plane within a closely fitting steel casing.
Hardness - The characteristic of water generally accepted to
represent the total concentration of calcium and
magnesium ions, usually expressed as mg/liter calcium
carbonate.
Heavy metal - One of the metal elements not belonging to the
alkali or alkaline earth group. In this study, the
classification includes titanium, vanadium, iron,
nickel, copper, mercury, lead, cadmium, and chromium.
9-3
-------
ion exchange - A reversible chemical reaction between a
solid and a fluid by means of which ions may be
interchanged from one substance to another. The
customary procedure is to pass the fluid through a bed
of the solid, which is granular and porous and has a
limited capcaity for exchange. The process is
essentially a batch type in which the ion exchanger,
upon nearing depletion, is regenerated by inexpensive
salts or acid.
Kiln (rotary) - A large cylindrical mechanized type of
furnace used for calcination.
Leaching - The process of extraction of a soluble component
from a mixture with an insoluble component, by
percolation of the mixture with a solvent.
Membrane - A thin sheet of synthetic polymer, through the
apertures of which small molecules can pass, while
larger ones are retained.
Milling - Mechanical treatment of materials to produce a
powder, to change the size or shape of metal powder
particles, or to coat one powder mixture with another.
Mother liquor - The solution from which crystals are formed.
Multi-Effect evaporator - In chemical processing
installations, requiring a series of evaporations and
condensations, the individual units are set up in series
and the latent heat of vaporization from one unit is
used to supply energy for the next. Such units are
called "effects" in engineering parlance as, e.g., a
triple effect evaporator.
Neutralization - The addition of acid or base to a solution
in order to bring the pH to a value of 7.
Oleum or fuming sulfuric acid - A solution Of sulfur
trioxide in sulfuric acid.
Oxidation - A chemical change in which the oxidation state
(positive valence) of an element is increased.
pH - Is a measure of the relative acidity or alkalinity of
water. A pH value of 7.0 indicates a neutral condition;
less than 7 indicates a predominance of acids, and
greater than 7, a predominance of alkalies. There is a
10-fold increase (or decrease) from one pH unit level to
the next, e.g.,, 10-fold increase of alkalinity from pH 8
to pH 9.
9-4
-------
Plant effluent or discharge after treatment - The wastewater
discharged from the industrial plant. In this
definition, any waste treatment device (pond, trickling
filter, etc.) is considered part of the industrial
plant.
Precipitation - The formation of solid particles in a
solution.
Pretreatment - The necessary processing given materials
before they can be properly utilized in a process or
treatment facility.
Process effluent or discharge - The volume of wastewater
emerging from a particular use in the plant.
Process water - Water which is used in the internal plant
streams from which products are ultimately recovered, or
water which contacts either the raw materials or product
at any time.
Reduction - A chemical change in which the oxidation state
(positive valence) of an element is decreased.
Reverse osmosis - A method involving application of pressure
to the surface of a saline solution forcing water from
the solution to pass from the solution through a
membrane which is too dense to permit passage of salt
ions. Hollow nylon fibers or cellulose acetate sheets
are used as membranes since their large surface areas
offer more efficient separation.
Sedimentation - The falling or settling of solid particles
in a liquid, as a sediment.
Settling pond - A large shallow body of water into which
industrial wastewaters are discharged. Suspended solids
settle from the wastewaters due to the large retention
time of water in the pond.
Sintering - The agglomeration of powders at temperatures
below their melting points. Sintering increases
strength and density of the powders.
Slaking - The process of reacting lime with water to yield a
hydrated product.
Sludge - The settled mud from a thickener clarifier.
Generally, almost any flocculated, settled mass.
9-5
-------
Blurry - A watery suspension of solid materials*
Sniff gas - The exhaust or tail gas effluent from the
chlorine liquefaction and compression portion of a
ehlor-alkali facility.
SolUte - A dissolved substance.
Solvent - A liquid used to dissolve materials.
Sublimation - The direct passage Of a substance from the
solid state to the gaseous state without appearing in
the liquid State.
Thickener * A device or system wherein the solid contents of
slurries or suspensions are increased by evaporation of
part of the liquid phase, or by gravity settling and
mechanical separation of the phases*
Total dissolved solids (TDS) - The total amount of dissolved
solid materials present in an aqueous solution*
Total organic carbon (TOC) - A measurement of the total
organic carbon content of surface waters, domestic and
industrial wastes* and saline waters*
Total suspended solids (TSS) - Solid particUlate matter
found in wastewater streams* which, in most cases, can
be minimized by filtration or settling ponds.
Turbidity - A measure of the opacity or transparency of a
sediment-containing Waste stream* Usually expressed in
Jackson units or Formazin units which are essentially
equivalent in the range below 100 units.
Vaporization - A change from a liquid to a gaseous state at
elevated or normal temperatures.
Wet scrubbing - A gas cleaning system using water or some
suitable liquid to entrap particUlate matter, fumes, and
absorbable gases.
Waste discharged - The amount (usually expressed as weight)
of some residual substance which is suspended or dis-
solved in the plant effluent.
Waste generated (raw waste) - The amount (usually expressed
as weight) of some residual substance generated by a
plant process or the plant as a Whole. This quantity is
measured before treatment.
9-6
-------
Water recirculation or recycling - The volume of water
already used for some purpose in the plant which is
returned with or without treatment to be used again in
the same or another process.
Water use - The total volume of water applied to various
uses in the plant. It is the sum of water recirculation
and water withdrawal.
Water withdrawal or intake - The volume of fresh water
removed from a surface or underground water source by
plant facilities or obtained from some source external
to the plant. The effluent limitations guidelines for
sodium dichrornate and by-product sodium sulfate plants,
based on the application of the best available
technology economically achievable, require no discharge
of process wastewater pollutants to navigable waters.
9-7
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ISiO ACKNOWLEDGEMENTS
The preparation of this report was accomplished through the
efforts of the staff of General Techno. ">gies Division,
Versar, Inc., Springfield, Virginia, under the direction of
Dr. Robert G. Shaver, Vice President.
Mr. Sam Morekas, Program Manager, Hazardous Waste Division,
through his assistance, leadership, careful review of the
draft report, and advice has made an invaluable contribution
to the preparation of this report.
Appreciation is extended to the following trade associations
for assistance and cooperation in this program:
The Chlorine Institute, Inc.
Manufacturing chemists Association
Salt Institute
Appreciation is also extended to the many industrial
inorganic chemicals producing companies, state and federal
agencies who gave us invaluable assistance and cooperation
in this program.
Also, our appreciation is extended to the individuals of the
technical staff of General Technologies Division of Versar,
Inc., for their assistance during this program.
Specifically, our thanks to:
Mr. E.F. Abrams, Senior Chemical Engineer
Mr. M.C. calhoun. Field Engineer
Mr. J.G. Casana, Environmental Engineer
Mr. M.A. Connole, Biological Scientist
Mr. M.G. DeFries, Senior Chemical Engineer
Dr. R.L. Durfee, Senior chemical Engineer
Ms. C.W. Forlini, Draftsman
Mrs. D.K. Guinan, Chemist
Mr. L.C. McCandless, Senior Chemical Engineer
Dr. L.c. Parker, Senior Chemical Engineer
Mr. E.F. Rissmann, Senior Environmental Scientist
Mr. D.H. Sargent, Senior Chemical Engineer
Mrs. K.M. Slimak, Environmental Scientist
Mr. R.C. Smith, Jr., Senior chemical Engineer
Dr. F.C. Whitmore, Senior Scientist
Acknowledgement and appreciation is also given to the secre-
tarial staff of General Technologies Division of Versar,
Inc. for their efforts in the typing of drafts, necessary
revisions, and final preparation of this document.
10-1
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AS. PhyjsicajL/Chemical Properties
Antimony Trioxide (Sb2O3)
This oxide of antimony is an amphoteric, white,
odorless, polymorphic crystalline powder* which is
slightly soluble in water (16.0 mg/liter at 15°C, 8.45
mg/liter at 25°C) and readily soluble in: warm solu-
tions of tartaric acid, or of bitartrates; acetic acid;
concentrated hydrochloric and sulfuric acids and strong
alkalis.1 Antimony trioxide sublimes in a high vacuum at
400°C; m.p. 655°C, b.p. 1425°C, d. 5.67, m.w. 291. 52. »
Antimony, Trichloride (SbC13)
Antimony trichloride (m.w. 228.13, d. 3.14,
m.p. 73°C, b.p. 223.5°C)« exists as a colorless,
transparent, crystalline hygroscopic mass which reacts
vigorously with moisture generating heat and HCl gas.3
At 0°C, antimony trichloride's saturation concentration
is 6016.0 g/liter of water.9 It is also soluble in
alcohol, acetone and acids.3 In contact with water,
antimony trichloride gradually hydrolyzes to antimony
oxychloride (SbOCl) . *
B.. Biological Properties
Although it has a slightly better prognosis, anti-
mony poisoning closely parallels arsenic poisoning,
except that vomiting from antimony may be more prom-
inent, perhaps because its compounds are less readily
absorbed than arsenicals.2 Temporary EKG changes are re-
ported in humans, and severe cardiac damage observed in
animals. Trivalent antimony compounds are many times
more lethal than pentavalent derivative. BAL
(2, 3-dimercapto-1-propanol) appears to be effective in
treating antimony poisoning, at least when it is due to
trivalent forms of the metal. Tolerance to antimony is
denied.2
Signs and symptoms of antimony poisoning in addi-
tion to the aforementioned include irritation and ecze-
matous eruptions of the skin, inflammation of the mucous
membranes of the nose and throat, metallic taste and
A-1
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stomatitis, gastrointestinal upset with vomiting and
diarrhea, and various nervous complaints, such as irri-
tability, sleeplessness, fatigue, dizziness, and mus-
cular and neuralgic pains* 3
Q-. iGvirgrunental Properties
As a contaminant in water and soil, the provisional
limit for Sb2O3 is 0.05 ppm as Sb.* The LD50 for rats
administered antimony trioxide orally is greater than 20
gm/kg body weight.7
Because of its solubility, land disposal of anti-
mony trioxide should include adequate safeguards against
leaching to surface or ground water supplies.
None
and Its Compounds
El3Y§i£§IdChemical Properties
Elemental Arsenic (As)
Metal lie- looking arsenic (a.w. 74.92, m.p. 818°c at
36 atm., d. 5.72) is a shiny silver-grey, brittle,
rhombohedral crystalline solid that darkens in moist
air. i It exists in two allotropic forms: a black,
amorphous solid and a yellow, crystalline solid.4 The
yellow modification, which has no metallic properties,
is obtained by sudden cooling of As vapor.* This yellow
arsenic is converted back to the gray modification upon
very short exposure to ultraviolet light.* Elemental
arsenic can be heated to burn in air with a bluish
flame, giving off an odor of garlic and dense white
fumes of As2O3.4 It loses its lustre on exposure to air,
forming a black modification and As2O3. * Arsenic is
attacked by HCl in the presence of an oxidant and it is
readily soluble in nitric acid.*
Arsenic Trichloride (AsC13)
AsC13 (m.w. 181.28, m.p. -16°C, b.p. 130.21°C,
d 2* 14 97) 9 occurs as a clear, almost colorless to pale
yellow corrosive oily liquid or needle-like crystals.3
A-2
-------
This arsenic chloride is soluble in concentrated HC1 and
most organic liquids* and is miscible with or solvent
for: chloroform, carbon tetra chloride, ether, iodine,
phosphorus, sulfur, alkali iodides, oils and fats. l
AsC13 is decomposed by water to As (OH) .3 and HCl.1 This
chloride fumes in moist air readily, liberating hydrogen
chloride. » It becomes saturated in water at a
concentration of 2.98 x 10* mg/liter.1
ic Pentasulfide (As2S5)
Arsenic pentasulfide (m.w. 544.62, sublimes and
decomposes at 500°C) 9 exists as a brownish-yellow,
glassy, amorphous, highly refractive mass.1 It will
react with steam or water to produce toxic and corrosive
fumes; it can react vigorously with oxidizing
materials. ' It is almost insoluble in water (at 0°C,
solubility 1.36 mg/liter)9 but solubilizes readily in
nitric acid, alkalies and alkali sul fides. Because of arsenic
pentasulfide's amphoteric nature, its solubility
increases as pH increases or decreases from pH 7. As2S5
decomposes to sulfur and the trisulfide when heated.*" ~"
Dibasic Sodium Ar senate (Na2HAsO4. 7H20)
Heptahydrated dibasic sodium ar senate (m.w. 311.91)
is anhydrous at 100°C; at about 50°C it loses 5 water
molecules (29% of total weight) . » It is a colorless,
odorless crystalline salt5 with a mild alkaline taste
which is readily soluble in water (at 0°c, 54.6 g
dissolve into one liter of solution; at 100°C,
solubility is 1000 g/liter)'; it is also soluble in
glycerol, and slightly so in alcohol.' The aqueous
solution of sodium arsenate is alkaline to litmus. l This
salt effloresces in warm air. *
Arsenic Djsulfide (As2S2)
Arsenic disulfide (m.w. 213.94, m. p. 307<>C,
b.p. 565°C, d. 3.5)' exists as deep red-brown, lustrous
monoclinic crystals which are practically insoluble in
water, very slightly soluble in hot CS2 and benzene1,
but readily soluble in K2S, NaHCO3« and alkali
hydroxides. l It will react with water or steam to
produce toxic and flammable vapors; it can react
vigorously with oxidizing materials.3
A£§enic Trisulfide (As2S3)
Arsenic trisulfide (m.w. 246.04, m.p. 300°C,
b.p. 700°C, d. 3.46)9 occurs as yellow monoclinic
A-3
-------
crystals9 or powder which change to a red form at
170°C.* It is insoluble in hydrochloric acid* but
dissolves in alkaline sulfide and carbonate solutions
and in nitric acid (decomposes).1 Arsenic trichloride's
solubility in water is 0.5 mg/liter at 18°c.9 It is
dangerous when heated to decomposition or in contact
with acid or acid fumes because it emits highly toxic
fumes of sulfur and of arsenic; it will react with water
or steam to produce toxic and flammable vapors; it can
react vigorously on contact with oxidizing materials.3
Properties
In all cases of arsenic poisoning it is presumably
the ion of arsenious acid, rather than the element
itself, which is the toxic principle.2 The in vivo
conversion to arsenite explains why all chemical forms
of arsenic eventually produce the same toxic syndrome.
One exception is gaseous AsH3 or arsine, which is a
potent hemolylic agent, unlike other arsenic
derivatives.2
Arsenic is notorious for its toxicity to humans.
Ingestion of as little as 100 mg usually results in
severe poisoning and as little as 130 mg has proved
fatal.5 Furthermore, arsenic accumulates in the body, so
that small doses may become fatal in time. A single
dose may require ten days for complete disappearance and
this slow excretion rate is the basis for the cumulative
toxic effect, chronic arsenosis is of slow onset and
may not become apparent for 2-6 years. Small eruptions
occur on the hands and the soles of the feet sometimes
developing into arsenical cancers. Liver and heart
ailments may also supervene.5
Finely subdivided arsenic compounds, such as
arsenic trioxide are significantly more toxic than
coarsely powdered material, since appreciable amounts of
the latter may be eliminated in the feces without
dissolving.* In acute poisoning, symptoms following
ingestion relate to irritation of the gastrointestinal
tract: nausea, vomiting, diarrhea, which can progress
to shock and death.6 In most cases the presenting
symptoms are those of severe gastritis or gastro-
enteritis.2 Because the lesions are due not to local
corrosion but to vascular damage from absorbed arsenic,
the first symptoms may be delayed several minutes or
even a few hours. Eventually a violent hemorrhagic
gastroenteritis leads to profound losses of fluid and
electrolytes, resulting in collapse, shock and death.2
A-
-------
Occasionally the alimentary symptoms are mild or absent,
in which case the presenting complaints are usually
referable to the central nervous system: headache,
vertigo, muscle spasm, stupor, delirium, and sometimes
mania.2 urinary excretion of arsenic is markedly
enhanced, without damage to the excretory organs, by the
administration of BAL (dimercaprol). If prompt, this
treatment suppresses most signs and symptoms of acute
poisoning.2
Several incidents have demonstrated that arsenic in
water may be carcinogenic.5 There have been several
instances where cancers of the skin, and possibly the
liver, have been attributed to arsenic in the domestic
water supply.5
The extreme toxicity of arsenates towards human
life can be considered the same for animal life as
well.6 Although sodium arsenate, for example, is not
highly toxic to fish, towards lower forms of aquatic
life the toxicity of sodium arsenate is variable.5 The
threshold concentration for immobilization of Daphnia
magna in Lake Erie water has varied from 18-31 mg/liter
as sodium arsenate (i.e. 4.3-7.5 mg/liter as arsenic).
The toxic threshold for the flatworm Polvcelis nigra, is
reported to be 361 mg/liter as arsenic.5
Qi Environmentai Properties
The water quality standard for arsenic and its com-
pounds is 0.05 mg/liter as As (DWS); a more ideal limit
would be 0.01 mg/liter.*
Because of arsenic's toxic nature, all precautions
must be taken to prevent run-off from farms and orchards
into streams and rivers where the arsenate compounds can
adversely affect aquatic plant and animal life.6
Although very low concentrations of arsenates actually
stimulate plant growth, the presence of excessive
soluble arsenic in irrigation waters will reduce the
yield of crops, the main effect appearing to be the
destruction of chlorophyll in the foliage.5
The lead and calcium arsenates after application to
plant surfaces, find their way to the ground when the
plant drops its leaves or when rainfall washes them from
the plant onto the ground.6 The compounds then reside in
the soil where they are not easily removed except by the
equally undesirable process of leaching and run-off into
nearby streams and lakes. The buildup of arsenic
A-5
-------
compounds in the soil has created the problem of soil
sterilization and the inability of any type of plant to
grow.6
One of the problems with toxic materials is their
tendency to concentrate through both aquatic and
terrestrial food chains.22 Aquatic macro- and
micro-flora and fauna accumulate heavy metals, such as
arsenic, in body tissues in significantly greater
concentrations than present in the surrounding
environment. These organisms are the food source for
fish and insects which retain the arsenic in the tissues
of the consumed organisms. The fish and insects are
consumed in turn by larger organisms; this process
continues to the organisms at the top of the pyramidal
food chain, such as man and large carnivorous birds and
mammals. The more links in the chain, the more severe
the bioaccumulation phenomenon.22
Because of the above discussed properties of
arsenic-containing wastes, the most environmentally
appropriate means of disposal is recovery and reuse.
Where not feasible, burial in a secure landfill is
necessary.
None
Asbestos
A.. Chemical/Physical Properties
"Asbestos" is a generic term for a number of fire-
resistant hydrated silicates that, when crushed or
processed, separate into flexible fibers made up of
fibrils noted for their great tensile strength.11
Although there are many asbestos minerals, only six are
of commercial importance: chrysotile, a tubular
serpentine mineral, accounts for 95% of the world's
production; the others, all amphiboles, are amosite,
crocidolite, anthophylli te, tremolite, and actinolite.
1 * The molecular formulas of these six asbestos minerals
are listed below. The asbestos minerals differ in their
metallic elemental content, range of fiber diameters,
flexibility or hardness, tensile strength, surface
properties, and other attributes that determine their
industrial uses and may affect their respirability,
deposition, retention, translocation, and biologic
reactivity.1 *
A-6
-------
Serpentine asbestos is a magnesium silicate the
fibers of which are strong and flexible so that spinning
is possible with the longer fibers*4 Amphibole asbestos
includes various silicates of magnesium, iron, calcium,
and sodium. The fibers are generally brittle and cannot
be spun but are more resistant to chemicals and to heat
than serpentine asbestos.*
Molecular Formulas of Asbestos Minerals;
Chrysolite Mg3Si205(OH)$*
Anthophyllite (MgFe) 7 Si8O22(OHF)J
Amosite (ferroanthophyllitej
Crocidolite
T remoli te Ca2Mg2Si22(OHF) 2
Actinolite Ca2(MgFe)£ SigO^l (OS,F) 2*
ical Properties
Asbestos is toxic by inhalation of dust particles;
the tolerance is 5 million particles per Cubic foot of
air (TLV,ACGIH recommended). Like Other cases of "dust
lung" diseases, asbestosis develops Slowly.* It becomes
manifest usually 20-30 years after the first eX-posure,
often long after exposure to asbestos has completely
ceased. Unexplained breathtlessness oft exertion and
productive cough often precede the disease by many
years.a
The essential lesion produced by asbestos dust- is a
diffuse fibrosis which probably begins aS a "eollar"
about the terminal bronchioles.3 Usually at leatst 1-7
years of exposure are required before a sferious degree
of fibrosis results.. There is apparently les's
predisposition to tuberculosis' than is" the- cfase with
silicosis. Prolonged inhalation- can cause eancer of the
lungs, pleura and peritoneum.3
Exposure to asbestos without development cJf
asbestosis has been shown to increase the risk of- lung
cancer.11 Other kinds off dust in addition to asbestos
most likely contribute to this development. In asbestos
workers who smoke, a 90-fold increase in the incidence
A-7
-------
of lung cancer over that in non-smokers has been
recorded. Some research data strongly suggests a
synergism of cigarette smoking and asbestos exposure in
the increased risk of lung cancer. It is not known
whether this is because of reduced clearance of
asbestos, transportation of cigarette-smoke carcinogens
by asbestos fibers, or the promotion by one factor of
cancer initiated by another. Cancer caused by asbestos
localizes most often in the lower lobes of the lungs in
contrast to the more common site of lung cancer in the
upper lobes.**
An otherwise rare tumor, called mesothelioma, has
been identified with asbestos.8 Mesotheliomas usually
involve the pleura but also originate in the peritoneum.
This malignant tumor spreads rapidly over the whole
abdominal cavity and into the lymph glands of the body.
As in other kinds of lung cancer, the condition starts
slowly with chest pain and breathlessness; the patients
seldom survive more than a year from the time the
diagnosis is established.8
All epidemiologic studies that appear to indicate
differences in pathogenicity among types of asbestos are
flawed by their lack of quantitative data on cumulative
exposures, fiber characteristics, and the presence of
cofactors.11 The different types, therefore, cannot be
graded as to relative risk with respect to asbestosis.
Fiber size is critically important in determining
respirability, deposition, retention, and clearance from
the pulmonary tract and is probably an important
determinant of the site and nature of biologic action.
Little is known about the movement of the fibers within
the human body, including their potential for entry
through the gastrointestinal tract. There is evidence
through that bundles of fibrils may be broken down
within the body to individual fibrils.11
Qi Envi ronmen. ta 1 Properties
This material is a hazard when air-borne, and a
possible hazard when water-borne in large
concentrations; however, it is insoluble in water.
Disposal by landfill with adequate protection against
surface erosion by wind or rain is the most
environmentally appropriate means of disposal.
s: None
A-8
-------
B§£iU!D and Its Compounds
Hi Physical/Chemical Properties
§!§!3§Qtal Barium (Ba)
Barium (a.w. 137.34, d. 3.5, m.p. 710°C,
b.p. 1500°C)« exists as a yellowish-white, somewhat
malleable, luminous, alkaline earth metal which is
easily oxidizable and hence must be kept Under petroleum
or some other oxygen-free liquid to exclude air.* This
element reacts readily with water, ammonia, halogens,
oxygen and most acids. It is decomposed by water or
alcohol with the evolution of hydrogen.* Barium is
pyrophoric at room temperature in powder form.4 When
heated to about 200°C in hydrogen, it reacts violently,
forming BaH2.4
Barium Chrgmate (BaCr04)
Barium chromate (m.w. 253.35, d. 4.498 at 15°C)« is
composed of yellow, heavy, monoclinic, orthorhombic
crystals* which are only slightly soluble in water (3.4
mg/liter at 16°C, 4.4 mg/liter at 28°C)», dilute acetic
or chromic acids but are dissolved or decomposed by
mineral acids.1 Barium chromate crystals are
combustible.*
Si Biological Properties
Barium
The acid-soluble barium salts (carbonate, chloride,
hydroxide, nitrate, acetate, sulfide) are highly toxic,
whereas the insoluble barium sulfate (used in radio-
graphy) is quite benign.2 The LD (oral) of barium
chloride can be as low as 1.0 gm but much larger doses
have been tolerated. For most of the acid-soluble salts
of barium, the lethal dose for adults appear to lie bet-
ween 1-15 grams. Death occurs within a few hours or a
few days.2 The usual result of exposure to the sulfide,
oxide and carbonate is irritation to the eyes, nose and
throat, and of the skin, producing dermatitis: the salts
are somewhat caustic.
