oEPA
United States
Environmental Protection
Agency
Industrial Environmental Research
Laboratory
Cincinnati OH 45268
EPA-600/2-79-2101
December 1979
Research and Development
Status
Assessment of
Toxic Chemicals
600279210!
Mercury
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution-sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/2-79-2101
December 1979
STATUS ASSESSMENT OF TOXIC CHEMICALS:
MERCURY
by
D. R. Tierney
T. R. Blackwood
Monsanto Research Corporation
Dayton, Ohio 45407
and
T. M. Briggs
PEDCo-Environmental, Inc.
Cincinnati, Ohio 45246
Contract No. 68-03-2550
Project Officer
David L. Becker
Industrial Pollution Control Division
Industrial Environmental Research Laboratory
Cincinnati, Ohio 45268
INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
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DISCLAIMER
This report has been reviewed by the Industrial Environmental
Research Laboratory - Cincinnati, U.S. Environmental Protection
Agency, and approved for publication. Approval does not signify
that the contents necessarily reflect the views and policies of
the U.S. Environmental Protection Agency, nor does mention of
trade names or commercial products constitute endorsement or
recommendation for use.
11
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FOREWORD
When energy and material resources are extracted, processed,
converted, and used, the related pollutional impacts on our
environment and even on our health often require that new and
increasingly more efficient pollution control methods be used.
The Industrial Environmental Research Laboratory - Cincinnati
(lERL-Ci) assists in developing and demonstrating new and im-
proved methodologies that will meet these needs both efficiently
and economically.
This report contains a status assessment of the air emis-
sions, water pollution, health effects, and environmental signi-
ficance of benzene. This study was conducted to provide a
better understanding of the distribution and characteristics of
this pollutant. Further information on this subject may be
obtained from the Organic Chemicals and Products Branch,
Industrial Pollution Control Division.
Status assessment reports are used by lERL-Ci to communicate
the readily available information on selected substances to
government, industry, and persons having specific needs and
interests. These reports are based primarily on data from open
literature sources, including government reports. They are indi-
cative rather than exhaustive.
David G. Stephan
Director
Industrial Environmental Research Laboratory
Cincinnati
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ABSTRACT
This report provides information on mercury, its sources and use,
environmental significance, health effects, control technology,
and regulatory action in progress. Approximately 1,900 metric
tons/yr of mercury are available annually for domestic use.
Sources of mercury include domestic ore smelting, secondary
metal recovery, and imports. An estimated total of 1,525 metric
tons/yr of mercury were lost to the environment in 1971 from
mining and smelting of metals, manufacturing operations, fuel
combustion, and use of industrial and consumer goods.
Mercury and many of its compounds are highly toxic; consequently,
control technology has been implemented in the form of mist
eliminators, wet scrubbers, direct and indirect condensers, and
absorbers. Wastewaters containing mercury have been treated by
sulfide precipitation, while sludges have been roasted under
high temperature to remove mercury. Most control technology
effectiveness is unknown.
Mercury has been designated as a priority pollutant for study
under the Federal Water Pollution Control Act. Ocean dumping of
mercury is prohibited except in trace amounts; the Food and Drug
Administration has established a limit for mercury in edible fish
of 0.5 mg/kg. Mercury ore refining and chloralkali plants are
regulated to 2.3 kg of mercury emission for a 24 hr period.
Further studies are needed to determine the population which may
be affected by mercury pollution. The efficiencies and cost of
control technology should be ascertained if human health hazards
caused by mercury exposure are to be avoided in an effective and
economic manner.
This report was submitted in partial fulfillment of Contract
68-03-2550 by Monsanto Research Corporation under the sponsorship
of the U.S. Environmental Protection Agency. This report covers
the period November 1, 1977 to December 31, 1977. The work was
completed as of January 20, 1978.
IV
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CONTENTS
Foreword iii
Abstract iv
Figures vi
Tables vi
Abbreviations vii
Conversion Factors and Metric Prefixes viii
Acknowledgement ix
1. Introduction 1
2. Summary 2
3. Source Description 5
Physical and chemical properties 5
Production 5
Process descriptions 7
Uses . 7
4. Environmental Significance and Health Effects .... 12
Environmental significance 12
Health effects 16
5. Control Technology 17
Air emissions 17
Wastewater effluents 18
Sludges 19
6. Regulatory Action in Progress 21
References ..... 23
v
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FIGURES
Number Page
1 Sources of mercury and industrial and commercial
usage in the United States, 1973 8
TABLES
1 Sources of Mercury, Their Magnitude, and Control ... 3
2 Physical and Chemical Properties of Mercury and Some
of its Compounds 6
3 Production of U.S. Mercury Mines in 1973 6
4 Producers of Mercury Compounds 9
5 Total Mercury Losses in 1971 for the United States
by Sector and SIC Category 13
6 EPA Mercury Regulations 22
VI
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ABBREVIATIONS
FDA — U.S. Food and Drug Administration
MEM — methoxyethylmercury
PMA — phenylmercury acetate
ppb -- parts per billion
ppm — parts per million
TLV — threshold limit value
VII
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CONVERSION FACTORS AND METRIC PREFIXES3
CONVERSION FACTORS
To convert from To Multiply by
Gram/second (g/s) Pound/hr 7.937
Kilogram (kg) Pound-mass (pound-mass
avoirdupois) 2.205
Meter3 (m3) Foot3 3.531 x 10l
Metric ton Pound-mass 2.205 x 103
Metric ton Kilogram 1.000 x 103
Metric ton Ton (short, 2,000
pound-mass 1.585 x lO"4
METRIC PREFIXES
Prefix Symbol Multiplication factor Example
Kilo k 103 1 kg = 1 x 103 grams
Milli m 10~3 1 mm = 1 x 10~3 meter
Standard for Metric Practice. ANSI/ASTM Designation:
E 380-76e, IEEE Std 268-1976, American Society for Testing and
Materials, Philadelphia, Pennsylvania, February 1976. 37 pp.
viii
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ACKNOWLEDGEMENT
This report was assembled for EPA by PEDCo-Environmental, Inc.
Cincinnati, OH, and Monsanto Research Corporation, Dayton, OH.
Mr. D. L. Becker served as EPA Project Officer, and Dr. C. E.
Frank, EPA Consultant, was principal advisor and reviewer.
IX
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SECTION 1
INTRODUCTION
Mercury and mercury compounds are utilized in many industrial
processes and commercial products. The largest uses of mercury
have been manufacture of electrical apparatus, industrial control
instruments, and mercury-based pesticides.
All three