A-9
-------
Acute poisoning occurs when either of the two
barium saltsr barium chloride (BaCl2) or barium car-
bonate (BaC03) is ingested.8 Barium is rapidly
transmitted to and from the bloodstream, since the
mucous lining of the bowels is extremely permeable to
the metal.8 During the first 30 hours after absorption,
barium is retained, especially by the muscles, after
which about 20 percent is eliminated by the bowels, only
about 7 percent through the urine.8 Barium also
accumulates in bones and lungs, but on the other hand,
liver, kidneys, brain, heart, and hair do not retain
barium.8 Once in the bloodstream, barium acts to
stimulate smooth, striated and cardiac muscle; the
result is violent peristalsis, arterial hypertension,
muscle twitching and disturbances in cardiac action.2
Motor disorders include stiffness and immobility of the
limbs, and sometimes of the trunk, leg cramps, twitching
of facial muscles, and paralysis of the tongue and
pharynx with attendant loss or impairment of speech and
deglutition.2 The central nervous system may be first
stimulated and then depressed.2 Kidney damage has been
described as a late complication, probably a result of
circulatory insufficiency. Because barium depolarizes
cell membranes, one is led to predict a hyperkalemia
rather than a depression of plasma potassium. Perhaps
barium induces renal tubular lesion that results in
large losses of potassium, but electrolyte analyses of
urine have not been reported.2 Although the barium metal
itself can be tolerated in large doses, the toxic dose
of barium chloride ranges between 0.2-0.5 gram and the
lethal dose up to 2.
-------
concentrated by goldfish from solution by a factor of
about 150.•
Barium chromate is highly toxic when ingested*; its
toxic nature is due mainly to the presence of chromate
in the compound, see "Chromium and Its Compounds" in
this section for detailed toxicological information.
C. Environmental Properties
The water quality standard for barium is
1.0 mg/liter.*
Radioactive P.r2eer,tie§i
<&£ Its ConffQQunds
a^ properties
Slem.en.tal Bgr.YHiu.jn (Be)
Beryllium (a.w. 9.0122, d. 1.8U, m.p. 1284-1300<>C,
b.p. 2970°C) » is a hard, brittle, light weight
grey-white metal which is soluble in acids (except
nitric) and alkalies.1 The steel-like hardness often
attributed to beryllium is localized in a thin film of
oxide on the metal.
Beryllium is a relatively rare element, found
chiefly in the mineral beryl. Although the chloride and
nitrate are very soluble in water, and the sulfate
moderately so, the carbonate and hydroxide are almost
insoluble in water.9
As the whole of its domain of stability lies well
below that of water, beryllium is theoretically a very
base metal; it is clearly a reducing agent, and very un-
stable in the presence of water and aqueous solutions. *•
In the presence of acid solutions it vigorously
decomposes water with the evolution of hydrogen,
dissolving as beryllium ions, Be++; in the presence of
strongly alkaline solutions, it dissolves once again
with the evolution of hydrogen, but this time gives rise
A-11
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to diberyllate ions (Be2O3)-2 and beryllate ions
(BeO 2) -*.
(Be (OH) 2)
Beryllium hydroxide (m.w. 43.03, d. 1.92)1 exists
as an amorphous white powder4 which is decomposed to the
oxide (BeO) at 138°C. It is soluble in acids and
alkalis.* At pH 9, beryllium hydroxide reaches a
saturation point, in pure water, at 1.12 x 10-*
mg/liter; as the pH decreases the solubility increases
such that at pH 5, the solubility of Be (OH) 2 is
5.06 x 10-* mg/liter.18
Beryllium Oxide (BeO)
Beryllium oxide (m.w. 25.01, d. 3.01, m.p. 2530 +
30°C, b.p. (ca) 3900°C) 9 occurs as a light, white1
amorphous powder* which, when 100 percent pure,
insulates electrically like a ceramic but conducts heat
like a metal.* It is soluble in acids and alkalis.*
Beryllium oxide solubilizes to the extent of 2.02 x 10-*
mg/liter. It is least soluble (1.60 x 10~») mg/liter at
pH 7.»8
Because of beryllium's amphoteric nature, compounds such as
Be (OH) 2 and BeO and hydrated beryllium oxide (Be2O(OH)2)
have pH dependent solubilities. At pH 9, Be20(OH)2's
solubility is 9.01 x 10-8 mg/liter whereas at pH 5 it
solubilizes in pure water up to 1.46 x 10~5 mg/liter.18 It
is least soluble at pH 7 (2.53 x 10-io mg/liter).18
ical Properties
In acute poisoning, beryllium gives rise to a chem-
ical inflammation of the lung tissue8. When exposed to
concentrations of beryllium of 20-60 micrograms for
about 50 days, workers in beryllium producing plants
developed transient inflammation of the upper air
passages, nose, pharynx, trachea, and upper bronchi,
which is followed by a pneumonia-like process with
fever, chills, cough, sputum, and shortness of breath.
If not fatal, the disease can last up to 3 months. Even
without further exposure, in about 6.3 percent of the
cases it is followed by the chronic form of the disease.
A-12
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Chronic berylliosis starts insidiously with pro-
gressive shortness of breath, weight loss, cough, and
slight production of phlegm.8 occasionally, the patients
have a low-grade fever and nausea. If much time elapses
between exposure and the development of the disease,
progressive shortness of breath is practically the sole
symptom. However, if the interval between exposure and
the disease is short or nonexistent, patients often
develop a profound progressive emaciation. They may die
within a few months. As the disease develops, granulo-
matous inflammation, the typical feature of beryllium
poisoning, is often followed by fibrosis (scarring) of
the lung tissue and by damage to the heart.
Beryllium is believed to interfere with the passage
of oxygen from the alveoli to the arterial blood, a con-
dition called "alveolar capillary block".8 An immune
mechanism is indicated by the fact that beryllium ions
have been found attached to protein molecules.
Although the pulmonary effects dominate the clini-
cal picture of berylliosis, other organs are also
involved, such as the liver, spleen, kidneys, and lymph
glands.8 Beryllium compounds have the capacity to cause
malignant tumors in laboratory animals, namely
osteosarcoma in rabbits and carcinoma of the lungs in
rats and monkeys. Whether or not patients with
berylliosis are prone to the development of lung cancer
has not been determined. Large doses of adrenal
steroids (cortisone preparations) constitute a useful
treatment for the disease.
In nutrient solution, at acid pH values, beryllium
is highly toxic to plants.5 At pH values above 11.2
however, beryllium appears to be beneficial to plants
with a magnesium deficiency, solutions containing 15-20
mg/liter of beryllium delayed germination and retarded
the growth of cress and mustard seeds in solution
culture.
A-13
-------
The results of testing the toxicity of three
beryllium salts toward fathead minnows and bluegills in
hard and soft waters are given below:
Toxicological Responses (96 Hour TLm) of Fathead
Minnows and Bluegills to be Salts5* ~"
Concentration of Beryllium in mq/1
Fathead^Minnows Blueqills
Compounds Soft Hard Soft ~~ Hard
Beryllium chloride 0.15 15.0
Beryllium sulfate 0.2 11.0 1.3 12.0
Beryllium nitrate 0.15 20.0
*Concentrations expressed in terms of ing/liter Be.
These results demonstrate that beryllium is considerably
more toxic in soft water than hard water.
QID§Iltal Properties
The water quality standard for beryllium and its
compounds is 1.0 mg/liter as Be.6
Detailed studies have indicated that there is no
preferential uptake or concentration of beryllium or
beryllium compounds from the environment by any animals
or plants, including humans.6
P.. Radioactive Propertiesi None
Cadmium and Its Compounds
A.. Physical/Chemical Properties
Elemental Cadmium (Cd)
Cadmium (a.w. 112.4 grams, m.p. 321°C, b.p. 767°C,
d. 8.6)9 occurs as a silver-white, blue-tinged lustrous
metal which oxidizes in moist air.1 It is insoluble in
water, slowly soluble in hot HCl, almost unattacked by
cold H2SO4, but converted into sulfate by hot H2SOU.»
Cadmium is readily soluble in dilute HNO3 and in
ammonium nitrate solutions. One hundred grams Hg
dissolves 5.17 grams of cadmium at 18°^* Solutions of
A-
-------
cadmium yield with H^S or Na2S a yellow precipitate
which is insoluble in excess Na2S.&
In the elemental form cadmium is insoluble in
water.3 Although the chloride, nitrate, and sulfate of
cadmium are highly soluble in water, the carbonate and
hydroxide are virtually insoluble. Hence at high pH
values, cadmium will be precipitated out.5
Cadmium Oxide (CdOJ
CdO (m.w. 128014110 da 8015J« exists in two species;
as either a dark brown infusible amorphous powder or as
cubic, brown crystals,,* Both decompose on heating at
900°C and sublime at 1559°C.2® Cadmium oxide is soluble
in dilute acids and ammonium salts.1 Because of its
amphoteric nature,, its solubility increases as its pH
decreases. At pH 11«3, cadmium oxide°s solubility in
water is 0.094 ppm as Cd** while at pH 9 its saturation
point is 761oO ppm as
Cadmium Hydroxide
Cadmium hydroxide (m.w0 m»6.43aff m.p. 300°C,
d. 4.79) is a whit© powder* consisting of trigonal or
amorphous crystals.3 It is soluble in ammonium hydroxide
and dilute acid and virtually insoluble in water (2.6
mg/liter at 25°C9| and alkalis.* Cadmium hydroxide
absorbs carbon dioxide from the air*; dehydration to CdO
occurs at 130°C-200®C«,
Cadmium Sulf ate (CdSO4&<,0-7H2O&
Cadmium sulfate occurs in several hydrated forms in
addition to an anhydrous form. Anhydrous cadmium
sulfate (formula CdSO4* m.Wo 208.48, d. 4.69,
m.p. 1000°c3) is a white powder of colorless, odorless
rhomboidal crystals*s**®* which is very soluble in water
(755.0 g/liter at 0°C, 60800 g/liter at 100°C) and
insoluble in alcohol.* The properties of the hydrated
forms are given below; all are very soluble in water and
almost insoluble in alcohol.«*>««>
A-15
-------
Physical/chemical Properties of Cadmium Sulfate
Hydrates
CdSO4.H20: m.w. 226.48, d. 3.79, transition pt.
108°C, monoclinic crystals'
CdS04. 4H20: m.w. 280.48, d. 305*
CdS04.7H20: m.w. 334.57, d. 2.48, transition pt.
40°C, colorless, monoclinic crystals'
3CdSO4.8H20: m.w. 769.50, d. 3.09, transition pt. 4°C,
colorless, odorless monoclinic crystals,
H20 solubility at 0°C 1130.0 g/liter<»
Cadmium Nitrate (Cd(NO3)2)
Cadmium nitrate exists in two forms hydrated and
anhydrous. Anhydrous cadmium nitrate (m.w. 236.41,
m.p. 350°C) is a colorless compound which is very
soluble in water (1090 g/liter at 0°C, 3260 g/liter at
60°C, 6820 g/liter at 100°C) and alcohol, and is soluble
in ethyl acetate.9 Cadmium nitrate tetrahydrate (formula
Cd(N03)2) .4H20, m.w. 308.47, d. 2.455, m.p. 59.4<>C,
b.p. 132°C9} is a white substance composed of amorphous
or hygroscopic needles.* It is very soluble in water
(2150 g/liter in cold water), soluble in alcohol and
ammonia and virtually insoluble in nitric acid.4
§i Properties
Cadmium is absorbed into the human organism without
regard to the amount already stored, nor does there
appear to be a mechanism to maintain a constant level in
blood and body fluids.a of 50-60 micrograms taken into
the system daily, about 2 micrograms are retained mainly
in the kidney and liver, the rest is eliminated in the
feces. Cadmium has no known biologic function. It is
toxic to practically all systems and functions of the
human and animal organism.• Cadmium inhibits the
functions of enzymes containing the sulfhydrile (SH)
groups, which are dependent on the presence of zinc,
cobalt, and other metals. There is evidence that
cadmium acts upon the smooth muscle of the blood
vessels, either directly or indirectly through the
agency of the kidneys.
The concentration and not the absolute amount
determines the acute toxicity of cadmium.14 Acute
poisoning may result from the inhalation of cadmium
dusts and fumes (usually CdO) and from the ingestion of
cadmium salts.2 Inhaled as a dust or aerosol, cadmium
salts (including even the relatively insoluble oxide)
A-16
-------
probably have a toilcity rating of "supertoxic" (with a
LD equal to or less than 5 mg/kg body weight) in man,
with death from fatal pulmonary injury. When swallowed,
cadmium compounds are much less lethal than when
inhaled, in part because they induce vomiting and so are
not retained. Although as little as 30 mg of soluble
cadmium salts has produced severe toxic symptoms when
ingested, death probably requires several hundred mg by
the oral route. A severe gastroenteritis is the chief
response to ingested cadmium, but both kidney and liver
injuries may occur and the kidney disorder has killed
experimental animals. In man the kidney damage appears
to be secondary to the appearance of a low molecular
weight protein in ':he urine. Cadmium produces more
profound changes in urinary excretion of amino acids
than do lead and mercury; urinary concentrations of
hydroxyamino acids, threonine and serine are
particularly elevated.2
Finely divided cadmium of a critical particle size
is inflammable and may generate lethal fumes of cadmium
oxide.2 The inhalation of 40 mg of cadmium with the
pulmonary retention of H mg has been estimated to be
fatal in man.2 In contrast to intoxication by ingestion
of cadmium, the deleterious activities following
inhalation of cadmium dust or fumes are largely limited
to the lungs and respiratory mucosa; although acute
renal necrosis can sometimes be precipitated by inhaled
cadmium fumes.2 Even brief exposure to high concen-
trations may result in pulmonary edema and necrosis of
the pulmonary epithelium. Other symptoms precipitated
by minor exposure include dryness of the throat,
coughing, headache, a sense of constriction in the
chest, shortness of breath (dyspnea) and vomiting.
A characteristic sign of chronic cadmium poisoning
is a microcytic hypochromic anemia; another significant
finding from a diagnostic standpoint may be the
formation of a yellow ring as a part of the tooth
structure in chronically exposed men.2 A severe
disabling emphysema without clinical or histological
evidence of chronic bronchitis was the uniform syndrome
exhibited by men chronically poisoned with cadmium
fumes.a
With regard to the toxicity of cadmium toward fish,
cadmium can disrupt energy production by the inhibition
of oxygen uptake.6 within the cells, this disruption can
occur at relatively low levels and be of such severity
as to cause the deaths of fish, particularly the blue
gill.6 Because cadmium acts synergistically with other
A-17
-------
substances to increase toxicity, the lethal concen-
tration for fish varies from 0.01-10.0 mg/liter
depending on the test animal, type of water,
temperature, and length of exposure.*
Environmental Properties
The water quality standard for cadmium and its com-
pounds is 0.01 ppm.6
One of the problems with heavy metals is their
tendency to concentrate through both aquatic and
terrestrial food chains.22 Aquatic macro- and micro-
flora and fauna accumulate heavy metals such as cadmium
in body tissues in significantly greater concentrations
than present in the surrounding environment. These
organisms are the food source for fish and insects which
retain the cadmium in the tissues of the consumed
organisms. The fish and insects are consumed in turn by
larger organisms; this process continues to the
organisms at the top of the pyramidal food chain, such
as man and large carnivorous birds and mammals. The
more links in the chain, the more severe the bioaccumu-
lation phenomenon.
2i Bildioactiy.6. Properties; None
Chlorinated Hydrocarbons
A-. Physiigal/Chemical Propertieg
The chlorinated hydrocarbon waste stream to which
this document relates is generated by purification of
chlorine gas in the chlor-alkali industry; the overall
properties of this waste are discussed below.
This dark-brown, tar-like waste is a mixture of
chlorinated compounds of varying degrees of complexity
which are partially polymerized. Therefore, a complete
compound analysis would probably identify a very wide
range of compounds from the simple compounds such as
C2H2C14 to very large, highly branched polymers. It is
sparingly soluble in water, but soluble in chlorinated
organic solvents, e.g. methylene chloride, and it is
flammable.
A-18
-------
The chlorinated hydrocarbons include a large number
of chemicals with high insecticidal activities. s They
are especially resistamt to degradation to nontoxic end
products,, and many persist for months or years following
application. Although most chlorinated hydrocarbons are
sparingly soluble in water, their solubility is still
greater than the 96 hour TLm values.5
The physical/chemical properties of several chlori-
nated hydrocarbons are gi^em below a
Trichloromethang ((Chloroform!) a (CHC13J is a highly
refractive? noraf lammable,; heavy „ very volatile,
sweet-tasting liqwid with a characteristic odor- At
25°C chloroform0 s solubility in water is 7o420 g/liter;
b0po
-------
ical Properties
A summary of the levels of several chlorinated hy-
drocarbons that produced minimal toxicity or no effects
when fed chronically to dogs and rats is given in Table
I.14 Limits for chlorinated hydrocarbons in drinking
water have been calculated primarily on the basis of the
extrapolated human intake that would be equivalent to
that causing minimal toxic effects in mammals (rats and
dogs). To determine a safe exposure level for man,
conventionally a factor of 0.1 is applied to human data
where no effects have been observed; whereas a factor of
0.01 is applied to animal data when adequate human data
are available for corroboration. A factor of 1/500 is
generally used on animal data when no adequate and
comparable human data are available.**
Regardless of how they enter organisms, chlorinated
hydrocarbons cause symptoms of poisoning that are sim-
ilar but differ in severity.11 The severity is related
to concentration of the chlorinated hydrocarbon in the
nervous system, primarily in the brain. Mild
intoxication causes headaches, dizziness, gastro-
intestinal disturbances, numbness and weakness of the
extremities, apprehension and hyperirritability. In
severe cases, there are muscular fasciculations
spreading from the head to the extremities, followed
eventually by spasm involving entire muscle groups,
leading in some cases to convulsions and death.
The substitution of a chlorine atom for a hydrogen
greatly increases the anaesthetic action of a member of
the aliphatic hydrocarbon series.6 In addition, the
chlorine derivative is usually less specific in its
action and may affect other tissues of the body in
addition to those of the central nervous system; in many
cases, the chlorine derivative is quite toxic. For
example, chloroform, in addition to its narcotic quali-
ties, may cause liver, heart and kidney damage.
As a general rule, the unsaturated chlorine deri-
vatives are highly narcotic but less toxic than the
saturated derivatives thus causing degenerative changes
in the liver and kidneys less frequently. In the
saturated group, the narcotic effect is enhanced with an
increase in the number of chlorine atoms. However,
there is less relationship between the number of
chlorine atoms present and the toxicity of the compound.
In dealing with these chlorinated hydrocarbons, it
must be remembered that a toxic action may result from
A-20
-------
Lir;;,?3 roi
Long-tern, levels with minimal of no effects
Calculated, moit'ur.um safe levels
from all sources of exposure
Intake from diet
Water
Compound
Aldrirr.
Chlordane
DDT
Diddrirr
> Endrin
M
• — i
Heptachlor
Heprachlor Epaxtde
Undone
MethaxycWoT
Toxaphene
Species
Rat
Dag
Man
Raf
Dog
Man
Rat
Dag
Man
Rat
Qog
Man
Rat
Dog
Mart
Rat
Dog
Man
Rat
Dog
Man-
Rat
Dog
Matt
Rat
dog
Man
Rat
Dog
Man
ppm TIT diet
0.5
T.Q
2.5
N.A.
N.A.
5.0
400.0
0.5
1.0
5.0
3.0
N.A.
0.5
4.0
N.A.
0.5
0.5
M.A.
50.0
15.0
N.A,
loo.a
4000.0
10.0
40Q.O
N.A.
Reference; mg/kg body
weight/day
(l> 0.083
(I) 0.02
0.003
(1) 0.42
N.A,
N.A.
(1) 0.83
(1) 8.Q
0.5
(T) O.C33
(!) Q.02
.. ;. O.C03
(5) 0.83
(8) O.C6
N.A,
(!) 0.083
Cl) 0.05
N.A.
(i) o.:-?i
(i) Q.C:
N.A,
(I) 8.3
VIC
1/500
. . 1/500
1/500
V500
. . . t . V'500
. ... yscxi
lAoa
1/500
1/100
1/100
(7) 1/10
1/5QO
. . 1/500
ma/kg/day
o.oooea
0.0002
0.0003
0.00084
O.QQ8
0.08
O.Q5 •
0.00083
0.0002
O.QQC3
Q.QQ166
0.00012
O.COO'68
0.00016
a. 000163
a. 00002
0.0166
0.0008
0.17
0.8
0.2
0.0034
0.016
mg/man/day mo/man/day % of Safe Level '
0.0581
Q.OI4 0.0007 5.0
0.021
0.588
T T
0.56
5.6 Q.02! 3.4
3.5
0.058!
tJ.Q'4 - 3.004C 35,0
0.021
0.1162
0.0084 0.00035 4.1
0.1162
0.0112 o.ooocr 0.6
O.Q'162
0.0014 C,OQ2" iSC.C
1.162
0.042 C.0035 3.3
11.9
56.0 1 T
14.0
0.23
1.12 T T
7is of Scfe Level recommended
limit (mg/l)
20 0.001
5 O.CG3
20 D.05
20 -3. 001
20 O.QOG5
2 O.COC;
J ", . COG ':
20 0.005
20 i-0
2 0.005
-------
repeated exposure to concentrations which are too low to
produce a narcotic effect, and which consequently are too
low to give warning of danger.6 Individual susceptibility is
also important when poisoning by this group of solvents is
being considered. Certain workmen may be seriously affected
by concentrations that seem to have no effect on fellow
employees in the same exposure.
The chlorinated hydrocarbons are also irritants to
the eyes and the mucous membranes.6 Repeated direct
exposure to the skin may result in dermatitis and poses
the additional danger of absorption through the skin.
In most instances, it is difficult to predict the
toxicity of chlorinated aromatic hydrocarbon compounds.6
However, in the case of most aromatic chlorine com-
pounds, their toxicity is usually no greater, and
frequently less, than that of the corresponding aromatic
h yd roc arbon s .
Qi Environmental Properties
Maximum allowable concentrations (MAC) and water
quality limitations for some chlorinated aliphatic
hydrocarbons which may be constituents in the waste are
listed below. The major portion of the waste is
expected to be much larger molecules. This type of
material is generally less toxic, more resistant to
decomposition and more environmentally persistent than
the compounds listed below.
Maximum Allowable Concentrations and Recommended
Water and Soil Limits for Selected Chlorinated Hydrocarbons6
Chlorinated_Ali2hatic Contaminant in
n MACJmg/1^ Water and Soil
Carbon Tetrachloride 25 1.95
Chloroform 50 6.0
1 ,2-Dichloropropane 75 17.5
Ethyl Chloride 1,000 130.0
Tetrachloroethane ----- 175.0
Dichloromethane 500 87.0
Trichloroethane 500 19.0
Vinyl Chloride ----- 38.5
Chlorinated hydrocarbons are generally stable, the
half-life of their residues range up to 20 years; their
high solubility in fat and low solubility in water
A-22
-------
enables them to penetrate into animal food products.8
because of theit relatively high vapor pressure, chlo-
rinated hydrocarbons have a tendency to evaporate from
soils and plants and to circulate widely in the
atmosphere* Their distribution does not depend on water
draining from agricultural land into streams or on
dumping of residues into sewers by manufacturers; most
of the chemicals move via the air* When sptayed on a
field, it evaporates and adheres to dust particles that
carry it long distances until it is precipitated by rain
or snow. Water becomes saturated with as little as 1-2
ppb. The portion that does not dissolve quickly enters
organisms living in water, particularly tiny inverte-
brate animals* Pish» which are extraordinarily
sensitive to many chlorinated hydrocarbons, feed on
these animals and further concentrate chlorinated
hydrocarbon compounds in their bodies. Birds feed on
fish and each link in the food chain presents an
increasing build-up of chemicals. Eventually,
chlorinated hydrocarbons reach humans when they consume
fish, birds, other animals and plants. The major
mechanism of removal of chlorinated hydrocarbons and
their residues from the soil is evaporation. The
effectiveness of some chlorinated hydtocatbons as
insecticides, as well as their long term hazard, is the
result of theit strong affinity fot fat. In insects and
other animals, chlotinated hydrocarbon insecticides
affect the central nervous system causing convulsions
and paralysis. In vertebrate animals they induce
degeneration of the heart muscle and of the liver. In
fish, they block oxygen uptake at the gills and cause
death by suffocation.
EU. Radioactive Progertiesi None
Shtomium Comgounds
&•. Chemical/Physical Properties
Chromium Hyjroxide (Cr (OH) 3.nH2Ol
The solubility of this amphoteric green gelatinous
precipitate* varies significantly with pH20* In the
presence of chloride ions, it is least soluble at
pH 8.5; 2.61 x 10-i4 g cr+3 is present in one liter of
saturated solution. At pH 9, 3.28 x 10-it g cr+Vliter
remain in solution; at pH 7, 3.28 x 10-l<> g Cr+Vliter
remain in solution.18 As the pH becomes more acidic the
A-23
-------
rate of solubilization increases rapidly. At pH 5 a
saturated solution of Cr(OH)3.nH2O will contain 5.2 x
10-i g cr+3/liter. At pH 3, 5.2~x 103 g Cr+3 will dis-
solve in a liter of water.18
In the absence of chloride ions chromium hydroxide
is dramatically less soluble.18 At pH 5 the saturation
concentration is 2.07 x 10-« g Cr+3/liter; at pH 7 and 9
the saturation concentration is below 5.2 x 10~12 g
Cr+3/liter. Please note that the data for Cr(OH)3 in
the absence of chloride ions may be too low. There is
some indication that this is theoretical data for the
nonhydrated form which is non-existent.18
Chromium hydroxide can be decomposed to chromic
oxide (Cr2O3) by heat.*
Chromic Oxide (Cr2o3)
The light to dark green trigonal crystals of
chromic oxide (m.w. 151.99, d. 5.21, m.p. 2435°C, b.p.
i»000°c)9 turn brown on heating but revert to a green
color on cooling.1 Because of this oxide's amphoteric
nature its solubility is pH-dependent. Chromic oxide is
least soluble at pH 7 (1.51 x IQ-to g Cr+3/liter) in
solutions devoid of chloride ions.20 In the absence of
chloride ions, at a pH 9, a saturated solution will con-
tain 0.0126 x 10~3 g Cr+3/liter.20 Acid treatment solu-
bilizes chromic oxide at a pH of 1, its solubility is
above 52 g/liter.
Chromium Chloride IIIL (CrCl2)
The lustrous white needles or fused fibrous mass of
this chromium salt (m.w. 122.90, d. 2.878, m.p. 824°C,
b.p. 1300°C)9 are very hygroscopic.1 Chromous chloride
is stable in dry air but oxidizes rapidly if moist; it
is a powerful reducing agent, chromium chloride is very
soluble in water giving a blue solution but insoluble in
alcohol and ether.
Chromium Chloride illll (CrCl3)
Chromium chloride III (m.w. 158.35, d. 2.76,
m.p. 1150°C, b.p.(subl) 1300°C)« exists in a hydrated
form, namely, chromium chloride hexahydrate (CrC13.6H2O)
as well as a nonhydrated form (CrCl3).l The hydrated
form has blue-gray rhombohedral, dark green triclinic or
A-24
-------
monoclinic, or light green crystals. It is very deli-
quescent in air. Chromium chloride hexahydrate is sol-
uble in water (585 g/liter at 25°C) • with dilute aqueous
solutions being violet and concentrated aqueous solu-
tions green. It is slightly soluble in acetone, soluble
in alcohol and practically insoluble in ether. This
chromium salt's solubility is pH-dependent such that its
solubility is greatly reduced at pH's greater than 5.»«
f Triyaleot Chromic Salts
The nitrate and sulfate salts are readily soluble
in water, but the carbonate is quite insoluble.9 Neu-
tralization of the soluble salts will precipitate
Cr(OH) 3.nH20.
Hexavalent Chromium Sajlts
of these compounds only the sodium, potassium and
ammonium chromates are soluble.9 Hexavalent chromium can
be reduced to the trivalent form by heat, organic matter
or reducing agents.
Us. Biological Properties
Trivalent Chromium Compounds
Trivalent chromium compounds are said to be less
toxic than the hexavalent chromium compounds.6 Eczema-
like skin conditions from trivalent chromium contact
have been reported. The toxicology literature discusses
the hexavalent compounds in considerable detail but the
available literature does not distinctly describe the
hazardous properties of the trivalent compounds by them-
selves.6 Internally, chrome salts act as an irritant
causing tissue corrosion in the gastrointestinal tract.
Complaints of bad taste in the mouth, vomiting and
bloody stools are often noted. In addition, the central
nervous system is often involved and dilated pupils,
coma, collapse, slow respirations, shock and death some-
times occur.6 In contact with the skin, chromium metal
and Cr+3 combine with proteins to form complexes in the
superficial layers.
A-25
-------
Hexavalent Chromium Compounds
The water soluble hexavalent compounds are
extremely irritating, corrosive, and toxic to human body
tissue; they penetrate surface tissue before they react.
Insoluble chromium compounds, on the other hand, are re-
tained in the lungs over extended periods of time and
play a role in the production of lung cancer.8 Chromium
in the hexavalent form is clearly a cause of Ulceration
and perforation of the nasal septum.8 The septum is par-
ticularly susceptible to the action of chromium not only
because of the immediate contact of inhaled particles
with the septum, but also because of its structure;
i.e., the mucous membrane covering this area is far less
vascular than the mucous membrane lining the rest of the
nasal fossae and thus is easily destroyed. Other sites
where ulcers may appear as a result of contact with
chromium*6 are the skin, the roots of the fingernails,
the knuckles, the eyelids, the edges of the nostrils,
the toes and rarely the throat.8
General
The chromium metal itself is stable and relatively
nontoxic because of its insolubility in water and body
fluids.8 Chromium, a trace element essential for sugar
and fat metabolism, is necessary for the action of insu-
lin.8 Chromium deficiency in the diet of animals causes
a syndrome simulating diabetes. A lack of chromium has
also been associated with atherosclerotic heart disease,
elevated cholesterol levels in the blood, and high fat
content of the aorta. In areas where atherosclerosis is
mild or absent, more chromium is found in body tissue
than where the disease is endemic.8
The toxic dose of chromium for man is reported to
be about 0.5 g K2Cr2O7.s The toxicity of chromium salts
toward aquatic life varies with the species, tempera-
ture, pH, valence, of the chromium, and synergistic or
antagonistic effects, especially that of hardness.5 Fish
are relatively tolerant of chromium salts, but lower
forms of aquatic life are extremely sensitive. There
appears to be no evidence to lead to a conclusion that
hexavalent chromium is more toxic toward fish than the
trivalent form. Toward fish and other aquatic organisms
the toxicities of trivalent and hexavalent chromium com-
pounds have been reported as given in Table 2: Table 3
summarizes the reported effects of hexavalent chromium
toward mammals.
A-26
-------
Table 2. Toxicities of Chromium Compounds to Selected
Aquatic Organisms9
Concentration
of chromium
2)3/1
52
5.2
20
1.2
2.0
5.2
0.05
0.21
1.4
40.6
0.7
148
Compound
SSfid
K2Cr2O7
K2Cr2O7
Cr2 (SOJJ) 3
Cr 2 (S04) 3
KCr (SO 4) 2
K2Cr2O7
Na.2CrO4
K2Cr2O7
Cr04
Type of
Organisms
Young eels
Brown trout
Rainbow trout
Sticklebacks
Sticklebacks
Young eels
Daphnia magna
Protozoan
(Microregma)
Gammarus pulex
Snail
E. coli
Polycelis nigra
Remarks
Tolerated for
50 hours
Toxic
Toxic at 18°C
Lethal limit
Survived only
2 days
Survived an aver.
of 18.7 hours
Killed in 6 days
Threshold effect
Total mortality
Hardwater TLm,
20 °C
Threshold effect
Toxic threshold
A-27
-------
Table 3. Toxicological Responses of Mammals to Hexavalent
Chromium**
Animal Route
Material
Average
Dose or
Concentration Duration Effect
Rabbit
6
Cat
Rabbit
Rabbit
Mouse
Mouse
Mouse
Dog
Dog
IH
SC
IV
IH
IV
IV
IV
SC
Chromates
K2Cr207
K2Cr207
Mixed dust
containing
1-50 mg/m3
20 mg
0.7 cc of 2%
solution per
kg body wt.
7 mg/m3 as
Cr03
1U hr/day
for 1-8
months
Zinc chromate 0.75 mg
K2Cr207
K2Cr2o7
K2Cr207
0.7 cc of 2%
solution per
kg body wt.
210 mg as Cr
210 mg as Cr
37 hours
over 10
days
1 dose
Pathological
changes to
lungs
Lethal
Fatal
Fatal
Fatal
Fatal
Rapidly .fatal
Rapidly fatal
*IH - inhalation; IV - intravenous; SC - subcutaneous.
Chromium is present in trace amounts in soils and
in plants, but there is no evidence that chromium is
essential or beneficial for plant nutrition.17
Generally, concentrations of trivalent or hexavalent
chromium in excess of 1.0 mg/kg of soil inhibit nitrifi-
cation. On the other hand, the addition of 5 mg of
chromium per kg of soil resulted in a slight increase of
the nitrogen content of peas. Chromium is picked up by
plants from the soil, for vegetables grown on soil irri-
gated with waste waters containing chromium had 3-10
times more chromium than those grown in similar soil de-
void of chromium containing irrigation water.17
A-28
-------
Environmental Properties
The drinking water standard is 0.05 mg/liter for
hexavalent chromium8; the recommended standard for tri-
valent chromium is likewise 0.05 mg/liter.6 The chromium
containing sludges when occurring as a result of the
standard reduction/hydroxide precipitation treatment
methods can present a twofold toxicological hazard if
landfilled.* The sludges can contain soluble chromium
salts and complexes which, if leached out of the fill,
can be detrimental. It is also possible for acid
species to be landfilled with the hydroxide sludges,
dissolve them, forming water soluble chromium compounds.
Those water soluble materials can find their way to a
potable water table from an inadequately placed landfill
site.*
One of the problems with heavy metals is their ten-
dency to concentrate through both aquatic and
terrestrial food chains.** Aquatic macro- and micro-
flora and fauna accumulate heavy metals such as cadmium
in body tissues in significantly greater concentrations
than present in the surrounding environment. These
organisms are the food source for fish and insects which
retain the cadmium in the tissues of the consumed
organisms. The fish and insects are consumed in turn by
larger organisms; this process continues to the
organisms at the top of the pyramidal food chain,, such
as man and large carnivorous birds and mammals. The
more links in the chain, the more severe the bioaccumu-
lation phenomenon.
p. Radioactive Propgrtiesi
C2ba.it and Its Compounds
Aj. Physical/Chemical Prgperti^g
Elemental cobalt (Co)
Cobalt (a.w. 56.93, m.p. 1493°C, b.p. 3550°C,
d. 8.92)* is a silver-grey, hard, magnetic, ductile,
somewhat malleable metal which crystallizes in hexagonal
or cubic form.» cobalt is stable in air or toward water
at ordinary temperature. It is readily soluble in
dilute nitric acid but only very slowly attacked by
hydrochloric acid or cold sulfuric acid. The hydrated
A-29
-------
salts of cobalt are red; the soluble salts form red
solutions which become blue on adding concentrated
hydrogen chloride.
CobaXtous Oxide (CoO)
The cubic green-brown crystals' of this salt
readily absorb oxygen even at room-tempe-rature. 4 It is
practically insoluble in water but is soluble in acids
or alkali hydroxides. Cobaltous oxide is easily reduced
to cobalt by carbon or carbon monoxide. Cobaltous oxide
reacts at high temperatures with silica, alumina, and
zinc oxide to form pigments.* It is formed by the
calcination of cobalt carbonate or its oxides at high
temperatures in a neutral or slightly reducing
atmosphere.7
Cobaltous-cobaltic Oxide (Co3o4)
Cobaltous-cobaltic oxide (m.w. 240.82, transition
point 900-950°C) is a grey-black crystalline powder
which above 900°C loses oxygen to form CoO.1 It absorbs
oxygen at lower temperatures but the crystalline
structure is unchanged. Co3_o4 absorbs water but no
definite hydrate has been identified. It is reduced to
elemental cobalt by carbon, carbon monoxide or H2. This
cobalt oxide is soluble in concentrated acids and
alkalis although practically insoluble in water.
Cobaltic Oxide (Co2O3)
This steel-grey or black powder (m.W. 165.88, d.
4.81-5.60, m.p. decomposes at 895°C)* is formed when
cobalt compounds are heated at a low temperature in the
presence of an excess of air or by oxidizing neutral
cobalt solutions with NaOCl.1 It is converted to Co3o4
above 265°C.* Although practically insoluble in water,
it is slowly soluble in hot HCl or hot dilute H2SO4 with
the evolution of C12 or O2.1
Cobaltous Chloride (Cod2)
Cobaltous chloride (m.p. 724°C in HCl gas,
d. 3.348, b.p. 1049°C, m.w. 129.84) is composed of
pale-blue hygroscopic leaflets which appear colorless in
very thin layers; this cobaltic salt turns pink on
exposure to moist air.1 Cobaltous chloride decomposes on
long heating in air at 400°C; it sublimes at 500°C in
HCl gas, forming iridescent, fluffy, colorless crystals.
It is soluble in water, alcohols, acetone, ether and
glycerol. Cocl2 also occurs in a hydrated form.
A-30
-------
Anhydrous cobaltous chloride becomes saturated in 96°C
water at a concentration of 1050 g/liter whereas at 7°C
its solubility is 450 g/liter.* In alcohol it is soluble
to the extent of 544.0 g/liter and in acetone 86.0
g/liter.«
Cobaltous Chloride HexahYdrate (COC12«6H2O)
This hydrated form of cobaltous chloride exists as
a pink to red, slightly deliquescent, monoclinic, pris-
matic, crystalline material.1 On heating, COC12.6H2O
(m.w. 237.93, m.p. 86.75°C, b.p.-6H2O at 110<>C)» loses
four water molecules at 52-56°c forming the dihydrate,
violet or blue crystals which are stable unless exposed
directly to moisture. It loses another water molecule
at 100°C giving a monohydrate, violet, hygroscopic,
amorphous solid or needles. The remaining water
molecule is lost at 120—140°c. Hexahydrated cobaltous
chloride is soluble in alcohols, acetone, ether and
glycerol. Its solubility in water at 0°C is 767.0
g/liter and in water at 100°C it solubilizes to the
extent of 1907.0 g/liter.«
Cobaltous material is an oxidizing material which,
in contact with organic or other readily oxidizable sub-
stances may cause a violent reaction or combustion.6
Cobalt salts hydrolyze to produce acid solutions. The
pH of a 0.2 M aqueous solution of cobaltous chloride
hyxahydrate is 4.6.*
Solutions containing cobaltous ions (Co++) are
relatively stable but cobaltic ions (Co***) are powerful
oxidizing agents and consequently they are unstable in
natural waters.s
B. Biological Properties
Elemental Cobalt
In humans, the level of cobalt toxicity is low,
about equivalent to a daily dietary intake of 150 ppm.e
Cobalt has been administered in the treatment of
nephritis, in infections, and in anemias during
pregnancy. However, its use has led to serious toxic
manifestations, including thyroid enlargement, myxedema
(a disease caused by thyroid deficiency) and congestive
heart failure in infants. In mice, rabbits, and
domestic animals, excessive doses of cobalt have caused
polycythemia which overtaxes the heart and is associated
with high blood pressure.8
A-31
-------
Little is known about the effect of cobalt as a
constituent of ambient air.a In hard metal manufacturing
it has been a source of pulmonary fibresis. Powdered
cobalt is used as a bonding material in the manufacture
of cutting tools that contain tungsten and carbide. In
such factories fine particulate dust measuring less than
2.0 microns in diameter is generated and spreads into
areas where it is not in use. Whereas powdered tungsten
carbide has little or no irritant effect on the lungs,
powdered cobalt produces chronic lung changes leading to
pulmonary fibrosis, with chronic cough and shortness of
breath. This disease is usually fatal if not diagnosed
early.
When ingested with food, cobalt affects the heart
and the thyroid gland.8 In 1965 and 1966 an epidemic of
a serious heart disease occurred in Quebec, Canada. Of
18 persons so afflicted, twenty died in shock. The
essential symptoms were shortness of breath, pain in the
heart and stomach area, cough, swelling of ankles, and
general weakness. After numerous agents had been ruled
out as the possible cause, it became apparent that the
only individuals who had contracted the disease were
those who had imbibed large amounts of beer. Changes in
the thyroid gland of the diseased persons showed
features characteristic of cobalt intoxication. The
disease was promptly eliminated upon discontinuance of
the use of cobalt in processing beer. Although the
doses of ingested cobalt compounds in these cases were
much greater than those of atmospheric contamination
these findings are of interest in view of the lack of
data concerned with long term cobalt ingestion and
inhalation in minute concentrations.
Qobaltous Conjegunds (Co*+)
Trace amounts of cobaltous ion appear td stimulate
the growth of some organisms.5 A definite growth
response in the protozoan ciliate, Tetrahvmena sp^, was
produced by 0.0005 mg/liter cf cobalt, while the optimum
total growth and rate of growth occurred at 0.008
mg/liter. The addition of 1-5 mg/liter of cobalt, as
cobalt chloride or cobalt sulfate, to a medium used in
the propagation of actinomycetes gave conspicuous
growth.
At higher concentrations, however, cobalt ions have
demonstrated pronounced toxic effects. The lethal
concentration for the stickleback, Gasterosteus
2£Uleatusx was 10 mg/liter of cobalt ion.5
A-32
-------
Below summarizes the toxicity of cobalt and two
of its compounds towards certain mammals.
Toxicological Responses of Selected Mammals to
Cobalt7
Co: ORI-rat LDLo: 1500 mg/kg
ims-rat TDLo: 112 mg/kg
CoCl2: ORI-rat LD50: 180 mg/kg
ORI-mouse LD50: 80 mg/kg
SCO-mouse LDLo: 100 mg/kg
ORI-guinea
pig LD50: 55 mg/kg
CoO: ims-rat TDLo: 90 mg/kg
Environmental Properties
The water quality standard for cobalt and its com-
pounds is 0.05 mg/liter as Co.6
p_._ Radioactive Properties ^ None
At Physical /Chemical, groperti.es
Copper (Cu)
Elemental copper (a.w. 63.54, m.p. 1083°C,
b.p. 2595°C, d. 8.94)9 dissolves readily in nitric and
hot concentrated sulfuric acid; it solubilizes slowly in
hydrochloric and dilute sulfuric acid but only when
exposed to the atmosphere.1 copper is more resistant to
atmospheric corrosion than iron, forming a green layer
of hydrated basic carbonate.4 It is noncombustible
except as powder.* Metallic copper is insoluble in
water. *
Cuprous Oxide (Cu2O)
Copper (I) oxide (m.w. 143.08, m.p. 1232°C,
b.p. 1800°C, d2S4 6.0)» exists as octahedral crystals*
or microcrystalline powder, the color varying from
yellow, red or brown, depending on the method of
preparation and the particle size. l This oxide is stable
A-33
-------
in dry air but gradually oxidizes to CuO in moist air.*
It is insoluble in water and alcohol but soluble in
hydrochloric acid, ammonium chloride, ammonium hydroxide
and slightly soluble in nitric acid.1
CAiPiic. Qxide (CuO)
Copper (II) oxide (m.w. 79.54, m.p. 1326°C,
d. 6.3-s6.49)» occurs as a black to brownish-black amor-
phous or crystalline powder or granules.» It is soluble
in dilute acids, alkali cyanides and (NH4)2CO3 solu-
tions; it is slowly soluble in ammonia.1 cupric oxide is
slightly soluble in water; at a pH 9 it solubilizes to a
concentration of 1.51 x 10~s mg/liter as Cu*+ in pure
water.18 As the pH decreases, the solubility of cupric
oxide increases such that at pH 5 its saturation
concentration is 313.0 mg/liter as Cu**.»»
Properties
Copper is found in traces in all plant and animal
life; it is believed to be essential for nutrition.5 The
physiological function of copper appears to be involved
in the metabolism of iron, for the utilization of iron
by the blood-forming organs does not occur properly in
the absence of copper. The copper requirement is re-
ported to be about 2 mg/day for children and 3 mg/day
for adults. s
In general, the soluble ionized salts of copper are
much more toxic than the insoluble or slightly disso-
ciated compounds.2 Probably the most poisonous salts are
the chloride and the subacetate. 2 cuprous chloride is
said to be twice as toxic as the more common cupric
salt, but no major toxicological distinctions are recog-
nized between the two valence states of copper.2 As the
sublimed oxide, copper may be responsible for one form
of metal fume fever.3 Inhalation of copper dust has
caused, in animals, hemolysis of the red blood cells,
deposition of hemofusion in the liver -and pancreas, and
injury to the lung cell} injection of the dust has
caused cirrhosis of the liver and pancreas,, and a condi-
tion closely resembling hemochematosiis, or bronzed
diabetes.3 However, considerable trial exposure to
copper compounds has not resulted in such disease. 3
As regards local effect, copper chloride and sul-
fate have been reported as causing irritation of the
skin and conjunctivae which may be on an allergic
basis. 3 cuprous oxide is irritating to the eye and upper
A-3U
-------
respiratory tract. Discoloration of the skin is often
seen in persons handling copper, but this does not
indicate any actual injury from copper.3
Copper resembles many other heavy metals in its
systemic toxic effects: widespread capillary damage,
kidney and liver injury, and central nervous excitation
followed by depression.2 Hemolytic anemias are described
in acute poisoning in man and chronic poisonings in
sheep. Copper appears to be less deleterious than most
heavy metals when ingested continuously in small
amounts, but chronic feeding to animals results in a
pigmentary cirrhosis of the liver.2
Acute poisoning from the ingestion of copper salts
is rarely severe, if the metal is removed promptly by
enesis.2 Vomiting is provoked chiefly by the local irri-
tant and astringent action of ionic copper on the
stomach and intestines.2 If vomiting fails to occur,
gradual absorption from the bowel may cause systemic
copper poisoning. Death is delayed for several days and
apparent recovery may be followed by a fatal relapse.2
A type of chronic copper poisoning in man is recog-
nized in the form of a metabolic disease called heredi-
tary hepatolenticular degeneration (Wilson's disease).2
Tissue copper levels are elevated in Wilson's disease,
and this accumulation has been noted to precede the
development of liver pathology, which may ultimately
prove fatal.2 If dietary copper intake is reduced and
urinary excretion promoted, the neurologic signs and
symptoms associated with Wilson's disease are alle-
viated. BAL, calcium disodium edetate and
sulfur-containing amino acids can mobilize tissue copper
stores for excretion; at least BAL has been shown to
produce some clinical improvement, but repeated
injections frequently give rise to undesirable side
effects.2
Because copper in concentrations high enough to be
dangerous to human beings renders water disagreeable to
taste, it is believed by some that copper is probably
not a hazard in domestic water supplies; although in
excessive quantities it has been found toxic to a wide
variety of aquatic forms, from bacteria to fish.5 The
toxicity of copper to aquatic organisms varies signi-
ficantly not only with the species, but also with the
physical and chemical characteristics of the water such
as its hardness, temperature, turbidity and carbon
dioxide content.5 In hard water, the toxicity of copper
salts is reduced by the precipitation of copper carbon-
A-35
-------
ate or other insoluble compounds.5 The toxicity of
copper to fish varies greatly depending on the presence
of magnesium salts and phosphates. In the control of
ChirgjiOjTms sj3._ larvae, copper and chlorine together act
synergistically to increase the toxicity of each acting
alone. The sulfates of copper and zinc and of copper
and cadmium are synergistic in their toxic effect on
fish. Synergism also exists between copper and mercury
and between copper and pentachlorophenate. On the other
hand, sodium nitrite and sodium nitrate have been
reported to decrease the toxicity of copper sulfate to
fish, and copper has shown evidence of decreasing the
toxicity of cyanide.5
Qi EjQYironmental Properties
The water quality standard for copper and its
oxides is 1.0 mg/liter as Cu.s
Many copper salts are highly soluble as cupric or
cuprous ions.5 Copper salts occur in natural surface
waters only in trace amounts, up to about 0.05 mg/liter
so that their presence is generally the result of pollu-
tion, attributable to the corrosive action of the water
en copper and brass tubing, to industrial effluents, or
frequently to the use of copper compounds for the
control of undesirable plankton organisms.5 The
chloride, nitrate and sulfate of divalent copper are
readily soluble in water, but the carbonate, hydroxide,
oxide and sulfide are not. s Indeed, cupric ions intro-
duced into natural waters at pH 7 or above will quickly
precipitate as the hydroxide or as basic copper
carbonate, CuCO3.Cu (OH) 2.H2O, to be removed by absorp-
tion and/or sedimentation. As a result, copper ions are
not likely to be found in natural surface waters or
ground water.5
Investigations of the chemical fate of copper salts
in the soil, especially with respect to organic matter
and carbonate content of the soil have been conducted.5
It was found that when copper sulfate was added to
irrigation water at a concentration of 20 mg/1, CuSOUer,
it reached an equilibrium in the soil at 1.0 mg/liter
after 6 hours at 20°C. Copper retention in the soil
appears to be correlated more with organic matter and
soil alkalinity than with the clay content of the soil,
and organic matter appears to be more effective than
carbonates in retaining copper.5
A-36
-------
One of the problems with heavy metals is their
tendency to concentrate through both aquatic and ter-
restrial food chains «>22 Aquatic macro- and micro- flora
and fauna accumulate heavy metals,, such as copper, in
body tissues in significantly greater concentrations
than present in the surrounding environment., Important
mechanisms for uptake of copper and other heavy metals
includes absorption from the soil and sediments by
plantse ingestion by stream bottom feeders and by
detrius feeders0 The aquatic macro- and micro- flora
and fauna are the food source for fish and insects which
retain the copper in the tissues of the consumed
organismso The fish and insects are consumed in turn by
larger organismss this process continues to the organ-
isms at the top of the pyramidal food chain? such as man
and large carnivorous birds and mammals. The more links
in the chain, the more severe the bioaccumulation
phenomenon„2 2
Di Radioactive Properties ^ None
Cyanides
A.. jghvsical/Chemical. Properties
Sodium Cyanide (NaCN)
Sodium cyanide JmoWo 49002, m,p* 563°Cff
b.p. Hi9°C}9 is a white, deliquescent, crystalline
powder3 which is odorless when perfectly dry; somewhat
deliquescent in damp air and emits a slight odor of
HCN.i It is freely soluble in water ^80.0 g/liter at
1<)°c, 820.0 g/liter at 35°C) but only slightly so in
alcoholo® The aqueous solution is strongly alkaline and
reipidly decomposes^; the solution readily dissolves gold
ar.d silver in the presence of air., a
Hydrogen Cy.aru.de JHCNJ
Hydrogen cyanide (m<>w° 27.,03, dqas 0.941, dliguid
0.687, mop. -1<4°Cr flash point Q°F)« is a colorless gas
or liquid xtfith a characteristic odor of bitter almondSo5
It is very weakly acid (does not redden litmus) and
bujrns in air with a blue flame o11 This cyanide boils at
26°C and is highly soluble as a gas or miscible with
tva-cer and alcohol as a liquid; it is slightly soluble in
etiier0 s In water, the ratio of cyanide ion to
urdissociated HCN is a function of pHos At pH values of
A-37
-------
7 or below* less than 1 percent of the cyanide molecules
ate in the form of cyanide ions at pM 8 only 6.1
percent, at pH 9 only 42 percent and at pM 10, fl7
percent of cyanide ia dissociated.9
When not absolutely pure or stabilized, HcM
polymerizes spontaneously with explosive violence* "
Hydrogen cyanide is a severe explosion hazard when
exposed to heat or flame by chemical reaction with
oxidizers.* In contact with alkaline materials, hydrogen
cyanides can polymerize or decompose explosively- The
liquid is commonly stabilized by the addtion of acids' «*
the solubility of HcN in water at -0.9°c is 0.81 moltt,
at -35°C is 3.09 molK and at H5.50°c it solubilize«s to
26.29
Ferric FerrofiV.anid£ (Fe4 (Fe(CN)6) 3J
Ferric ferrocyartide (m.w. 859*3)* exists as a dark
blue powder1 or crystals* which ate insoluble in dilute
acids, organic solvents, water, alcohol and ether but
soluble in concentrated MCl and H2SO
-------
Few poisons are more rapidly lethal than cyanide.
The inhalation of hydrogen cyanide commonly produces
reactions within a few seconds and death within
minutes.2 MCN in aqueous solution (hydrocyanic acid) is
readily absorbed from the skin and from all mucous
membranes, but the alkali salts are usually toxic only
when ingested* The average lethal dose of HCN taken
orally is believed to lie between 60 and 90 tng (1 to 1*5
grains), this corresponds to about 1 teaspoonful of a 2
percent solution of MCN and to about 200 mg tootussium
cyanide. The lethality of most derivatives is regarded
as proportional to the content of readily available
cyanide. The mortality rate is high, but in nonfatai
cases recovery is generally complete. Rarely
neuropsychiatric sequelae are observed* as in carbon
monoxide poisoning*2
Cyanide in reasonable doses (10 mg or lesa) is
readily converted to thiocyanate in the human body and
in this form is much less toxic to man.44 Usually,
lethal toxic effects occur only when the detoxifying
mechanism is overwhelmed.14 In the detoxification
mechanism the cyanide is converted to the thicyanate ion
by an enzymatic reaction which is mediated by the enzyme
rhodanese.2 This enzyme is widely distributed in
tissues, but the greatest activity is found in the
liver.2 The body has a large capacity to detoxify
cyanide, but the rhodanese system responds slu the
complex ions are relatively harmless.14 The tobi.L
cyanide content of such solutions is not a reliable
index of their toxicity since HCN derives from
dissociation of the complex ions, which can be greatly
influenced by pH changes. A more than thousand fold
increase of the toxicity of the nickelocyan.ide complex
is associated with a decrease of pH from 8*0-6.5. A
change in pH from 7.8-7*5 increases the toxicity more
than tenfold.14
Numerous investigators have shown that the toxicity
of free cyanide increased at reduced oxygen concentra-
tions. The toxic action is known to be accelerated
A-39
-------
markedly by Increased temperature, but the influence of
temperature during long exposure has hot been
demonstrated.*9 The toxicity of cyanide to diatoms
varies little with change of temperature and was a
little greater in soft water than in hard water.14 For
Ni^zchia iinearisjt concentrations found to cause a 50
percent reduction in growth of the population in soft
water (44 mg/liter Ca-Mg as CaC03) were 0.92 mg/liter
at I2°$t 0*30 mg/liter at 82°F» and 0.28 mg/liter at
B6°F* Cyanide appears to be more toxic to animals than
to algae* **
Ferric £errocy,§riide
Perrocyanides as such are of a low order of
toxicity, although highly toxic decomposition products
can form upon mixing them with hot concentrated acids.3
Acid, basic or neutral solutions of ferrocyanides
liberate hydrocyanic acid upon strong irradiation.3
Potassium ferrocyanide in which the iron is in the
reduced condition is readily soluble in water but the
complex ions decompose slowly to release cyanide ion.*
Sodium ferrocyanide in aqueous solutions decomposes
under the action of sunlight to release cyanide ion and
HcN. It has been shown that solutions containing the
ferro and ferricyanide complexes become highly toxic to
fish through photodecomposition upon exposure to
light."
Si invi£g.nme,Qtal prgeer^ieg
The water quality standard for the cyanides (HCN or
NaCN) is 0.01 mg/liter as Cfl.» Ferrocyanides and
ferricyanides are less toxic than HCtt or NaoH, but can
release cyanide ion which forms HCN in the presence of
heat and sunlight*** The relationship between potassium
ferrocyanide and concentration resulting CN-
concentrations in bright sunlight are as followsi
The Release of CM- by Photodecomposition of
Potassium Ferrocyanide1*
Concentration of ttesuiting Concentration
KlFe(CN)6 in (mg/1) of CM- in mg/liter
1 0.05-0.16
2 0.36-O.U8
3 0.72
5 0.50-0.8U
A-UO
-------
No water quality standard is available for ferro-
cyam.dess howeverff the concentration of ferrocyanides
should be such that no more than 0.01 mg/liter of
cyanide ion would be released to the water under optimal
conditions for ferrocyanide decomposition. Therefore
0.2 mg/liter is the recommended limiting concentration
in water and
D, Radioactive Propertiesi N
Fluorine and Its Compounds
hs. Physical/Chemical grogerties
Fluorine (F2J
Fluorine flaoWo 18.9984, b.p. -188°C0 m.p0 -217.8°C,
dgas» *sp do-200°ca a«, flash point -219.6°CJ9 is a
highly toxic and corrosive pale yellow gas with a sharp,
penetrating and characteristic odor0° Fluorine is the
most powerful oxidizing agent known,, reacting with
practically all organic and inorganic substances with
the exception of the inert gases,, metal fluorides in
their highest valence state and e. few pure completely
fluorinated organic compounds-s Fluorine decomposes
water giving hydrofluoric acid (HFJ„ oxygen fluoride
(OF2) g hydrogen peroxide,, oxygen and ozone. It reacts,
with nitric acidp forming the explosive gas fluorine
nitrate (N
-------
but the dry crystals or powder can be stored in glass
bottles. i
Calcium Fluoride (CaF2)
Calcium fluoride (m.W. 78.08, d. 3.18,
b»p. c.a. 2500°C) * occurs as either a white powder or
cubic, colorless crystals which luminesce upon heating.1
calcium fluoride is only slightly soluble (15 mg/liter)
at neutral pH's but as the pH of the solution decreases
its solubility increases. See Figure 1.*3
Hydrogen HU2£ide (HF)
Hydrogen fluoride (m.w. 20.01, m.p. -83.1°c,
b.p. 19.5UQC, dliquid 0.988)» is a colorless, fuming,
mobile liquid or colorless gas* which is infinitely
soluble in water, dissociating to hydrogen and fluoride
ions.* It is also soluble in alcohol, slightly soluble
in ether and soluble in many organic compounds, e.g.
benzene, toluene, m-xylene, tetralin* Many compounds
are soluble in HF. * White anhydrous HF is one of the
tnost acidic substances known but in aqueous solution it
is a weak acid (K=7.4 x 10-*).* Hydrogen fluoride
dissolves silica, silicic acid and glass*1
Biological Properties?
Fluorine/Fluoride
Fluoride is a "general protoplasmic poison," but it
is not possible yet to describe in detail the mechanism
by which it produces death.2 At least four major
functional derangements are recognized. Inhibition of
one or more of the enzymes controlling cellular
glycolysis may result in a critical lesion. Inhibition
of eholinesterase activity noted in Vitro, however,
probably plays no irole in fluorine poisoning even though
pretreatment of rats with fluoride increased their
sensitivity to succinylcholine, demiton and parathion*
shock due td fluid and electrolyte loss, central
vasomotor depression and perhaps direct depression of
vascular smooth muscle is an important contributory
cause of death. Mild renal pathology (acute congestion
and cloudy swelling of tubular cells) has been described
in human fatalities but death in acute renal failure
appears to be unknown both in man and animals, chronic
administration does not result in significantly more
renal injury. Finally, the binding or precipitation of
calcium as CaF2 has been suggested as the mechanism
A-U2
-------
l,000r
o 0.2 0.4 0.6 as 1.0
HYDROCHLORIC ACID CONCENTRATION (NORMALITY)
APPENDIX FIGURE I
SOLUBILITY OF CALCIUM FLUORIDE
IN HYDROCHLORIC ACID SOLUTIONS
A-41
-------
undetlying many divetse signs and symptoms in fluoride
poisoningi particularly if death is delayed* It is hot
certain as to whether or not calcium binding plays a role in
manifestations of central nervous system poisoning such as
depression and occasionally epileptiform convulsions and
respiratory failure* *
Besides being an inhibitor of glycolysis by virtue
of its inhibition of the enzyme enoiase, fluorine
through its inhibition of other enzymes inhibits energy
metabolism via the tricarboxylic acid cycle both by
blocking the entry of pyruvate and fatty acids and by
inhibiting succinic dehydrogenase.* Therefore, fluoride
is not simply a glycolysis inhibitor but rather a
general inhibitor of oxidative metabolism.
chronic endemic fluorosis due to high concentra-
tions of natural fluoride in local water supplies is
characterized by mottling of the teeth, osteosclerotic
changes in the skeleton and sometimes central nervous
uystem involvement.2 Fluorosie illustrates important
toxicological properties of fluoride but not onus that
are relevant to acute fluoride poisoning. Fluoride
poisoning can be induced by any soluble compound which
dissociates fluoride ion*2 Hydrogen fluoride is less
toxic than fluorine; the TLV is 3 ppm, 30 times that of
fluorine.6
Hydrogen Fluoride
The ingestion of an estimated 1*5 grama of hydrogen
fluoride produced sudden death without gross pathologic
iamage*2 On the other hand, the repeated ingestion of
•small amounts of HF has resulted in moderately advanced
fluoride osteosclerosis in mart. Thus, hydrogen fluoride
is capable of inducing the systemic manifestations of
both acute and chronic fluoride poisoning. It possesses
an additional hazard, however* because of its corrosive
properties.* Respiratory exposure to high concentrations
of HF fumes characteristically results in hemorehagic
pulmonary edema in man and animals* The potential
hazard of this local reaction is equivalent to that of
Hcl or So2» Even though pulmonary involvement may
dominate the clinical picture and the pathologic
findings, systemic fluoride poisoning may still be the
cause of death.2
Hydrogen fluoride, per se, is reported to be harm-
ful to fish at UO mg/liter and lethal at 60 mg/liter.
It appears that the concentrations of fluoride will not
A-4U
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interfere with the specified beneficial uses given:
Water Quality Criteria for Specific
Beneficial Uses of Water-Fluorides5
Domestic water supply 0.7-1.2 mg/liter
Industrial water supply 1.0 mg/liter
Irrigation water supply 10.0 mg/liter
Stock watering 1.0 mg/liter
Aguatic life 1.5 mg/liter
Sodium Fluoride
Clinical data indicates that the sodium salt of
fluorine lies near the borderline between toxicity
classes of "very toxic" (LDhuman 50-500 mg/kg) and
"extremely toxic" (LDhuman 5-50 mg/kg).2
Calcium Fluoride
Calcium fluoride is considered moderately toxic
with the lethal dose for humans ranging from 500-
5000 mg/kg of body weight.2 While oral ingestion of
solid calcium fluoride would immediately release toxic
quantities of fluoride, it would take a daily
consumption of 3-10 liters of saturated calcium fluoride
solution over a period of many years to produce
f luorosis.
Although calcium fluoride does not deserve
designation as a "severely hazardous" material as do
leads, cadmiums etc. , it is a potentially hazardous
substance whose disposal obviates regulation. Calcium
fluoride should be termed "moderately hazardous" whose
Level III disposal technology would necessitate a
disposal site isolated from natural ground water, and
with surface coverings of clay, graded so as to
virtually eliminate the entry of water into the waste.
Evidence offered by industry counter to the
position that calcium fluoride is a potentially
hazardous waste is exerpted below. The judgment of the
authors is that, while factual, they do not establish
the non- hazardous nature for this material:
(1) !i=.§L 2§E£-. of Healthx Education and Welfare
Toxic Substances List .U97J Edition^
A-45
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There are an estimated 15,000 separate sub-
stances included in this list of 25,043 items
which includes cross-referencing. Calcium
ZiiJ2£i^§ is not included in this comprehensive
ii§ting of toxic substances.
(2) California State Water Resources Control Board
~ ^W§£§! Quality Criteria^ .(January 1973
Reprint)
Under the heading "Calcium Fluoride" on
page 153 this document cites a report stating
"the oral LD50 for guinea pigs is more than
5.0 grams/kg of body weight" and "the lethal
dose required to kill the fish tinea vulgaris,
is reported to be 30,000 mg/1, which is
far greater than the solubility."
These toxicological levels for Calcium
Fluoride are quite similar to those reported
for various domestic animals and numerous
types of aquatic life in the section on sodium
chloride (pages 264 and 265) of the California
"Water Quality Criteria" Reference.
(3) In testimony submitted to the Illinois Pol-
lution Control Board during hearings held in
1973 and 1974 on a petition to increase that
state's effluent and water quality limitations
for fluoride (IPCB No. R73-15), Dr. William F.
Sigler (Dept. of Wildlife Science, Utah Uni-
versity) stated "in the presence of calcium,
magnesium or a number of other things, it
(fluoride) becomes substantially less toxic
(R135)." Dr. Leonard A. Knauss appeared before
The Board representing Olin Corporation as
their Manager of Environmental Hygiene and
Toxicology. Dr. Knauss testified, "If the
fluoride is taken into the body in the form of
a calcium fluoride solution, very little, if
any, of the fluoride will be deposited in the
bony tissue mainly because the bony tissue is
composed of a calcium based material and,
therefore, it probably would be excreted
almost exclusively as calcium fluoride."
(R 322).
Other testimony at the Illinois hearings noted
that sodium fluoride is far more soluble than
calcium fluoride and therefore fluoride
toxicity studies on aquatic life are almost
A-46
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invariably done using sodium fluoride, because
salciuQ} iluQEidg Simply. will nSfe Dissolve §£
£2ncentratioQ§ high enough to have any,
detectable gfj[gst; 2Q £bg sgecigs exposed.
Qi Environmental P
Owing to their origin in only certain types of
rocks and only in a few regions, fluorides in high
concentrations are not a common constituent of natural
surface waters, but they may occur in detrimental
concentrations in ground waters. s in general, water
containing less than 0.9-1.0 mg/liter of fluoride will
seldom cause molt led enamel in children, and for adults
concentrations less than 3-U mg/liter are not likely to
cause endemic cumulative fluorosis and skeletal
effects.9
Fluoride added to soil or water has little or no
effect on the fluoride content of plants grown in such
soil.3 The effects of fluorides in drinking water for
animals in analogous to those for humans. Fluoride ions
appear to have direct toxic properties toward aquatic
life, and in addition there seems to be a relationship
between the fluorides in water and the condition of the
teeth of the fish.
The recommended provisional limits for fluorine in
the atmosphere, in potable water and in marine habitats
are as follows*:
Contaminant provisional Limit
In_Air
Fluorine 0.001 ppm
Contaminant
in_ Water
Hydrogen fluoride
(as F2/H2O reaction
product) 0.10 ppm
D. Radioactive Properties: None
A-U7
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Lead and Its Comgounds
Properties
Elemental Lead (Pb)
Elemental lead (a.w. 207.19, d. 11.34, m.p.
327. 4°C, b.p. 17U4°C)2<> is a bluish-white, silvery, gray
metal.1 It is highly lustrous when freshly cut but
tarnishes upon exposure to air.1 Because of lead's
softness and malleability it can be easily melted, cast,
rolled and extruded.1 Lead is soluble in hot
concentrated nitric acid, in boiling concentrated
hydrochloric or sulfuric acid, and in acetic acid.
Lead is attacked by pure H2O and weak organic acids in
the presence of oxygen but is resistant to tap ft2Q,
hydrofluoric acid, brine and solvents.1
Lead Carbonate (PbCO3)
Lead carbonate (m.w. 267.20, d. 6.6, m.p. (dec)
315°C) 9 exists as white, pcwdery crystals which are
soluble in acids and alkalis, e.g. acetic acid or dilute
nitric acid with effervescence.1 Neutral lead carbonate
is insoluble in ammonia, alcohols and practically
insoluble in water (solubility at 20°C 0.0017 g/1) . •
Neutral lead carbonate is usually accompanied by the
impurity basic lead carbonate.
Basic Lead Carbonate (2PbCO3«Pb(OH) 2)
This lead carbonate (m.w. 775.60, d. 6.86,
m.p. (dec) UOO°C) * is a white amorphous powder which is
soluble in acids (especially nitric acid) , slightly sol-
uble in aqueous CO2 and insoluble in alcohols.* Basic
lead carbonate solubilizes to the extent of 1.1-1.7 mg
of PbCO3/l at 20<>C.9
Lead Sulfide (PbS)
Lead sulfide (m.w. 239.28, d. 7.13-7.7, m.p.
1 114°C,b.p. (subl) 1281°C) « occurs as the mineral galena
which exists as either silvery metallic crystals or a
black powder1 that is sparingly soluble in water (0.86
mg/1 at 18°C/102.8 mg/1 at 25°C) , alcohols and alkalies
but soluble in acids such as HNO3 and hot dilute HCl.
A-48
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j£§d Sulfate
Lead sulfate (mow. 303028, d. 6.12-6.39, m0p.
UTOOCJ19 is a white rhombic crystal with water
solubilities of 42.5 mg/1 (250C) 0 28 mg/1 (0°C) and
56 mg/1 (40°c)ee It is slightly soluble in concentrated
H2SOJJ but is insoluble in mogt acids. Lead sulfate is
soluble in ammonium salts.9
Lead Chr ornate (PbCrOjJ)
The yellow or orange crystals of lead chromate are
(m.Wo 323,22 „ d. 6o123r m.p. 844°CJ soluble in acids
(e.g. dilute HNO3J and solutions of fixed alkali
hydroxides but insoluble in acetic acid and ammonia.*
Lead chromate is one of the more insoluble lead salts -
one liter of water dissolving 0.2 mg» »
Lead Monoxide (PbO)
This compound Jm.w. 223.21 0 do 9.53 <, m.p. 888°C*
b.p. 1i*72°C)8* consists of a yellow to yellowish- red „
heavy a odorless powder or minute tetragonal crystalline
scales. i At 300-450°C in the air it is converted into
Pb3O4 but at higher temperatures it reverts back to
PbOo a Lead monoxide is insoluble in alcohol but is
soluble in acetic acid? dilute HNO3? ammonium chloride „
strontium chloride and in warm solutions of fixed alkali
hydroxides.* Its solubility in water is 17.0 mg/1. c
Lead Tetrxide
(JmoWo 685.63, d. 9.1? b0po(dec») 500°C)« is a
bright -red, heavy powder which is insoluble in water and
alcohol. & It is soluble ins hot HCl with the evolution
of C12? acetic acids; excess glacial acetic acid; dilute
nitric acid in the presence of H2O2. a Lead tetroxide is
an oxidising agent and therefore will react t-jith certain
reducing agents. ^
2L§§cJ Dioxide (PbO.2J
Lead dioxide (m.Wo 239.21^ d. 9.37S,, m.p0(decj
290°C)9 consists of dark brown hexagonal crystals3 which
evolve oxygen when heated „ first forming Pb3_pt* and at
high temperatures PbO. a This lead oxide is soluble in
glacial acetic acid,0 in dilute HCl with the evolution
of C12,a in dilute nitric acid in the presence of H2O2»J
in alkali iodine solutions with the liberation of iodine
and in oxalic acid or other reducer s.^ Lead dioxide is
..nsoluble in water and alcohol. It is an oxidizing
A-
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agent and hence, reacts with reducing material; it is a
dangerous fire risk in contact with organic materials.*
Lead Hydroxide (Pb(OH)2)
Lead hydroxide (m.w. 241.20, d., 7.592, m.p. (dec)
145°CJ * exists uj a white, bulky pov/der* which is
soluble in alkalis, nitric or acetic acid and fixed
alkali hydroxides. * Its solubility at pH 9 is 8.54 mg
Pb+*/l and at pH 7 is 150.0 mg Pb++/l, and as the pH
decreases further lead hydroxide's solubility increases
by more than an order of magnitude, 2® It absorbs CO2
from the air and decomposes at 14.5°C«*
iead Holy.bdate (pbMoO4)
PbMooa (m.w. 367.16, d. 692, m.p. 1060»1070°C) • is
a yellow powder which decomposes in concentrated H2SO4* 3
It is soluble in acids and KOH ami insoluble in water
and alcohol. It is noncombustible.
al Properties
The toxicity of the various .lead compounds appears
to depend upon:3
aj) . the solubility of the compound in the body
fluids;
bj. the fineness of the particles of the compound,
solubility being greater-: in proportion to the
fineness of the particles;
ctj . conditions upon which the compound ii3 being
used; where a lead compound i;:? used as a
powder, contamination Oi: the atmosphere will
be much less where the pcn/dex: is kept damp.
The solubility of some of the lead compounds in the
blood serum at 25°C in mg/liter are;2*
Pbo 115:>*0
Pb 570 ,,0
PbS04 43.7
PbC03 33.3
Lead is poisonous in all forms. It is one of the
most hazardous of the toxic metaln because the poison is
cumulative and toxic effects are many and severe.2 Of
the various lead compounds, the carbonate, monoxide and
sulfate are considered to be more toxic than elemental
lead or other lead compounds* The toxicity of lead
A-50
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chromate is less than would be expected, due to its low
solubility. All of the lead compounds are sufficiently
soluble in digestive juices to be considered toxic.2
In soft H2O, lead may be very toxic whereas in hard
H20 equivalent concentrations of lead are less toxic.
Calcium in a concentration of 50 mg/1 has destroyed the
toxic effect of 1.0 mg/1 of lead.3 Immunity to lead
cannot be acquired and sensitivity to lead seems to
increase with exposure.
Lead may enter the human system through inhalation,
ingestion or skin contact.6 Direct skin contact is of
negligible importance in connection with inorganic lead
compounds. However, in the case of organic lead
compounds, skin contact can be a real hazard. Indus-
trially, inhalation of dust, mist or fumes, is the chief
method by which lead and its inorganic compounds may
enter the body.6
Lead poisoning is rated as 10 times more liable to
occur from breathing lead dust than from swallowing
it.21 This is probably due to the fact that the liver
filters out swallowed substances like lead and removes
them from the blood before harm can be done. If they
are breathed, they are taken up by the blood stream,
pumped all over the body and thus make themselves felt
more readily than would otherwise be possible. Lead is
thought to be toxic only when present in the systemic
circulation. Thus it can be stored by the body and only
becomes a danger when it is returned to circulation in
greater amounts than the body can safely eliminate.21
Following ingestion of a large amount of any
insoluble lead salt (especially the acetate, carbonate
or chromate), the signs and symptoms are due largely to
local irritation of the alimentary tract.2 If absorption
is sufficient, pain, leg cramps, muscle weakness,
paresthesias, depression, coma, and death may follow
within 1 or 2 days. Three clinical syndromes are
recognized in the diagnosis of chronic plumbism:2
a). The alimentary type is characterized by
anorexia, a metallic taste, constipation and
severe abdominal cramps (lead colic due to
intestinal spasm)2;
b). The neuromuscular type is characteristic of
adult plumbism which consists of peripheral
neuritis limited to the extensor muscles.
Weakness or paralysis may occasionally be
A-51
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accompanied by arthralgia and myalgia, but
sensation is otherwise unaffected. AS
produced in laboratory animals a decrease in
motor nerve conduction velocity is associated
with segmental demyelination*2
c). The cerebral type of lead poisoning (lead
encephalopathy) is the most common type in
children fincephalopathy is a complication in
about 50$ of lead poisoning cases and the
mortality rate amontf patients developing
cerebral involvement is about 25fc.*
•The daily intake of lead in food/beverages is
approximately 043 mg which the human body is capable of
eliminating daily* However* if more lead is ingested
than excreted (0.3-1*0 mg/day)9 a condition exists which
is teferred to as "chronic lead poisoning", which may
develop within weeks or months** Many acute poisonings,
however, subside without sequelae, since the absorption
of lead from the bowel is inherently slow and
incomplete.« Presumably this outcome is also favoured by
vigorous treatment. As long as the body, however,
contains excessive amounts of lead fixed in the tissues,
symptomatic recurrences are an ever present threat. In
all recurrent episodes there is a characteristic rise in
the lead concentration of the body fluids and excreta.*
A lead content of blood greater than 0.005* and of urine
greater than 0.08 mg/1 support a diagnosis of lead
poisoning.*
Lead accumulates in bones, where it replaces
calcium.8 Bones store almost one half of the total body
pool, with long bones (arms and legs) accumulating about
3 times more than flat bones (breast bone, vertebrae)•
Becker and coworkers found Sppm lead in ancient bones
500 years old in comparison to 50 ppm which is present
in bones today. They implicated contemporary air
pollution as the primary cause of this increase.* With
advancing age, some of the metabolized lead accumulates
in soft tissues* Newly absorbed lead is retained in the
body as lead triphosphate, especially in liver, kidneys,
pancreas, and aorta.8
Plants growing on soils containing 1 ppm of lead
have shown 20-25 ppm lead per gram in their ash.
Samples taken from different portions of a plant vary
considerably in their lead content.8
A-52
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It is thought that inorganic lead salts in
irrigation water may be toxic to plants although toward
giant kelp, Macrocystis pyrifera^ lead was found to be
less toxic than Hg, Cu, Cr+*, Zn and Ni.s Lead nitrate
produced no deleterious effects on the rate of photo-
synthesis of kelp in sea H2O during a 4-day exposure at
4.1 mg Pb/liter.s
The toxicity of lead and some of its compounds
towards certain rodents is shown below:
Toxicological Responses of Rodents to Lead
and Lead Compounds
PbC03 (neutral) ipr-LDca: 124 mg/kg, guinea pig7
(basic) orl-MLD: 1.0 g/kg, guinea pig1
PbSO4 ipr-LD50: 300 mg/kg, guinea pig7
Pb (elemental) ipr-LDLg: 100 mg/kgr guinea pig7
Pbo ipr-LD50: 400 mg/kg, rat7
Pbo2 ipr-LDLo: 115 mg/kg, guinea pig7
C. Environmental Properties
The water quality standard for all lead compounds
is 0.05_mg/l as lead.* The solubilities of all lead com-
pounds discussed in this report fall above this
concentration: Pb(OH)2, 150 mg/1; PbO, 64 mg/1; PbSO4,
42 mg/1; PbC03 . Pb(OH)2, 1.1-1.7 mg/1; PbCO3, 1.7 mg/1;
PbCrO4, 0.1 mg/1, therefore surface disposal or
landfilling procedures must provide for adequate
protection of surface and ground waters. Disposal by
landfill techniques in a California Class I type
disposal site would be adequate providing a "California
type" climate exists; in other areas protection would
need to be more rigorous.
Under certain conditions lead is solubilized as
either the chloride or the sulfate which are both
slightly soluble and hence landfill disposal of lead is
not recommended under certain conditions.6 The
characteristics of water, soft or hard, that appear to
be conducive to plumbo-solvency, include comparative
absence of calcium and magnesium bicarbonates, low pH,
high dissolved oxygen, and high nitrate content.
A-53
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one of the problem* with heavy metal* is their
tendency to concentrate through both aquatic and
terrestrial food chains.*" Aquatic macro- and micro*
flora and fauna accumulate heavy metals such as lead in
body tissues in significantly greater concentrations
than present in the surrounding environment* These
organisms are the food source for fish and insects which
retain the heavy metals in the tissues of the consumed
organisms* the fish and insects are consumed in turn by
larger organisms, this process continues to the
organisms at the top of the pyramidal food chain, such
as man and large carnivorous birds and mammals* The
more links in the chain* the more severe the bioac cumu-
lation phenomenon*
For lead and its compounds, this bioac cumulative
phenomenon is less acute, lead accumulates in the bones
(and/or sxoskeleton) of animals in somewhat greater
proportions than in other tissues*8 since the bones and
exoskeleton of most larger animals are not consumed* the
lead contained therein is not available to top carni-
vores* Also lead compounds tend to interact with soil
^articles to form complexes which are not readily
available to plant uptake. Although plants do accumu-
late lead from soil and because lead is translocated
poorly* it tends to remain in the roots and return to
the soil when the plant dies. Leaves readily accumulate
air- borne lead compounds in the leaf tissue, and most of
the lead will still be in the leaves when they are con-
sumed by other organisms*
Properties! flgne
ManaaneBe fiiaxJL&s (Mn02)
&t PbvBical/qheniical Properties
Mno2 (m.w. 86.94, d* 5.026)« Is a black,
crystalline manganese salt4 which is insoluble in water*
nitric acid and sulfuric acid but is soluble in hydro-
chloric acid with the evolution of Cl£« * In the presence
of hydrogen peroxide or oxalic acid it dissolves in
dilute H2S04 or HttoJ.* Manganese dioxide is a strong
oxidizerT hence it should not be heated or rubbed with
organic matter or other oxidiaable substances, such as
sulfur, sulfides, phosphides, hypophosphites, etc.4
Manganese dioxide decomposes to Mn£0l and oxygen at
539«C. »
A-54
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Biological Properties
Manganese is essential for the nutrition of both
plants and animals, apparently as an enzyme activator.5
It is especially abundant in the reproductive parts of
plants, seeds being highest while woody sections contain
the least manganese. Nuts contain the highest
concentrations (22.7 mg/kg) and sea foods the lowest
(0.25 mg/kg). Manganese has been used to enrich soil,
yet in some concentrations it may be phytotoxic.5
Diets deficient in manganese result in impaired or
abnormal growth, symptoms of central nervous system dis-
turbance, anemia and possibly interference with repro-
ductive functions.e These conditions have been
associated with a low level of liver aldolase, an enzyme
involved in carbohydrate metabolism, and of bone
alkaline phosphatase activity, a condition that can be
rectified by administering manganese. The metabolism of
chlorine is linked with that of manganese; both decrease
liver fat in rats and birds.• The daily intake for a
normal human diet is about 10 mg. It is absorbed very
slightly and deposits mainly in the liver and kidneys.
Typically, human toxicity to manganese and its
salts is the result of chronic inhalation of the dust or
fumes.2 Manganese salts are poorly absorbed from the
alimentary tract, hence acute systemic intoxication does
not normally occur after ingestion. Systemic poisoning
may occur from chronic ingesticn or inhalation of
manganese or one of its salts, although the consensus is
that the only significant mode of entry is by inhalation
of dusts or fumes.2
The clinical symptoms of manganese intoxication
involve malfunctioning of the central nervous system,
probably by enzyme inhibition.* Warning and diagnosis is
complicated by an incubation period of 6-30 days prior
to the onset of symptoms. A controlled, clinical study
of Chilean miners suggests that a positive correlation
exists between nutritional deficiency and susceptibility
to manganism.*
In concentrations not causing unpleasant tastes,
manganese is regarded by most investigators to be of no
toxicological significance in drinking water.5 However,
some cases of manganese poisoning have been reported in
the literature. Excess manganese in the drinking water
is also believed to be the cause of a rare disease
endemic in Manchukuo. That manganese may be toxic is
also indicated by the reports that 0.5-6.0 grams of
A-55
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manganese pet kg of body weight administered daily to
rabbits has stunted growth and interfered with bone
development.*
Whereas acute intoxication involves the respiratory
system (manganese pneumonia, nose bleed, nasal conges-
tion J j chronic manganese poisoning affects the central
nervous system, mainly the midbrain between the
cetebellum and the cerebral cortex.0 The disease causes
disorders in mentation, disofientation* impairment of
memory and judgment, acute anxiety and even delusions.
Exposure to heavy concentrations of dusts or fumes for
as little as three months may produce chronic manganese
poisoning, but usually cases develop after 1-3 years
exposure.a The central nervous system is the chief site
of damage. If cases are removed from exposure shortly
after the appearance of symptoms, some improvement in
the patient's condition frequently occurs though there
may be some residual disturbances in gait and speech*
When well established, however, the disease results in
permanent disability.*
Plants apparently absorb manganese primarily in the
divalent state.1* Lowering the soil pti or reducing soil
aeration by flooding or compaction favors the reduction
of manganese to this form and thereby increases its
solubility and availability to plants. Heavy
fertilization of acid soils without liming (particularly
With materials containing chlorides, nitrates* or
sulfates) may also increase manganese solubility and
availability.
In moderately well-drained soils, manganese toxi-
city is generally found only if the soil pH is below
about 5.5, however, in flooded soils, the reducing
conditions produced can result in temporary toxic con-
centrations of divalent manganese at a pH approaching
7.0. This reduction process is favored by higher soil
temperatures. Manganese toxicity in plants is
characterized by marginal chlorosis and cupping at
youmj leaves and speckling of older leaves, which is
associated with localized manganese accumulations. Such
necrotic spots in barley leaves have been prevented by
adding soluble silicon to the nutrient solution,, The
beneficial effect of silicon was attributed to a
redistribution of manganese within the plant, rather
than to reduced manganese uptake. In severe cases of
manganese toxicity, plant roots turn brown, but this
A-56
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generally occurs only after the tops have been
noticeably injured. »•
Manganese toxicity can be reduced by increasing the
concentrations of other cations (calcium, zinc, copper,
and magnesium) that compete for absorption by plants in
the growth medium. In addition some elements appear to
interact with manganese inside the plant and thereby
affect its toxicity. Manganese toxicity has been
associated with iron deficiency in pineapple. The
addition of iron salts to the growth medium can reduce
manganese toxicity in tobacco, rice and clover.19
Environmental Properties
As a contaminant in water and soil the provisional
limit for manganese dioxide is 0.05 ppm. *
Like iron, manganese occurs in the divalent and
t rival en t form.9 The chlorides, nitrates and sulfates
are highly soluble in water; but the oxides, carbonates,
and hydroxides are only sparingly soluble. For this
reason, manganic or manganous ions are seldom present in
natural surface waters in concentrations above rl.O
mg/liter. In ground water subject to reducing
conditions, manganese can be leached from the soil and
occur in high concentrations. Manganese frequently
accompanies iron in such ground waters and in the
literature the two are often linked together.8
Manganese occurs in the atmosphere mainly as
manganese oxide, which interacts rapidly with other
pollutants, such as sulfur dioxide and nitrogen dioxide,
to form water-soluble manganese compounds.8
Marine organisms are capable of concentrating man-
ganese in their bodies to many times above the
concentration in seawater; manganese enrichment factors
for shellfish, compared with their marine environment,
range from 1,100 to 13,500; and for algae, as 60,000
(from 0.002 mg/kg in seawater to 120 mg/kg in the
algae) . Manganese concentration factors of up to
100,000 times an initial seawater concentration of 0.001
ppm for marine plants, and a manganese concentration
factor of up to 100 times for fish have been reported.19
similarly concentration factors for man and terrestrial
mammals are 3-4 and 10, respectively.19
A-57
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The availability of manganese to plants is affected
by numerous soil characteristics, including the
concentration of total or easily reducible manganese in
soil parent materials , concentrations of other cations
and total salts, pH, cations-exchange capacity, drainage,
organic matter content, temperature, compaction, and
mlcrobiai activity* Small changes or inherent
differences in these soil characteristics can determine
whether the Soil content of available manganese will be
deficient, adequate, or toxic for a given crop.4*
2*. EMioactive P£oBertiesi
fc4g.rgu.jy, gnd I£§ Cg
tal Me.rc.ury. (Hg)
Mercury (at*wt4 200.59, nup. -38.89<>c, b.p.
356. 9°C, v.p. 1mm at 126*2°C, d*<>4 13. 5939) « is a
silver-white, heavy, mobile, liquid metal which is
slightly volatile at ordinary temperatures1! with every
degree rise in temperature its volatility rises 10
percent. » It is insoluble in hydrochloric acid, water,
alcohol and ether but is soluble in sulfuric acid upon
boiling and readily soluble in nitric acid.* Mercury has
an extremely high surface tension engendering it with
Unique rheological behavior 4* This metal is converted by
heating with concentrated ti2j30i into mercurous or mer-
curic sulfate (depending on the excess of the acid at
the time of heating).4 When pure, mercury does not tar-
nish on exposure to air at ordinary temperature, but
when heated to near the boiling point, mercury slowly
Oxidizes to HgO. l
Mercuric chloride (tigC12)
Mercuric chloride (rtuW* 2t1.52» dk 3,4, nup. 2t7°C,
b.p. 302°C9) is a white aubstande which occurs as
crystals, granules, or powder*4 Hgcl2 volatilizes
Unchanged at about 300°C, it is slightly volatile at
25°C and appreciably so at 100ttd*4 its Solubility in
water is 69.0 g/liter at 20°C and U80 g/liter at 100<*C«J
the pH of a .2 molar aqueous Solution is 2.2.1 Hgcl2 is
amphoteric; therefore its solubility is increased by HCl
or alkali chlorides. HgC12 is soluble in alcohol (very
soluble in hot alcohol) , benzene* ether, glycerol and
acetic acid. 4
A-58
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Mercuric Oxide (HgO)
Mercuric oxide (m.w. 216.61, d. 11.14, m.p. (dec)
500°C») is soluble in water as follows: 53 mg/liter at
25°C, 395 mg/liter at 100°C.• It exists in two forms,
red and yellow.
Red mercuric oxide is a heavy, bright red or
orange-red, odorless, crystalline powder or scales, its
color is yellow when finely powdered. HgO (red)
decomposes into its elements when exposed to light* or
when heated to 500°C3. At 400°C it becomes dark red-
black but becomes red again upon cooling. Amphoteric
HgO (red) is soluble in dilute HCl or HNO3 and Solutions
of alkali cyanides or alkali iodides; it is slowly
soluble in alkali bromides, and insoluble in alcohol.*
Yellow mercuric oxide is an odorless, amorphous
yellow to orange-yellow powder* which turns red when
heated; the yellow color returns after cooling1 which
decomposes to its elements at 500°C.3 It is stable in
air but turns dark upon exposure to light.* Other
physical properties and solubilities are the same as
those of the red form, but the yellow form is more
reactive because the particles are more finely divided.1
Mercurous Sulfate (Hg2S04)
Mercurous sulfate (m.w. 497.24, d. 7.57) is a white
to yellow crystalline powder which decomposes when
heated* and becomes gray on exposure to light. *• Hg2SOj»
is soluble in nitric and sulfuric acids; its solubility
in water is 600 mg/liter at 25°C and 900 mg/liter at
100°C.»
Mercuric Sulfide (HgS)
Mercuric sulfide (m.w. 232.68, sp.gr. 8.06-8.12,
m.p.(sub) 583.5°C)9 precipitates out as a bright scar-
let-red powder or hexagonal red crystals which blacken
on exposure to light, particularly in the presence of
water or alkali hydroxides.1 When it is ignited in air
it decomposes into elemental Hg and sulfur, the latter
burning to SO2.J Mercuric sulfide is practically insol-
uble in water~(at 18°C, solubility is 1.25 x 10~s
g/liter) and alcohol but is soluble in aqua regia with
separation of sulfur in warm hydriodic acid with the
evolution of H2S. *•
A-59
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Ik
When heated With Na|C03» mercury salts yield me-
tallic Hg and are deduced to metal by H2o£ in the
presence of alkali Hydroxide.* Soluble ionized mercuric;
salts give & yellow precipitate of HoO with NaOH and a
ted precipitate df HgtjJ With alkali iodide.* Metcutous
salts give a black precipitate with alkali hydroxides
and a white precipitate of calomel with HCl of soluble
chlorides. They ate slowly decomposed by sunlight* i
Mercury is a cumulative protoplasmic poison) after
absorption it circulates in the blood and is stored in
the liver » kidneys 4 Spleen and bone. It is eliminated
in the urine, feees, sweat, saliva and milk* Adequate
evidence how exists to ascribe differences among various
forms of mercury poisoning to differences in the biolog-
ical distribution and excretion of the causitive agents
and their metabolites,* Respiratory exposure to mercury
vapor results in the retention of high initial concen-
trations in the lungs. A large proportion of this lung
burden is absorbed and gradually cleated. Transiently,
high concentrations are said to exist in the brain and
may be related to the high incidence of central nervous
System signs seen after this type of exposure. The kid-
neys, however, eventually accumulate the greatest pro-
portion of the total body burden.8
Mercury poisoning may be acute or chronic with the
latter being the more prevalent of the twa types* Symp-
toms and signs involving the central nervous system are
these most commonly sefen in chronic poisonings of
inorganic mercury, the principal features of which are
tremors and psychological disturbances.8 Intoxication
from mercury vapor or frbm absorption of mercuric salts
may be due, in both cases t to the action of the mercuric
ion. « Metallic merdUry vapor is able to diffuse much
more extensively into the blood cells and various
tissues than inorganic mercury salts, but once distri-
buted, most of it is oxidiated to the mercuric form. In
most cases of industrial exposure to mercurials, symp-
toms of mercury poisoning were observed only among wor-
kers who had been exposed ttt mercury levels above 100
micrograms/M3 ih air.*
A- 60
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Elemental Mercury
Metallic mercury constitutes a special case in the
toxicology of mercury compounds since dangerous symptoms
are recognized only after inhalation or prolonged skin
contact.2 In respiratory exposures, Hg vapor diffuses
through the alveolar membrane and reaches the brain
where it interferes with coordination; severe non-
productive cough and dyspnea sometimes precede symptoms
of systemic mercury poisoning.2 Inhalation of mercury in
concentrations of 1200-8500 micrograms/M3 in air results
in acute intoxication, affecting primarily the digestive
system and kidneys, and is characterized by a metallic
taste, nausea, abdominal pain, vomiting, diarrhea, head-
ache and sometimes albuminuria.* After a few days the
salivary glands swell, stomatitis and gingivitis
develop, and a dark line of mercuric sulfide forms on
the inflamed gums. Death as a result of extreme exhaus-
tion frequently occurs with poisoning of this degree of
severity.6
Inorganic Mercury
The action of inorganic mercury differs
considerably from that of organic methyl mercury.8
Inorganic mercury usually settles in and damages the
liver and kidneys, especially the kidney tubules (the
portion of the nephron involved in reabsorption of vital
agents from the urine). In the small intestines it ac-
counts for diarrhea. Mercury vapor diffuses readily
through the alveolar membrane and reaches the brain,
where it interferes with coordination.8
Organic Mercury
The discovery of the facile, biological conversion
of mercury and its compounds to methyl mercury have
brought into question the wisdom of any large scale use
of mercury and its inorganic and organic compounds.*
Organic mercury compounds may enter the body by in-
halation, skin absorption or ingestion.* There is evi-
dence that inhalation of organic mercury vapor and
aerosols may be more detrimental than the other means of
entry since absorption through the respiratory tract
leads to a higher rate of accumulation of mercury in the
brain.•
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The toxicoiogic effect^ of arganomeretlriais are
strongly influenced by the nature of the organic portion
of the molecule** Shott chain alkyl mercury compounds
(e.g. methyl and ethyl mercury) are relatively stable in
the body and may circulate for a long time unchanged in
the blood | methyl mercury has a biological half- life in
man of about 70 days. The stability of the alkyi mer-
curials, particularly methyl mercury* favors their aecu-
mulation in the body where they are found principally in
the brain. Thus, more than 98 percent of the mercury
found in the brain is in the form of methyl mercury.6
Aromatic mercury compounds, methoxyaikyi mercurials
and most other organic mercury compounds are degraded to
inorganic mercury in the body** Therefore, the physio-
logical and toxicologicai behavior of the nonalkyl or*
ganomercurials resembles that of Inorganic mercury com-
pounds, with preferential accumulation in the kidneys
and more rapid excretion than the short chain alkyl
analogs**
The symptomatology of acute and chronic poisoning
from methyl and ethyl mercury is similar! including
numbness and tingling of the lips or hands and feet,
ataxia, disturbances of speech, concentric constriction
of the visual fields, impairment of hearing, and emo-
tional disturbances** with severe intoxication the symp-
toms are irreversible* children born to mothers with
exposure to large amounts of methyl mercury exhibited
mental retardation and also cerebral palsy with convul-
sions. *
Because so few cases of toxicity have appeared from
phenyl marcurials exposure, even to high levels in air
over a period of years, it is apparent that these com-
pounds are low in toxicity relative to other forms of
mercury ** clinical and experimental evidence suggests
that a similar conclusion is applicable to methoxy ethyl
compounds.
oj Hg Compounds Cowards Aquatic & Terrestrial
Life
The lethal concentrations of mercury compounds for
Various aquatic organisms* are summarized as follows*
for mercuric chloride, the lethal concentrations in ppb
are: f^ £Ol,i (bacteria), 200? §chen£i§mus. sj^ (phyto-
plankton) , 30 j ^icrorggrria. SELs. (protozoa) , 150} Daphnia
tnagna (aooplankton) , 6 { {jgrinogammagug ffiariaus (amphi-
pod) , 100 1 Uglycglia oiara (f latworm) t 270t Bivalve lar-
A-62
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vae (Mollusca), 27; Stickleback (fish), 4-20; Guppy
(fish), 20; Eel (fish), 27; Rainbow trout (fish), 9200.*
The lethal dose of mercuric chloride for rats is 37
mg/kg body weight.7
%
For mercuric nitrate, the lethal concentrations in
ppb are: Guppy, 20; Stickleback, 20; Merjcierella enig-
matica (polychaete), 1000; Mesospheroma oregonesis (iso-
pod), 15. The lethal dose for mice is <* mg/kg body
weight.6
No toxicity data are available for Hg, HgSO4 or
mercuric diammonium chloride, as mercuric sulfate decom-
poses in cold water into *a yellow insoluble basic sul-
fate and free H2SO4, and both Hg and mercuric diammonium
chloride are insoluble in cold water. It is to be noted
however, that Hg and all inorganic Hg compounds dis-
charged into the aquatic environment could eventually be
biologically converted into the more toxic methyl Hg by
anerobic microorganisms, which can then be taken up by
living aquatic organisms.6
Environmental Properties
The O. S. Drinking Water Standards for Mercury 6
Compounds is summarized in the table below.
1 'cl ; U.S. Drinking Water Standards for Mercury23
Contaminant in H2Q and Soil Provisional Limits
Mercury 0.005 ppm
Mercuric Chloride 0.005 ppm as Hg
Mercuric Nitrate 0.005 ppm as Hg
Mercuric Sulfate 0.005 ppm as Hg
Mercuric Diammonium Chloride 0.005 ppm as Hg
Through the food chain mercury becomes more concen-
trated as it is taken up by its various links; mercury
penetrates the surface of plankton by passive absorp-
tion.8 In contrast, fish take up methyl mercury both
through consumption of food, mainly plankton, and
through their gills. Fish that breathe faster end eat
more than other species, such as the tuna, concentrate
more mercury in their bodies during their lifetime than
other fish. The older the fish, the greater is the mer-
cury concentration in its body. The metal accumulates
A-63
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ih it& body fate* A long ire tent ion time in some fiah ,
(mercury's half-life is 200 days) accounts for added
accumulation, feirds that eat fish concentrate even mote
mercury in their body* Whales and seals have been found
to contain very high levels of mercury.*
A terrestrial bioaccumulation of mercury also
occurs. Mercury is accumulated by growing plants, it is
absorbed through leaves and roots and is subsequently
transmitted to the remainder of the plant." Rodents and
ungulates accumulate mercury from the plants » and carni-
vores feeding on these animals accumulate even more mer-
cury. therefore, the organisms at the top of the food
chain tend to accumulate the greatest amounts of mer-
cury.
Pyop.ertie,si
Alcohoi
A*. £liy.5ical/Chem.lc.ai
Methanol (m.W. 32*04, hup* -97«8°C, b.p. 64.5°C,
flash point 12°C, d«o^ . 8100)» is a clear, colorless,
highly polar, mobile liquid.4 It has a slight alcoholic
odor when purej crude methanol may have a repulsive,
pungent odor* Methanol is flammablei it burns with a
non-luminous, bluish flame* The alcohol is miscible
with water, ethanol, ether, benzene, ketones and most
other organic solvents . Methanol forms azeotropes with
many compounds.4
•
Methyl alcohol Is readily absorbed from the gastro-
intestinal and respiratory tracts.2 Once absorbed
methanol is eliminated so slowly that it can be regarded
as A cumulative poison** It is detoxified in the body by
oxidation to formaldehyde and formic acid, both of which
are toxic. As little as two teaspoonfuls is considered
toxic if irtdested. * The fatal dose in matt lies between
2-8 02.; this range implies a high variation in
individual susceptibility.8 Death may be prompt, but it
is usually delayed for several days and the mortality
rate is high. The prognosis improves if treatment is
instituted before visual disturbances appear* * Though
A-6U
-------
single exposures to fumes may cause no harmful effect,
daily exposure may result in the accumulation of
sufficient methyl alcohol in the body to cause illness.
The symptoms of methyl alcohol poisoning result
from a combination of factors of which a characteristic
metabolic acidosis appears to be the trigger.2 central
nervous depression is due partly to this acidosis and
partly to cerebral edema. Acidosis is the result of
methanol oxidation to formic acid which accumulates and
reduces severely the body's alkali reserve. For unknown
reasons, other organic acids including lactic acid also
tend to accumulate. The severity of essentially all
symptoms in methanol poisoning is said to be
proportional to the intensity of this delayed acidosis.
Visual disturbances, which are the most distinctive
aspect of methanol poisoning in man, may become evident
soon after the severe phase begins. The ocular lesion,
which involves chiefly the ganglion cells of the retina,
is a destructive inflammation followed by atrophy. In
the acute phase the retina is congested and edematous,
and the edges of the optic disk may be blurred. The
result is bilateral blindness, which is usually per-
manent unless treatment is prompt and energetic. It is
generally agreed that metabolically formed formaldehyde
is responsible for the ocular lesions in methyl alcohol
poisoning. Since ocular damage has yet to be reported
in cases of formaldehyde poisoning, it would appear that
formaldehyde must be generated at the site of the lesion
to produce damage.
Ethyl alcohol, when consumed at the same time as
methanol, prolongs the latent period before toxic symp-
toms appear.2 It also has been observed that even severe
symptoms of methanol poisoning are alleviated by the
ingestion of ethanol; and for this reason the
recommended treatment includes ethanol in small
quantities. The mechanism of this protection lies in
the ability of ethyl alcohol to inhibit the metabolic
oxidation of methanol, even though this rate is
inherently slow. In rats, methanol oxidation requires
liver catalase which is inhibited by ethanol.
Although the distribution of methanol in the body
has been reported to parallel closely that of ethanol,
which in turn is distributed in proportion to the water
content of various tissues, some evidence indicates that
methanol may be re-excreted into the stomach over
periods of several days following ingestion.2
A-65
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Although for human consumption tttethanoi is very
toxic, and email amounts of it will lead to blindness
and 10 mls4 has caused deatht aquatic life has a greater
tolerance of this substance*9 Trout Withstand 10,000
fog/liter in tap water for two hours without apparent
inHUfVj but itt distilled water With 250 mg/iiter
goldfish died in 11-15 hours* The same effect was noted
with ethyl alcohol* Pot fingeriing trout in natural
waters, up to 8100 mg/liter of methyl alcohol had no
harmful effects in 2U houteu
al Properties
The water quality standard fot methanol is 13.0
mg/liter. *
Methanol can be biode^raded very rapidly by
unacclimated activated sludges and is very susceptible
to biological attack in lakes and streams. This is due
in part to the fact that methahol and most alcohols are
either naturally occurring or are normal components of
sewage. Thus the best method of disposal is via
municipal sewage treatment plants, provided the rate of
discharge is uniform**
(Ni)
Elemental nickel (at.no. 28, m.W. 58.71, d. 8.908,
m.p. 1453<»C, b.p. 2732°C, V.p. 1mm at 18100C)» is a
hard, lustrous, silver-grey ferromagnetic metal which
crystallizes in face-centered cubes.1 Its electrical
resistivity is 6. 844 microhms-cm at 20°C* * Nickel is
malleable and is readily fabricated by hot- and
cold-working.4 It is corrosion resistant at ordinary
temperatures, and burns in oxygen forming NiO. The
solubility of elemental nickel in pure water at 20°C is
12.7 mg/liter; *e it is Soluble in dilute nitric acid,
slightly soluble in hydrochloric and sulfuric acids, and
insoluble in ammonia and Strong alkalis.*
kel HyJr.Qxide (Ni (Ott)^*nH20)
A-66
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Nickelous hydroxide (m.w. 92.7, d.4.1, m.p.(dec)
230°C)9 is composed of light green crystals3 or is an
amorphous apple-green powder.1 When ignited in air at
about
-------
injury, myocardial weakness and central nervous
depression. Pulmonary effects are predominant after a
respiratory exposure to gaseous nickel earbonyl.*
Injestion of large doses of Ni» as a Mi compound
(1-3 mg/kg body weight), has been shown to cause
internal disorders, convulsions and asphyxia in doge**
Nickel dermatitis can be induced in humans through
contact with nickel-plated articles, industrial expo*
sures to nickelous dusts or baths or internal exposure
to nickel*4* the symptoms compose two levels! 1) a
simple dermatitis at the area of contact, the typical
"nickel itch'*, consisting of burning and itching of the
exposed skin. There is marked variation on individual
susceptibility to the dermatitis. It occurs more
frequently under conditions of high temperature and
humidity when the skin is moist, and chiefly affects the
hands and arms) and 2) a chronic eczematous reaction, in
which erythema occurs, and later nodules, which may
eventually form pustules, appear in the web of the
fingers and the forearm.**
In many green plants, degree of absorptions of Mi
by the roots appears to be dependent upon the soil pM.ie
Raising the pH of serpentine or high nickel solids by
the addition of lime usually somewhat alleviates the
toxic effects of nickel. The excessive absorption of
nickel is thought to reduce the cation exchange capacity
of roots in such diverse plants as oats, beans, peas,
sunflowers, and tomatoes.** Nickel is extremely toxic to
citrus plants.3 It is found in many soils in California,
generally in insoluble form but excessive acidification
of such soil may render the nickel compounds soluble,
causing severe injury or death of plants*8
QJI Environmental, £rop_ertieg
The provisional limit in water and Boil for nickel
and its compounds is 0.05 trig/liter.*
Little information concerning accumulation in org-
anisms, magnification in food vebs and mechanisms of
transport throughout the environment is available for
nickel and its compounds. The biomagnification pheno-
mena which involves moat heavy metals appears to be
effective for nickel as well, with the major exception
that plants are so sensitive to Ni that relatively
little is accumulated before its toxic effects result in
the death of the plant.
A-68
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§di°§c£iye £r.op.er>£iesj.
affl §03
A.. Physical/Chemjicajl Properties
Elemental, Niobium (Nb)
Niobium (a.w. 92.906, d. 8.57, m.p. 2468+10°C, b.p.
4927°C)» is a gray or silvery, ductile metal which does
not tarnish or oxidize at room temperature; it reacts
with oxygen and halogens only when heated.4 It is not
attacked by nitric acid up to 100°C, but vigorously
attacked by a mixture of nitric and hydrofluoric acids
and by aqua regia but it is attacked by alkaline
solutions to some extent at all temperatures.*
Niobium PentachlorJ.de (NbCIS)
Niobium pentachloride (m.w. 270.17* d. 2.75,
m.p. 204. 7°C, b.p. 254°C) » exists as a yellow, crystal-
line, deliquescent solid which decomposes in moist air
with the evolution of hydrogen chloride fumes.* This
niobium salt is soluble in alcohol, ether, carbon
tetrachloride and sulfuric acid.*
Niobium. Pentoxide (Nb2o5)
Niobium pentoxide (m.w. 265.81, d. 4.47,
m.p. 1460°C)» occurs as white, orthorhombic crystals
which are Insoluble in water but soluble in hydrogen
fluoride, fused potassium hydrogen sulfate, or
carbonates or hydroxides of the alkali metals.3
Niobium Pentoxide Hydrate (NblOS'xH^O)
This hydrated niobium salt is soluble in concentra-
ted H2S04, concentrated HCl, HP and alkalis; it is in-
soluble in NH3.9
BS. Biological Properties
There is to date little data available with regard
to the toxicity of niobium and its compounds towards
humans. The inhalation of niobium nitride has been
A-69
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reported to precipitate gradual reactive changes itt the
cells of the alveolar epithelium and connective tissues
of lymphatic tracts of the lunge. The presence of high
concentrations of the substance as dust in the air
causes a considerable cellular proliferation with the
development of pneumosci erotic foci 4 The maximum
permissable concentration of niobium hitiride in the air
is suggested to be set at a level of 10 mg/m*.a*
Limited animal experiments show high toxicity for
some salts of niobium* but low oral toxiclty for niobium
pentachioride. i Effects seen have been attributed to
ehfcyme inhibition.*
Properties;
£h.osfi|io|;us a.nc| l£s. Compounds
4 Profier.ties
Elemental £hosjgh.orUB
Elemental phosphorus (a.w. 30*979) exists in three
dllotropic forms i white, black and red.*
White lisilowl Bfcosfih.gsus. (m.p< 4U.1«C,
b.p* 280°C, d(solid, 20°C) 1*82,
d (liquid, 4U.5°c) 1.745) is & colorless or yellowish,
transparent* wax-like crystalline solid which darkens on
exposure to light. * This allotrope aulbimes in vacuo at
ordinary temperatures when exposed to light* When it is
exposed to air in the dark, it emits a greenish light
and gives off white fumes. Its solubility in water is
3*3333 mg/liter in absolute alcohol, 2500 tng/liter and
in absolute ether, 9800 mg/iiter. White phosphorus is
also soluble in chloroform (25,000 mg/liter) , benzene
(28,571 mg/liter, and is very soluble in carbon
disuifide (1.25 x 10» mg/iiter). one gram of
phosphorus dissolves in 80 ml. of olive oil, 60 ml. of
oil of turpentine, and about 100 ml. of almond oil. it
ignites at about 30°c in moist airi the ignition tem-
perature is higher when the air is dry. White
phosphorus combines directly with the halogens to form
tri- or pent a- halides; it combines With sulfur to form
sulfldes. This allotrope reacts with several metals to
A-70
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form phosphides and yields orthophosphoric acid when
treated with nitric acid. It reacts with alkali
hydroxides with the formation of phosphine and sodium
hypophosphite. »
Slack phosphorus (d. 2. 25-2. 69) » is a black
crystalline or amorphous solid resembling graphite in
texture. » It is produced from the white modification
under high pressures. It does not ignite spontaneously
as does the white allotrope. It is insoluble in organic
solvents. »
Red phosphoruft (d. 2.34, triple pt. at 589. 5°C,
sublimes at t16°C)9 a violet-red, amorphous or crystal-
line powder, is obtained from white phosphorus by
heating at 240°C with a catalyst.1 It has high
electrical resistivity; it is much less reactive than
white phosphorus . Red phosphorus properties are
intermediate between those of the white and black forms.
The red allotrope is insoluble in organic solvents and
only very slightly soluble in water1. It is soluble in
phosphorus tribromide and absolute alcohol. Red
phosphorus catches fire when heated in air to about
200°C and burns with the formation of the pentoxide. If
in contact with KC1O3, KMn04, peroxides and other
oxidizing agents, explosions may result. * ;
phosphorus Pentasulfide (P2S5)
Phosphorus pentasulfide (m.w. 222.29, d. 2.03,
m.p. 280°C, b.p. 523°C)9 is composed of light-yellow or
greenish- yellow deliquescent crystalline masses with an
odor similar to that of hydrogen sulfide. * P2S5 is
decomposed by water forming H3PO4, SO2 and H2S. 2 It is
soluble in carbon disulfide, in aqueous solutions of
alkali hydroxides*; its solubility in CS2 is 2200
mg/liter.9 In air it forms phosphorus pentoxide which
is a strong irritant.1
£h°§&h2£.U5 Sesquisulfide (Tetra phosphor us Trisulfide)
(PUS3)
PJIS3 (m.p. 172°C, b.p. U07.8°C, d. 2.0)« exists as
a yellowish- green crystalline mass which is soluble in
carbon disulfide but is insoluble in cold water* and is
decomposed by hot water, yielding H2S. l Its solubility
in carbon disulfide at 20 °c is about 60 percent (w/w) . *
Phosphorus sesquisulf ide is soluble in benzene V111.1
g30/iiter)« and similar hydrocarbons. Phosphorus
sesquisulfide is considered dangerous because when
A-71
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heated it emits highly toxic fumes of oxides of
phosphorus and sulfur.31
Properties
Phosphorus
Phosphorus is a general protoplasmic poison that
is slowly absorbed through the gastrointestinal and
respiratory mucosae.2 Its toxieity is enhanced when the
element is dissolved ih solvents such as alcohol or
perhaps digestible fats and oils like castor oil.
Liquid petroleum, however, retards absorption and
decreases phosphorus toxicity. Finely divided
particles and emulsions are more toxic than coarse
grained preparations, and bile salts are said to be
important for phosphorus absorption* perhaps because
of the water content and the low oxygen tension,
particles of elemental phosphorus are relatively stable
for long periods of time in the alimentary tract. The
free element, however, is thought to be the toxic form
in tissues, some phosphorous is thought to be slowly
oxidized to harmless acids, which are gradually excreted
by the kidneys.2
The acute fatal dose of phosphorus for an adult is
between 50-100 mg or approximately 1 mg/kg body weight.4
Recovery, however, has occurred after 0.8 and 1.5 grams*
The prognosis for phosphorus poisoning is generally
poor, and even in modern times the fatality rate is
about 50 percent. The classical picture of acute PJ4
poisoning develops in three stages* Gastrointestinal
symptoms occurring shortly after ingestion arise from
local irritation, but unlike the response to a truly
corrosive poison, the effects may not be immediately
evident and sometimes ate so mild as to escape
recognition. Vomiting is almost always present; early
hematemesis may reflect gastric erosion, whereas late
hematemesis usually Indicates a depression of plasma
prothrombin. Secondary to hepatic damage, "explosion of
smoke from the mouth'1 probably describes phosphorus
fumes, and vomltus and feces may be luminescent or
fuming, other symptoms in this period are secondary to
the gastroenteritis or impending vascular collapse. In
many cases stage two is a relatively symptom-free period
of several days. In the third stage of systemic
intoxication, gastrointestinal symptoms are severe. The
liver undergoes acute degeneration and fatty infil-
tration with accompanying metabolic disturbances.
A-72
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Hemorrhage may occur at many sites because of depletion
of clotting factors.2
Phosphorus may also act directly to inhibit
protein synthesis in the liver.2 Hypoglycemia is often
observed; its early appearance (stage 1) is a grave
prognostic sign, as is early azotenia, hepatomegaly or
toxic delirium.2
The long continued absorption of small amounts of
phosphorus can result in necrosis of the mandible,
commonly referred to as "phossy jaw".3 Long continual
absorption particularly through the lungs, and through
the gastrointestinal tract can cause a chronic poisoning
(the most common symptom of which is necrosis of the
jaw). It can also cause changes in the long bones, and
seriously affected bones may become brittle, leading to
spontaneous fractures. It is especially hazardous to
the eyes and can damage them severely. It also has
adverse effects on the teeth. The yellow form of
phosphorus when it comes into external contact with
the eyes, can cause conjunctivitis with a yellow tint.
If the material is inhaled, it can cause photophobia
with myosis, dilation of pupils, retinal hemorrhage,
congestion of the blood vessels and rarely an optic
neuritis.3
White phosphorus is highly toxic to fish. The 96
hour LC50's are less than 50 ppb for all fish studied,
and the incipient lethal level is probably less than 1
ppb for most fish. Phosphorus poisoning appears to be
accumulative and irreversible, though the cause of
mortality has not been determined. The most obvious
symptom of phossy water poisoning, other than death of
the victim, is the red color acquired by the belly and
head of certain fish, particularly herring. White
phosphorus can be expected to cause extensive tissue
damage wherever it accumulates. Tissues of the gills,
kidneys, liver and spleen may undergo substantial
disintegration. However, the symptoms of phosphorus
intoxication, including death, are not necessarily
related to tissue destruction.
Phgspjiorous Sesguisulfide
The toxicity of P]*S3 administered orally to rabbits
is 100 mg/kg.*
A-73
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pentagultide
Phosphorus pentasulfide is only a tnild irritant in
its pure solid stated it can cause alight akin
irritation upon contact and serious irritation to the
eyed and mucous membranes. The major hazard associated
with phosphorus pentasulfide is a result of the rapid
decomposition o£ i»Us.10 upon contact with moisture into
toxic and flammable hydrogen sulfide (H^B) and
phosphoric acid (H3PO4)» Phosphorus pentasulfide is
also extremely dangerous when heated- The fumes emitted
ate phosphorus pentoxlde which has a recommended TLV of
0.1 mg/m* of air, and the oxides of sulfur which are
also toxic (TLV of 5 ppm for B02). tn addition,
phosphorus pentasulfide has also been known to react
with acids and oxidizing agents to yield the same
products as the reaction with water.6
ta.3. Pr.pj2ery.es
The standard for phosphorus ift water and soil is
0.005 mg/liter as P, while the provisional limit for
phosphorus pentasulfide in soil or water is 0.05
mg/liter as P.*
Phosphorus does not occur free in nature, but is
found in the form of phosphates in several minerals and
it is a constituent of fertile soil, plants, and the
protoplasm, nervous tissue and bones of animal life.8 It
is an essential nutrient for plant and animal growth,
and like nitrogen it passes through cycles of decom-
position and photosynthesis. It combines directly with
oxygen, sulfur, hydrogen, the halides and many metals.*
Evidence indicates15 (a) that high phosphate con-
centrations are associated with eutrophication of waters
manifest in unpleasant algae or other aquatic plant
growths when other growth-promoting factors are
favorable; (b) that aquatic plant problems develop in
reservoirs or other standing waters at phosphate values
lower than those critical in flowing streams; (c) that
reservoirs and other standing waters will collect
phosphates from influent streams and store a portion of
these within the consolidated sediments} and (d) that
initial concentrations of phosphate that stimulate
noxious plant growths vary with other water quality
characteristics, producing such growths in one
geographical area but not in another.1*
A-74
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Critical phosphorus concentrations will vary with
other water quality characteristics.»* Turbidity and
other factors in many of the nation's waters negate the
algae-producing effects of high phosphorus
concentrations when waters are detained in a lake or
reservoir, the resultant phosphorus concentration is
reduced to some extent over that in influent streams by
precipitation or uptake by organisms and subsequent
deposition in fecal pellets or the bodies of dead
organisms. No recommendation can be made because of the
complexity of relationships between phosphate
concentrations in water, biological productivity and
resulting problems such as odor and filtration
difficulties.**
Although there .are no definite published reports on
the kinetics of oxidation of elemental phosphorus in
water, it appears that the rate is highly dependent on
the degree of dispersion.19 At concentrations (ca. 10
micrograms/liter) well below the accepted solubility
limit of 3 mg/liter with the dissolved oxygen content
unspecified, elemental phosphorus disappears by a first
order process with a half-life of 2 hours at about 10°C
0.85 hours at 30°C. At concentrations (50-100 mg/liter)
well above the solubility limit, with a dissolved oxygen
content of 6-7 mg/liter, the same reaction has:a
half-life of 80 hours at 30°C and 240 hours at 0°C. The
relatively small temperature effect combined with the
large inverse concentration effect is consistent with a
diffusion controlled process. The oxidation of
colloidal phosphorus in seawater is reported to be
measurably slower than in fresh water, suggesting that
the high salt content brings about agglomeration of the
phosphorus particles. Thus, rapidly moving fresh water
should lose elemental phosphorus faster than quiescent
seawater.15
white phosphorus is readily taken up by fish and
other aquatic organisms directly from the water.15 Fish
may also acquire lethal quantities of elemental phos-
phorous through the food chain, since the macroinver-
tebrates studied have a much higher tolerance for white
phosphorus than fish. The symptoms of phosphorus
intoxication are passed onto brook trout when they are
fed muscle tissue from phosphorus -poisoned cod.
Furthermore, elemental phosphorus can be passed on to
humans, since a considerable portion, 25 percent or
more, remains in the muscle of the fish after
processing, storage, and cooking.ls
A-75
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Elemental Bglgniujij (8e)
Selenium (a.w. 78.96)* exists in several allotrdpic
forms i amorphous, crystalline or red, and grey or
metallic;*! the amorphous form (d. 4.28) ranges front a
dark red to black powder which is soluble in cat bon
disulfide, methylene iodide; benzene or quinoline. Only
the red allotrope (m.p. 144°c, d. 1.42) has a sharp,
well-defined melting point; it boils at 685°C forming
dark red vapors.* The crystalline/red aiiotrope's dark
red translucent crystals are metastable and change into
the grey form on heating. The crystalline/red form is
soluble in dilute aqueous caustic alkali solutions, in
aqueous potassium cyanide solution and in potassium
sulfite solution* It burns in air with a bright blue
flame, forming the dioxide and emitting a characteristic
odor resembling rotten horse-radish. * The red form
combines directly with hydrogen and with the halogens
(excluding iodine) and is oxidized to selenious acid by
nitric acid and to selenic acid by sulfuric acid..* It
reduces hot aqueous solutions of silver and gold salts
with the formation of silver selenide and metallic gold,
respectively.1 The grey ot metallic form (m.p. 217°C,
d*°U U.81) is the most stable allotrope. * Its lustrous
grey to black hexagonal crystals are insoluble in water
and alcohol; very slightly soluble in carbon disUlfide
(20 tng/liter) and soluble in ether. *
in common with almost all metals, sufficiently fine
selenium powder may explode in ait to form the water
soluble selenium dioxide.* selenium will react with
acids to form the highly toxic H2Se gas.6
Ferrous Seienide (FeSe)
Ferrous selenide (m.w. 134.81, d. 6.78) is a black
mass with a metallic luster. 4 It is stable in air but
decomposes when heated in O2.4 It is practically
insoluble in water but is soluble in flcl with the
evolution of H2Se. *
A-76
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l Properties
Selenium dioxide readily dissolves in water pro-
ducing selenious acid.1* Intense local irritation and
inflammation of the skin and mucous membranes occur upon
contact. Selenium dioxide, selenious acid, and selenite
may be absorbed through the skin, resulting in internal
accumulation. Allergic dermatitis to selenium dioxide
may develop, especially in fairheaded people.1* Sodium
thiosulfate is used to treat exposure. Selenium
oxychloride is a severe vesicant, capable of producing a
third degree burn which is extremely painful and slow to
heal. Dimethyl selenide produces acute sore throat and
pneumonitis. 16
Surveys have shown that dental caries rates of
permanent teeth were significantly higher in seleni-
ferous areas than in non-seleniferous areas. There is
also a tendency for malocclusion and gingivitis in
seleniferous areas.5
Selenium is transmitted from the mother to the
fetus. Reduced reproductive rates and weakened
offspring occur in selenium-deficient mothers.
Excessive selenium may act as a teratogen. The majority
of the evidence indicates that selenium compounds can
function as anti-tumor agents rather than carcinogens. 16
Although elemental selenium has low systemic toxi-
city, dust or fumes can cause serious irritation of the
respiratory tract. Workers exposed to fine elemental
dust collect the dust in the upper nasal passages,
producing catarrh, nosebleeding, and loss of smell.16 A
few cases of selenium dermatitis have occurred.
Exposure to fumes of elemental selenium produces frontal
headache, intense irritation of the eyes and naso-
pharyngeal passages, slight difficulty in breathing, and
uvular edema. Exposed workers recovered within three
days and no ill effects persisted.
Selenium poisoning occurs naturally among cattle,
sheep, horses, pigs and even poultry in both chronic and
acute forms. 5 Chronic poisoning of the alkali disease
type results from the ingestion of food stuffs (corn,
wheat, barley, oats, grasses and hay) containing 10-30
ppm solution.18 The selenium is predominantly present in
the proteins of these feeds. The amount of selenium is
related to the availability of soil selenium. The
general symptoms of alkali disease include lack of
vitality, anemia, stiffness of joints, lameness,
roughened coat, loss of hair, and hoof lesions and
A-77
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deformities. Death may occur within two months after a
horse is placed in a seleniferous pasture. The heart
and liver exhibit the most damage - the heart becomes
soft, flabby and atrophied. Fibresis is evident in the
liver and kidneys.16
Minute concentrations of selenium appear not to be
harmful to fish during an exposure period of several
days; however, constant exposure to traces of selenium
has caused disturbances of appetite and equilibrium,
pathological changes, and even deaths of fish after
several weeks.5 concentrations considered safe for human
beings over a period of weeks have been toxic to fish.
Environmental Properties
The drinking water quality standard for selenium
and its compounds is 0.01 mg/liter as Se.*
Selenium may enter animals in several ways. The
predominant route is through ingestion of vegetation
containing high levels of selenium. Animals readily
absorb inorganic and organic selenium through the small
intestine. Monogastric absorption is more efficient
than ruminant. 70-80 percent of the selenium is quickly
excreted in the urine, breath, perspiration, and bile.
The remaining selenium becomes bound or incorporated
into the blood and tissue proteins and is only slowly
eliminated. Carnivores obtain selenium by eating prey
fed on seleniferous forage. Selenium in drinking water
is another source. Small amounts of selenium may be
inhaled, as animals, plants, and microorganisms all
produce volatile selenium compounds.16
Soil selenium enters the food chain by plant accu-
mulation. In seleniferous soils, certain species of
plants prevail which easily accumulate selenium levels
toxic to livestock. In fact, the presence of certain
plant species is steadfast evidence of a seleniferous
zone, crop plants grown on such soils, if they them-
selves survive, may also contain selenium levels
poisonous to livestock.16
Plants vary in their ability to absorb seleniumj
the final selenium concentration in the plant will be
determined by such factors as the species and age of the
plant, che season of the year and the concentration of
soluble selenium compounds in the root zone.3 Cereals
and grains concentrate selenium from the soil, the
amount depending on the chemical condition of the
A-78
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selenium, the type of crop, and the sulfate content of
the soil. High sulfates diminish the uptake of sele-
nium. Plants have been injured by selenium in the soil,
however, injury to plants can be reduced or prevented by
sulfate ion, when it is present in a concentration about
12 times as high as that of selenium.9
The selenium in young soils occurs predominantly in
an inorganic form not utilizable by crop plants.1*
Selenium accumulator plants and some bacteria can func-
tion as selenium converters, removing the selenium from
the soil and returning it in an inorganic form, which
can be absorbed by other plants. The established
biological valence transformations of selenium are
reduction reactions. Selenate, and selenite can be
converted to elementary selenium and selenoorganics by
plants and microorganisms. Evidence for microbial
oxidation of selenium is the lack of buildup of organic
selenium compounds in nonsterile soils. However, the
oxidative stages in the selenium cycle may be abiotic,
as about 80 percent of elementary selenium as dust in
moist air is converted to selenium dioxide, which reacts
with water to form selenious acid. Selenite is the most
unstable form of selenium, and may be readily oxidized
to selenate.16
Organic selenium and some selenium salts are easily
leached from soils, and the selenium content of irri-
gation waters, springs, and shallow pools may be quite
high in seleniferous regions.16 In alkaline soils, much
of the selenium may be trapped by reaction with iron
oxides. Iron selenium compounds are quite insoluble
under basic conditions, and the selenium available to
indicator plants and microoorganisms, but not crop
plants. Acidification of the soil by microbe action can
cause the conversion of insoluble inorganic selenium to
soluble forms.16
Dt Radioactive Properties; None
Silver and Its Compounds
A-79
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fti. EJteif.al/Shejnical Properties
Silver (Ag)
Silver (a.w. 107.87, m.p* 960. 5°C, b*p. 2212°C, d.
10*5) * Is a soft, ductile and malleable, lustrous white
solid* with a face-centered cubic structure. * It resists
oxidation, but tarnishes in air through reaction with
atmospheric sulfur compounds (sulfur and HS) and ozone.4
Ag is the best conductor of heat and electricity and is
more malleable and ductile than any other metal except
gold. This metal is insoluble in water and in most
acids; readily soluble in dilute nitric acid, KCN, in
hot concentrated sulfuric acid; it is superficially
attacked by ticl« * In the presence of air or oxygen,
silver solubilizes in fused alkali hydroxides and alkali
cyanides.1 Most silver salts are photosensitive.1
Silver Cijl2rid.e (Agclj
Silver chloride (m.w. 143*32, d« 5.56, m.p* 455°C,
b.p. 1550°c) is a white powder with cubic crystals which
exists in nature as the mineral cerargyrite. it is
soluble in ammonium hydroxide, sodium thiosulfate
potassium cyanide', concentrated sulfuric acid,
potassium bromide^, concentrated hydrochloric acid,
ammonium chloride, mercuric nitrate and Silver nitrate4}
its solubility in water is *89 mg/liter at 10°C«, 2
mg/liter at 25°C4 and 21 mg/liter at 100°c»{ it is
insoluble in alcohol and dilute acids4* AgCl darkens
upon exposure to light and finally turns black, it
exists in several modifications differing in conduct
toward light and in solubility in various solvents.
AgCl can be melted, cast and fabricated like a metal.3
er Nitrate (AgNO3) CiH«l (3>c4>
Silver nitrate (m.w* 169.87, d, c and 9520 at 190°c; the resulting pH of a
saturated aqueous solution of AgN03 is about 6.
A-80
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Silver Oxide (Ag^O)
Silver oxide (m.w. 231.74, d. 7.143, m.p.(dec)
300°C) is a heavy, odorless, brown-black cubic powder
with a metallic taste which breaks up into its
constituents upon exposure to sunlight; moist Ag20
absorbs carbon dioxide. It is soluble in potassium
cyanide solution, ammonium hydroxide, acids e.g. dilute
nitric acid, and sodium thiosulfate solution; it is
virtually insoluble in alcohol. The solubility of Ag£O
in water is 13 mg/liter at 20°C and 53 mg/liter at 80°c.
Its solubility is pH dependent. As pH decreases
solubility increases such that below pH 5, Ag2_O is
freely soluble. As pH increases above pH 7 solubility
decreases to pH 12, the pH at which Ag2,0 is least
soluble (.92 mg/liter). Above pH 12 solubility
increases.
Silver Hydroxide (AgOH)
Almost no information is available on the
properties of silver hydroxide. Because of its high
solubility in water and the preferential formation of
Ag2O (discussed previously), it is virtually non-
existent.
B. Biological Properties
Although the essentially insoluble chloride, bro-
mide, iodide, and oxide of silver are generally
non-irritating and relatively benign, some silver salts
have been found to be irritating to skin and mucous
membranes.* The ingestion of corrosive silver nitrate
(AgNOJ) has been responsible for most cases of acute
silver poisoning. The symptoms are those of a severe
gastroenteritis and shock, with vertigo, coma, con-
vulsions, and death.2 Chronic exposure to silver salts
may cause argyrism, solely of cosmetic concern.2
Argyrism is characterized by a greyish-blue discol-
oration of the skin.
Silver poisoning is treated like acute copper poi-
soning, except that gastric lavage should be performed
with sodium chloride solutions.2 Apparently BAL has not
received a therapeutic trial in acute poisoning. In
cases of argyria (result of chronic exposure to silver),
BAL has been found not to increase the excretion of
silver.2
A-81
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Environmental proper, ties
The water quality standard for silver and its com-
pounds is 0*05 tng/iiter as Ag. *
from silver ores (Aggs, AgCl, fete*) silver ions
be leached into ground waters and surface waters* but
since many silver salts such as the chloride * BUlfide,
phosphate and arsenate are insoluble* siivefc ions cannot
be expected to occur in significant Concent ration in
natural waters.9
£§£lioaictive Siogertiesx Jtone
m Sulfa^e (SrS04)
al^Shefflisalj frrgjjerties
Strontium suifate (m.w« 183. 63* m.J?. 1605°C,
d* 3.96)* is a white, odorless* crystalline powder which
is appreciably soluble in alkali chloride solutions. *
ltd solubility in water at 17.4°c is 114.3 mg/liter J at
32,3°C is 114.3 mg/liter, and at 2.5°C is
113.3 mg/liter. strontium suifate^ solubility in 2
percent hydrogen chloride solutions is 1250.0 mg/liter,
and 1430.0 mg/liter in 8 percent nitric acid solutions.
It is insoluble in alcohol and dilute sulfuric acid.*
BA Biological Properties
Strontium is present in plant and animal tissues in
trace concentrations, but it occurs in much higher con-
centrations in bone structures.8 There is ho evidence
that strontium is essential for plant nutrition, but
there are indications that it is necessary for the
growth of animals and especially for calcif icatioh of
bones and teeth, in human a the strontium content of
bones has been given as 120-234 mg/kg in contrast with a
tissue concentration of less than 0.1 mg/kg. Toxicolog-
ically, no evidence has been Uncovered to show that non-
radioactive strontium salts taken orally by mart or
animals produces deleterious action*9 Its toxicity is
probably on the same order of magnitude as calcium since
the strontium ion is chemically and biologically similar
to it. The oxides and hydroxides of strontium are
moderately caustic materials. As with other compounds,
the toxicity may be a function of the aniort*
A-82
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The toxicities of a few strontium compounds towards
rodents are summarized below.
Toxicological Responses of Rodents to
Strontium compounds7
IVN rat LD2J): 123 mg/kg
IVN mouse LD50: 148 mg/kg
BrF2: IVN rat LD20: 625 mg/kg
SrBr2: ipr rat LD50: 1000 mg/kg
IVN rat LD50: 1000 mg/kg
With the advent of nuclear fission and weapons
testing, strontium came to the forefront of publicity as
one of the inevitable constituents of fall-out. » Owing
to its long half-life and its tendency to accumulate in
bone structure, Sr-90 is ranked second only to Ra-226 as
a hazard to human health.
£i EnvironmentaJ. Properties
There are no water quality standards except that
for dissolved solids, 250 mg/liter.
From studies utilizing radioactively labelled
strontium, it was discovered that crop plants tend to
accumulate strontium from soils and water.9 Plants do
not appear to discriminate between calcium and strontium
in soil moisture and hence the ratio of these two
elements in plant tissue tends to be the same as their
ratio in the soil solution. The uptake of strontium by
plants can be reduced by adding calcium to the soil or
applied water.s
Measurements of the uptake of strontium by aquatic
macrophytes during 7 days exposure in hard river water
containing strontium9 showed concentration factors
varying from 30 to 74 for six species.5 In soft water,
however, watercress had a concentration factor of 200
after 28 days in contrast to 55 in hard water. Other
experiments showed concentration factors for watercress
in the order of 600 to 800 in soft water (20 mg/liter of
CaCO3) and less than 100 in hard water (300 mg/liter of
CaCO3). The increase in calcium and magnesium ions
appears to militate against the uptake of strontium.
For Porphvra^ sp.. an edible seaweed in South Wales, the
concentration factor was only 0.05-0.3.9
A-83
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Planktonic algae have also been Shown to cOhOen-*
trate strontium.3 concentration factors fot algae have
been reported at Values ranging from 8 to 3060. Pot
marine bacteria* a concentration factor of about 100
been given.
strontium concentrates in the flesh* bones* and
scales of rudd fish by factors of 2.6* 71 and 209
respectively.5 For lobsters, concentration factors of
300 in the shell, and 2.0 in the flesh Were reported*8
The probable accumulation factor for goldfish (the Whole
fish) is 150.s
It is evident that the major hazard to humans of
strontium and radiostrontium (leached from soils and
Water contaminated with fallout from nuclear explosions
or waste products from nuclear reactors) lies not in
direct consumption but in plants and fish that accumu-
late this element.9
ELi BMioactive Properties; None
Sulfur Dioxide (SO2)
4*. PhYjjdcal/Chemical Properties
Sulfur dioxide (m.w« 6C is 228»0 g/iitet and at 90PC
is 5.8 g/liter.* 302 is also soluble ih chloroform*
ether, acetic acid and
Si2i23i£Si Properties
sulfur dioxide is a highly irritant gas Which ifl
often cited as a dangerous atmospheric constituent in
smog areas*2 Inhalation produces all grades of
respiratory tract irritation* sometimes with pulmonary
edema. The vapor concentration probably determines the
mode of death, for example* Suffocation from reflex
-------
respiratory arreat (very high concentration), pulmonary
edema (moderate concentration), or systemic acidosis
(low concentration).2 There is some indication of
individual susceptibility.
The gas is dangerous to the eyes, as it causes
irritation and inflammation of the conjunctiva.3 in
moist air or fog, it combines with water to form
sulfurous acid, but it is only very slowly oxidized to
sulfuric acid. Concentrations of 6-12 ppm cause
immediate irritation of the nose and throat, while 0.3-1
ppm can be detected by the average individual possibly
by taste rather than by the sense of smell. 3 ppm has
an easily noticeable odor and 20 ppm is the least amount
which is irritating to the eyes. 10,000 ppm is an
irritant to moist areas of the skin within a few minutes
of exposure.3
Sulfur dioxide chiefly affects the upper
respiratory tract and the bronchi.3 It may cause edema
of the lungs or glottis, and can produce respiratory
paralysis. More than 90 percent of the inhaled gas is
absorbed in the airways above the larynx. The degree of
irritation of sulfur dioxide, sulfuric acid, and
sulfates to the respiratory tract is dependent largely
on their concentration in the atmosphere and the size of
the particles. The size that causes most irritation to
the respiratory •tract is about 1 micron in diameter or
slightly less; but even larger sulfuric acid particles,
which do not reach the lower airways, induce
constriction of bronchi associated with severe coughing
as the result of reflex action.
An important feature of the biologic behavior of
sulfur oxides is their interaction with other
pollutants.B Aerosols of soluble salts of iron,
manganese or vanadium in concentrations of 0.7 mg/m3 to
1 mg/m3 induce a three-fold increase in airway
resistance in experimental animals. These substances
form droplets in the humid respiratory tract and thus
permit solution of sulfur dioxide. Furthermore they are
catalytic agents for the oxidation of sulfur dioxide to
sulfuric acid. Sulfuric acid mist at 8 mg/m3 combined
with 89 ppm of sulfur dioxide produced greater injury to
lungs, greater alterations in respiration, and greater
retardation of growth than either one alone.
The combination of sulfur dioxide with hydrogen
peroxide (H2O2) at concentrations of 0.29 mg/m3 for five
minutes, with particle size of 4.7 microns, induced a
synergistic effect.8 However, when hydrogen peroxide was
A-85
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associated with the game concentration of sulfur dioxide
but of reduced particle sisse (11*8 microns)* no
potentiating effect occurred.
inhalation of sulfur dioxide together with
particles of sodium chloride (0.04 micron^ in diameter)
accounted for greater airway resistance than inhalation
of sulfur dioxide alone.* However, no such synergism
occurred when the size of Nad particles was increased
to 2.5 microns at the same concentrations.
the interaction of particulatee With sulfur dioxide
in animals is a highly complex process and does not
always parallel that in humans.8 Experiments with normal
human volunteers have failed to demonstrate consistent
potentiation of the response to sulfur dioxide by sodium
chloride particles.8
Concentrations of less than 1 ppm of sulfur dioxide
are believed to be injurious to plant foliage.3 Sulfur
oxides tend to dry up the plant* which then assumes A
light ivory or tan color* fl The injury to leaves
originates and concentrates between their veins. Often
the veins themselves begin to bleachout. Grasses, Which
have two layers of palisade cells, collapse throughout
the thickness of their blade* on evergreens t sulfur
oxides induce a reddish discoloration either at the tips
of the needles or as a band over their entire lengths
subsequently the dead tissue shrivels Up* fiulfuric
acid, which is formed in the atmosphere by sulfur oxides
(303) in the presence of moisture, produces Small
necrotic (dead) areas simulating burns* They are
surrounded by a black ring With its edges slightly
erased.
£JL gnvironmen.tal Properties
In domestic water, sulfur dioxide and sulfites are
deleterious primarily in that they lower the pH Value
ahd increase corrosivity.s By being oxidized and
utilizing dissolved oxygen, on the other hand, sulfites
may retard corrosion.
The recommended ACGlH's threshold timit Value for
sulfur dioxide is 5 ppm in air (13 mg/m3 air) and 0.65
nig/liter in soil and water.* About 80 percent of all
sulfates constitute particles below two microns in
diameter.8 These particles suspended in the atmosphere
account for reduction of visibility, a characteristic
feature of sulfur oxide pollution.
A-86
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Bi Radioactive Properties; Hone
Vanadium Compounds
A.. Chemical/Physica^ Properties
Vanadium Pentoxide (V2O5)
Vanadium pentoxide (m.w. 161.88, d. 3.357)' is a
yellow to red orthorhombic crystalline powder with a
melting point of 690°C and which decomposes at approxi-
mately 1750°C.* This salt of vanadium is soluble in con-
centrated acids and alkalis, forming vanadates1; its
solubility in cold water is 8 g/liter.« It is insoluble
in alcohol.1 Its acid solutions are reduced by S02,
Zn + HCl, and by evaporation with HCl. ~
Vanadium Dichlorije (VC12)
Vanadium dichloride (m.w. 121.85, d. 3.23,
m.p. (subl)e910°C)« is comprised of apple-green*
deliquescent hexagonal plates.3 It is soluble in alcohol
and ether and decomposes in hot water.4 ;
Vanadium Trichloride (VC13)
Vanadium trichloride (m.w. 157.30, d. 3.00,
m.p. (dec) <*25°c)» is a mass of pink deliquescent crystals
which are soluble in absolute alcohol and ether and
which decompose upon heating and in water.4
Vanadium Tetrachloride (VC1U)
Vanadium tetrachloride (m.w. 192.75, d. 1.816,
m.p. -28 + 2°C, b.p. 1U8.5°C)» is a reddish brown liquid
which is soluble in absolute alcohol and ether.4 It de-
composes slowly to vanadium trichloride and chlorine
below 630°c.4 It is nonflammable.4 It is soluble in and
decomposes in water; it is also soluble in absolute al-
cohol, ether, acetic acid and chloroform.9
Vanadium Tetroxide (V2O4)
This blue-black powder (m.w. 165.88, d. U.339)« is
derived from V2O5 by oxalic acid reduction or carbon re-
A-87
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Vanadium tetroxide in eolubli itt Heidi and al«
aii8,« it is least *oliible in water at pH 5 (25«C) with
ft solubility of 1,11 it 10-* g VWiiteti at pH 9 (
Vanadium tetrdkide's saturation eonainttatiort itf 9*09
salts of vanadium way have valences of 2» I* 4 and
§4 The tetra- and pehta- vsieht salt* ate generally
Boluble* but the ttrlvalent naiti of fluoride, akidei and
ate insoluble. »
considering the tact that doaea o£ vanadium ate ra-
pidly exdreted in tha urini and the f(eaes» and that com-
plete olearance of the vanadium from the animal usually
occurs two to three we eke after vanadium administration
has ceased - it appears that the tonic effects of vana-
dium are primarily exhibited when exposed to it aa
duet,
to Vanadium ffentoxide in amounts greater
than the inhalation tolerance (dust) o,S, (fume) 0.1
mg/m* air generally will induce signs and symptoms of
vanadium poisoning which include pallor* greenish- black
dia color at ion of the tongue* paroxysmal cough, conjunc-
tivitis, dyspnea and pain in the chest, bronchitis and
radiographid reticulation. • the symptoms of exposure to
Vanadium-laden dusts are generally acute and relief oc-
curs promptly when the irritant is removed* A greenish-
black tongue with septic teeth and lingual furring is
indicative of vanadium- expo sure but not necessarily
poisoning* The green color is believed to be due to the
deposition of quadrivalent vanadium in the tongue and
gums, systemic poisoning due to over exposure to vana-
dium dusts can occur, when this happens vanadium alters
human metabolism in the following waysi*
It inhibits the synthesis of cholesterol* of phos-
pholipids, and of other lipids. cholesterol , a pre-
cursor of the all important adrenocorticai hormones*
affects a great number of metabolic processes* especial**
ly the metabolism of salt, water, minerals and carbohy-
drates . a
A-88
-------
It inhibits the formation of cystine, cysteine, and
methionine, the three basic sulfur-containing consti-
tuents of skin, hair, and nails. Methionine has a
sulfur-bound methyl group that enters into the produc-
tion of adrenalin, choline and creatine."
It interferes with the utilization of iron in the
synthesis of hemoglobin. Vanadium also leads to accumu-
lation of serotonin, a crystalline protein and powerful
constrictor of blood vessels found chiefly in brain
tissue and in the blood."
Vanadium chlorides
The toxicity of vanadium chlorides administered
orally to a rat are as follows:7
VC12 LD50 = 540 mg/kg body weight
VC13 LD50 =350 mg/kg body weight
VC1U LD50 =160 mg/kg body weight
Vanadium Compounds
The toxicity of vanadium compounds is principally a
function of the rate of administration or exposure.»*
Vanadium salts are considered highly toxic in a number
of species when given by intravenous or subcutaneous in-
jection. Since most vanadium compounds are poorly ab-
sorbed from the gastrointestinal tract, they exhibit a
low order of toxicity by the oral route. Most of the
orally ingested vanadium is excreted in the feces. Ele-
vated urinary vanadium levels reflect vanadium exposure,
and systemic vanadium is rapidly eliminated from the
body by the kidneys.
Anionic vanadium is said to be more toxic than
cationic.2 Humans have tolerated 150 mg of vanadium so-
dium tartrate intramuscularly, and 1-8 mg sodium met-
avanadate by mouth.2 Dimercaprol (BAL) exerts no ap-
parent therapeutic benefit in vanadium-poisoning, but
calcium disodium edetate and disodium catechol disulfo-
nate are both effective antidotes in animals.2
Researchers have found that aerial parts of plants
have the lowest vanadium content with the roots having
nearly the same content as the soil in which the plant
was growing. Though the total supply of trace elements
in the soil has a definite bearing on the amount found
A-89
-------
in the corn plant* the factors which influence the
availability of the elements (pH, mineral form, solubil-
ity) ate more important in determining plant uptake*
Plants take up vanadium through the roots especially at
acidic ptt*g«*» Toxic amounta can be accumulated if in-
sufficient iron is present. Borne plants such a* Cleomeja
fififii. appear to be vanadium-accumulatorB.»«
Microbial action play it a strong role in determining
the availability of vanadium in the soil4 the bi-, tri-
and pentavalent states of vanadium make it amenable to
mierobial attack* Specific autotrophic bacteria oxidiie
the reduced forms of vanadium to obtain a part or all of
their energy for growth and multiplication. tron-
oxidifcing bacteria okidize vanadium in acidic leaching
solutions* The oxidieed vanadium is more soluble in
aqueous solutions and, therefore* capable of transport
in ground water. Sulfate-reducing bacteria clay an im-
portant role in developing the reducing conditions under
which the various bacteria operate. Vanadium promotes
nitrogen assimilation by soil microorganisms*
Marine plants and invertebrate animals generally,
seem to contain vanadium in higher concentrations than
terrestrial plants, insects and vertebrates} there exist
both marine and terrestrial organisms which tend to ac-
cumulate vanadium. Among the marine organisms which do
are the tunicates*** Apparently they can concentrate
vanadium from sea water with their pharyngeal mucous
sheath. Vanadium serves as the metallic element in the
tunicate blood* existing oomplexed to pyrrole rings in a
structure similar to bile salts.**
Vanadium forms the vanadyl cation (Vo) the salts of
which are soluble, it also forma the anion vanadate
(Vo4) . tt is likely, therefore* that any vanadium salts
occurring in waste water will remain in solution. » time
treatment of vanadate would probably produce caHVOU.2tt^o
whose solubility is below that of the corresponding
phosphate.
The proposed drinking water standard for vanadium
is 5.0 tng/iiter. * The 08HA standard for exposure to
vanadium dust and/or fumes is 0*05 mg/m*»A
Radioactive Ptopertieai Nqne
A-90
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AS. Phvsical/Cheinica^ Properties
Elemental lieg (Zn)
Zinc (a.w. 65.37, m.p. 419. 4°C, b.p. 907°C,
d. 7.14)9 ia a hexagonal crystalline, lustrous,
bluish-white metal which is stable in dry air and
becomes covered with a white coating of basic carbonate
on exposure to moist air. Pure zinc is very slowly
attacked by dilute sulfuric or hydrochloric acid; the
presence of a small amount of another metal e.g. copper,
tin, lead, accelerates the action of the acids. This
metal is slowly soluble in acetic acid and ammonia
water; soluble in nitric acid and readily soluble in
solutions of fixed alkali hydroxide with the evolution
of hydrogen. * zinc foil will ignite in the presence of
moisture.
Zinc Chloride (ZnCl2)
Zinc chloride (m.w. 136.29, d. 2.907, m.p. 290°C,
b.p. 732°C3) is a deliquescent white granular powder
composed of cubic crystals, granules, fused pieces or
rods. It is extremely soluble in water (4320.0 g/liter
at 25°C, 6150.0 g/liter at 100°C») in dilute
concentrations some zinc oxychloride (Zn2oci2) is
formed.1 The pH of a concentrated solution of zinc
chloride is approximately 4.O.1 ZnClJ is very soluble in
dilute hydrochloric acid, alcohol, glycerol and
acetone. »
Zinc Hydroxide (Zn(OH)2)
Zinc hydroxide (m.w. 99.38, d. 3.053, m.p. (dec)
125°C) is a colorless, rhombic powder which is soluble
in acids and alkalis, forming zinc salts and zincates
(HZnO2-; ZnO2— ) The water solubility of this amphoteric
compound varies with pH; it is least soluble at pH 9.2
(1.04 mg/liter) . Solubility increases as pH increases
or decreases from 9.2; at pH 7 its solubility is about 2
g/liter; at pH 5 its solubility is about 1000 g/liter.9
Zinc Yellow
Zinc yellow is toxic by ingestion.* Toxicological
properties are due to both zinc and chromium. The
A-91
-------
toKieelogieai jsropertifcB due tb chromium are discussed
under "chromium and its CdtnpoundB" ih this section*
1400 BuiSfi (ZMO)
Bihtt oxide (m,w. 81,38, d, 9,at, m.p. W3«C)« is a
coarse white of grayish* odorless* bitter-tasting powder
which absorbs carbon dioxide Irom the ait** it ia only
slightly soluble in water (1*6 tog/lite* at 29"C)« but is
readily soluble in dilute acetic of mineral acids* in
ammonia, ammonium carbonate and fitted alkali hydroxide
solutions.*
feinc yellow (m.w. about 3*00) 10 an odorless»
yellow or greenish yellow fine powder Which is Slightly
soluble in water^ and soluble in dilute acide, e.g.
acetic acid.i
Zinc i& not inherently a tokic element to man, how-
ever, when heated, it evolves a fume of «lnc oxide
which, when inhaled freeh, can cause a disease known as
"brass founders' ague" Of ''brass chills*"91 It is
possible for people to become immune to it* However,
this immunity can be broken by cessation of exposure of
only a few days* zinc oxide dust has also been known to
block the ducts of the sebaceous glands and give rise to
a popular pustular eczema in men engaged in packing this
compound in barrels.3 Zinc oxide dust which is not
freshly formed is virtually innocuous, there is no
cumulative effect to the inhalation of ainc fumes.
fatalities, however, have resulted from lund damage
caused by the inhalation of high concentrations of zinc
chloride futnea.a
Soluble salts of Bind have a harsh metallic tastei
small doses can cause nausea and vomiting, while larger
doses cause violent vomiting and purging** So far as can
be determined, the continued administration of zinc
salts in small doses has no effect in man except those
of disordered digestion and constipation* Another local
manifestation of zinc salts is their caustic effect on
the skin leading to ulcerations.*
A-92
-------
Exposure to zinc chloride fumes can cause damage to
the mucous membrane of the nasopharynx and respiratory
tract and give rise to a pale grey cyanosis.' Chloride,
because of its caustic action, can also cause ulceration
of the fingers, hands and forearms of those who use it
as a flux in soldering. This condition has even been
observed in men who handle railway ties which have been
impregnated with this material. It is the opinion of
some who work with it that it is carcinogenic.0
The particle size of zinc oxide and zinc chloride
is largely responsible for the type and degree of res-
piratory symptoms and for their differing toxic
effects.*
It is towards fish and aquatic organisms that zinc
exhibits its greatest toxicity.8 In soft water, concen-
trations of zinc ranging from 0.1-1.0 mg/liter have been
reported to be lethal, but calcium is antagonistic
toward such toxicity. Zinc is thought to exert its
toxic action by forming insoluble compounds with the
mucous that covers the gills, by damage to the gill
epithelium, or possibly as an internal poison. The
sensitivity of fish to zinc varies with species, age and
condition of the fish, as well as with the physical and
chemical characteristics of the water. Some acclimati-
zation to the presence of zinc is possible, and
survivors from batches of fish subjected to dissolved
zinc have been less susceptible to additional toxic
concentrations than fish not previously exposed. It has
also been observed that the effects of zinc poisoning
may not become apparent immediately, so that fish
removed from zinc-contaminated to zinc-free water (after
4-6 hours of exposure to zinc) may die 48 hours later.9
The presence of copper appears to have a syner-
gistic effect on the toxicity of zinc.5 There is little
toxic action of zinc precipitated from solution in
alkaline water, almost all of the toxicity is attri-
butable to the zinc remaining in solution.3 They also
showed that the toxicity of zinc sales to sticklebacks
in soft water is reduced by the addition of calcium
carbonate; hence the calcium ion rather than the car-
bonate ion appears to be the antagonistic factor.5
The toxicity of zinc salts is increased at lower
concentrations of dissolved oxygen in about the same
proportion as for lead, copper and phenols, e.g. the
lethal concentration at 60 percent saturation of
dissolved oxygen is only about 0.85 that at 100 percent
saturation.5
A-93
-------
hag a toidd effect tottatds pirotdBaa and bac-
teria* but not neatly as pronounced ae copper," As
little aa 0.1 mg/iitetf of aims will have an effect upon
biochemical oxygen demand and 82 • 8 mg/ liter zinc will
eauee a 90 percent drop in the 5-day BObi in
concentrations up to 1.0 mg/liter zinc is reported to
stimulate nitrification, but 10 mg/litiar is inhibitory.
In very email amount e, aino hag been reported to be dan-
ger oU a for oysters and in large amounts to impart a
blue-green color. Toward emails » toxic action by einc
has been reported at 1*0 mg/liter in natural water and
ae low as 0.05-0*10 mg/iiter in distilled
Mo estimates of the acute oral tokieity of zinc
oxide were located, and it is assumed that no human
fatalities have resulted from ingest ion of the pure
oxide. Because zinc okide is soluble in dilute mineral
acids (presumably including gastric juice) , it probably
shares to a limited extent the toxic actions of
water-soluble "ainc salts. «•
Freshly formed fumes of 2inc oxide , as from
welding, may cause metal fume fever with chills, fever,
tightness in the chest* cough and leUkocytosiSt*
g%g>perti,es
Many fcinc salts (e.g. Kinc suifate and *inc
chloride) ate highly soluble in water | hence it is to be
expected that zinc might occur in many industrial
wastes 4» on the other hand, zinc salte such as the
carbonate, oxide and sulfide, are insoluble in water and
consequently it is to be expected that some zinc will
precipitate and be removed Readily in most natural
waters.9
one of the problems with heavy metals ie their ten-
dency to concentrate through both aquatic and terres*
trial food chains. 2 2 Aquatic macro* and micro- flora and
fauna accumulate heavy metals such as cine in body
tissues in significantly greater concentrations than
present in the surrounding environment. These organisms
are the food source for fish and insects which retain
the zinc in the tissues of the consumed organisms, the
fish and insects are consumed in turn by larger
organisms} this process continues to the organisms at
the top of the pyramidal food chain, such as man and
large carnivorous birds and mammals. The more links in
-------
the chain, the more severe the bioaccumulation phenom-
enon.
The drinking water quality standard for zinc is 5.0
mg/liter.*
Bi Radioactive Properties; None
Zirconium Chloride
A.. Chemical/Physical Properties
Zirconvl Chloride (ZrOC12)
ZrOCl2 in contact with water produces octahydrate,
zrOd2.8H2O, tetragonal crystals.» Zirconyl chloride is
freely soluble in water and alcohol.1 Aqueous solutions
behave like solutions of polymers (tetramers) of hy-
drated ZrOOH+ and chloride ions. The pH is about equal
to that of HCl of the same molarity.» Aqueous ZrOC12
solutions have considerable solvent action on sparingly
soluble sulfates, such as calcium sulfate, due to re-
moval of sulfate ion from the solution by complexing
with the zirconium atom.1 The free acid in ZrOC12 solu-
tions may be neutralized, and a solid compound,
ZrooHd.nH2o can be recovered. It is highly polymerized
in solution and amorphous in the solid state.1 This com-
pound is mildly acidic and has been used in the prepara-
tion of body deodorants and antiperspirant prepara-
tions.1
The octahydrate, ZrOCl2«8H20, loses 6H2O at 150°C
and 8H20 at 210°C.*
B.. Biological Properties
So far as is known, the inherent toxicity of zir-
conium compounds is relatively low. Animal studies
indicate neither acute nor systemic injury in response
to zirconium compounds given orally for as long as two
years.5 Even 20 percent zirconium oxide in the diet was
not harmful. The LD50 values for oral administration of
zirconium salts to rats, expressed as zirconium, to
range from 853 mg/kg of body weight for the nitrate to
2290 mg/kg for sodium zirconyl sulfate.8 Deaths in
rabbits have been caused by zirconium through intra-
A-95
-------
venoue injections of relatively large dogea on the order
of 1&0 ffltf/kg body ' 4* -
Moat of! the ttircohium eompottndb in common uae
and considered td be ihetti* pulmonary granu-
loitia Iri JlireoniUttt workers has betert reported and aodiutti
eirconiurti ia«t^e hae been held tee|3t»rieible fot akin
Although Bircotiium ehlotidc, nitrate and aulfatea
are salable in Hao* the earbonate^ hydroxide * oxide* and
silicate are highly insoluble. & AH a consequence, any
dlBsolved Kireonium that reaches natural waters Mill be
precipitated quickly and retnoved by adsorption or eed-
itnentation.*
££0fifi£tie.si
1. Stecheri P.G,, ed. *he Merck Xndek* Rahway, Merck and
, 1963. 8th edition*
2. Q lea eon, M«» K.E. Ooaeelin, H.C. Hodge, B.P. Smith.
CiiUicai ^oi{iQ3ifiiy fl| CSffliSUjifti j&odj&tgj. Baltim
The wIlliamB and MilKittfl co«» 1969. 3rd edition.
a ax, Ntl» fegnjgrojg Sroc^tieg pj
Mew Yoirk, Van tiostrand Reinhold company, 1966*
a. Hawley, d,(3. Shfi Condensed Cbej»jcal Dictionary. Mew
York* Vah Noettand Re in ho id company, 19T1. 5th edition.
9. McKee, Y«SI., M.W« Woil| edSi Water Quality criteria.
Resources Agency of California State Water Quality
Control Board, 1963. 2nd edition.
6. Recommended Methods of Seduction. Neutralization,
kecovery or Disposal of Hazardous Waste. Vols t, tf,
VI, V1I1, X, XII, Xtlt. TRW Systems Group. Re don do
Beach, California, 1913.
A-96
-------
7. Christensen, H.E., ed. Toxic Substances List, 1973
Edition. U.S. Department of H.E.W. (National Institute
for Occupational Safety and Health)„ Rockville, MD?
1973.
8. Waldbott, G.L. Health Effects of Environmental
Pollutan^-Ji St. Louis, C. V. Mosby Company, 1973.
9- Handbook of Chemistry and Physics, 52nd edition.
Cleveland, The Chemical Rubber Company/ 1971-72.
10. Fluorides. Washington, D. C., National Academy of
Sciences, 1971.
11. Asbestos^ The Need for and Feasibility of Air Pollution
Controls. Washington, D. C., National Academy of
Sciences, 1971.
12. Chromium. Washington, D. Caf National Academy of
Sciences, 1974.
13. Buchanan, W.D. Toxicjty of Arsenic Compounds„ New
York, Elsevier Publishing Company, 1962,
14. Water Quality Criteria. Washington* D= C,f National
Academy of Sciences and National Academy of Engineering,
1972,
15. Burrows, D., J.C. Dacre. Mammalian Toxicology; and
Toxicity to Aguatic Organisms of White Phosghorus and
UPhossy. Water±n Nashville,, Associated Water and Air
Resources Engineers, Inc.e 1973»
o
16. Preliminary Investigation of Effects on the Environment
of Bpron^ Indium, Nickelj. Selenium^ TinA V§S§
-------
20. Dean, J.A., ed. tangej.s Handbook of Chgmistry^ JQth ed.,
New Ygrkx McGraw-Hill igpk £gmeaayjL 1973..
21. Jacobs, M.B. The AnalyticaJ. Toxj.coj.Qqy of Industrial
|jD2£2aQic Poisons^ New York, Interacience Publishers,
1967."
22. Odum, E. P. Fundamentals of Ecology., Philadelphia, W.B.
saunders company, 1971. 3rd edition.
23. Public Health Service Drinking Water Standards.. Public
Health Service (U.sT Dept. of H7E.*w7) , 1?62.
24. Kosova, L.V. and A. A. Yarosheva. "Action of Niobium
Nitride on Animal organisms'*.
25. Linke, William, ed. Solubilities of Inorganic and
Metalorganic Compounds. 4th ed. 1958.
A-98
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APPENDIX B
Private Waste Contractors and
Service Organizations
Large_multi^site_integrated hazardgus_waste contractors
Rollins Environmental Services,
P. O. Box 23U9 Inc.
Wilmington, DE 19899
Browning-Ferris Industries, Ind.
300 Fannin Bank Bldg.
Houston, TX 77002
waste Management, Inc.
900 Jorie Boulevard
Oak Brook, IL 60521
SGA Services, Inc.
99 High Street
Boston, MA 02109
Integrated multi-treatment
complexes and disposal ser-
vices; 3 sites.
Integrated national treat-
ment and disposal facili-
ties; about 100 sites -
mostly landfill but including
5 chemical fixation stations.
Integrated national treat-
ment and disposal facili-
ties; about 50 sites -
mostly landfill.
Integrated national treat-
ment and disposal facilities;
about 50 sites -. mostly land-
fill, but with waste treat-
ment subsidiaries.
B. Hazardous waste treatment and recovery contractors
Chem-trol Pollution Services,
P. O. Box 200 Inc.
Model City, NY 1U107
Hyon Waste Treatment Services
Chicago, IL 60607
Chemical Control Corp.
Elizabeth, NJ 07207
Conservation Chemical Co.
P. O. Box 6066
Gary, IN U6406
Liquid treatment and
secured landfill dis-
posal.
Integrated waste treatment
facility - biological, chem-
ical incineration.
Liquid and solid chemical
processing and incineration.
Treatment and disposal of
liquid and hazardous wastes„
B-1
-------
conservation chemical co.
P. 0. Box 6304
Kansas City, MO 64126
Industrial Waste Disposal Co.,
Dayton, oh 45401 Inc.
Nelson chemical Co.
12315 Behaefer Highway
Detroit, Ml U8227
Evor Phillips Leasing Co.
Old Bridge, NcT 08851
Erievtay Pollution Control* Inc.
33 industry Drive
Cleveland, ott UU101
Industrial Tank, Inc.
210 Berrellesa Street
P. o» Box 831
Martinez, CA 9U553
Bio-Ecology Systems, inc.
4100 1!. Jefferson Avenue
Grand Prairie, TX 73050
Systems Technology
Franklin, oH U5005
Enviroiunental Waste control,
26705 Michigan Avenue Inc.
inkster, Ml U81U1
Western Processing Co.
Kent, WA 98031
Pollution Controls, inc.
P* 0. Box 238
Shacopea, MM 35379
Pollution Abatement Wastes
Oswego, NY 13126
Treatment and disposal of
liquid and hazardous wastes.
Treatment and disposal
plant.
Wet chemical treatment of
cyanides, chrome, plating
solutions and similar wastes
amenable to this approach.
Industrial liquid transpor-
tation and treatment -
ocean disposal.
industrial waste treatment
and chemical fixation.
Liquid transporting, treat-
ment, and disposal} class 1
hazardous waste disposal
sites, state of CA.
Liquid treatment of metal
processing wastes (plating
etc) chemicals, acids,
incineration.
Hazardous waste treatments.
Liquid treatment of acids,
alkalies, pickle liquor.
Contractor for chemical
reclamation.
incineration and liquid
waste treatment.
industrial waste disposal)
landfill and incineration.
B-2
-------
Aztec Mercury
P. O. Box 1676
Alvin, TX 7,7511
Wood Ridge Chemical Corp.
Division of Troy Chemical Co,
Park Place East
Wood Ridge, NJ
SGC Industries
Old Bridge, NJ 08857
Renner, Inc.
Box 3224
Port Arthur, TX 776UO
Environmental Sciences, Inc.
Chemfix Division
505 McNeil ly Road
Pittsburgh, PA 15226
Mercury recovery from in-
dustrial wastes.
Reprocessors of mercury
wastes.
Chemical fixation processes.
Landfilling and chemical
fixation*
Chemical fixation on-site and
off-site mobile treatment
Units.
C. General^purpose landfill cgQtractors_and .services
Koski Construction Co.
5841 Woodman Avenue
Ashtabula, OH UUOOU
Knickerbocker Landfill
Malvern, PA 19355
Potts town Disposal Services
Pottstown, PA~ 19U64
Scientific Inc.
17 E. Second Street
Scotch Plains, NJ 07076
Sanitas Waste Disposal of MI
15500 Schaeffer Road
Detroit, MI
Tork Construction
Wisconsin Rapids, WS
Impervious base settling
pond.
Lined landfill.
Lined landfill.
Landfill operators accepting
liquids.
Contractor for disposal in
commercial landfill*
Contractor for disposal in
private landfill.
B-3
-------
G ene ra 1 jurgos e_§e£ureO§Ldf iii_SSQtracto£B_aad^Be£vi ces
Nuclear Engineering Co* t inc.
Hutatbourne Park
9200 Shelby Road
Louisville, KY
Wescon» Irtc«
P. o. Box 564
245 Third Avenue E.
Twin falls, IA 83301
Industrial Hazardous Waste
Land Disposal Site
Route 2
Lindsay, OK 74052
Resource Recovery Corp*
Pasco, WA 99301
Chemical Processors, Inc.
5501 Airport Way South
Seattle, WA 98100
County Sanitation Districts
of Los Angeles county
2020 W. Beverly Boulevard
Los Angeles, CA 90057
Ventura Regional County
Sanitation District
181 S. Ash Street
Ventura, CA 93001
Wescon, Inc.
P. O. Box 564
21*5 Third Ave., E.
Twin Falls, IA 83301
Primarily nuclear waste dis-
posal} hazardous container-
ized waste burial plus some
liquid chemical treatment?
3 sites*
Hazardous wastes secured
disposal.
Hazardous materials land-
fill.
Interrelated companies -
liquid. Sludge and solid
hazardous chemical dis-
posal by evaporation plus
secured landfill.
See above
Municipal Class I disposal
sites; State of CA*
Municipal class I dis-
posal site - State of CA.
Hazardous waste disposal;
abandoned missile base.
B-4
-------
E- Peep Welling Contractors
Sonics International
P. 0. Box 47088
Dallas, TX 75247
U.S. Pollution Control, Inc.
5024 S. Quaker
Tulsa, OK 74101
Deep welling of acids and
other chemicals.
Contractor for disposal
of hazardous industrial
wastes deep well and land-
fill.
F. Ocean^Disposal Contractors
Modern Transportation
Kearney, NJ 07032
Safety Products and Engineering
3 Maiden Street
W. Quincy, MA 02169
Ocean disposal.
Ocean disposal hazardous
waste.
G• solid Waste Consultants
Chemical Buyers Service, Inc.
P. O. Box 2065
Berkeley, CA 97400
International Hydronics
Princeton, NJ 08540
Emcon Associates
326 Commercial Street
San Jose, CA 95112
Chemical recycling contrac-
tors.
Consulting process engineers
for waste treatment facil-
ities.
Environmental consultants -
landfill geology and design.
H• Miscellaneous^Seryices
Quality Septic Tank Service
A & B Quality Drain Service
Capital Heights, MD 20027
Contee Sand & Gravel Co., Inc.
Box 460
Laurel, MD 20810
Contractors for waste sludge
hauling.
Land disposal.
B-5
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Appendix C
Cost Conversion Indices
Costs for treatment and disposal reported herein were based
on mid-1973 pricing. Table C-1 presents applicable indices
(or estimates) for converting to December 1973 dollars.
Based on this table, we estimate the average cost increase
to be approximately +H% between the two dates. The price
increase for particular cost elements (i.e. land, labor,
energy, etc.) may be applied individually for those
treatment/disposal situations in which the total is
particularly influenced by an element which varies
significantly from the H% average. In light of the goal of
± 25% accuracy for most cost estimates, we do not believe
such corrections to be significant.
C-1
-------
Table C-1
Comparison of Costs, June, 1973 and Dec.. 1973
Ihdex _
Element Source JBi_13 Dc^TS Change
Construe- CE Plant 144.5 148.2 . +2.6%
tion Cost Index
Boeckh Index 155.3 157.7 + 1.0%
(Commercial & •
Factory Bldga.)
Eguiement M&S Equipment 342.9* 349.5** +1.9%
Cost
Wholesale Price
Index (BLS)
Gas Fuels 128.0 137.6 + 7.5%
Electric Power 128.4 135.9 +5.8%
Petroleum Prod.,
Refined 146.6 252.0 + 71.9%
Labor Hourly Earnings
Current Labor
Statistics, (BLS)
Contract 6.35 6.70 + 5.5%
Construction
Chemicals & Allied 4.46 4.60 + 3.1%
Products
Transpor- No applicable + 5-10%
tation index found (est.)
Land Telecon; ——• + 5%
~ Soc. of Ind. (est)
Realtors
*2nd Quarter «73 **4th Quarter «73
U01207
C-2
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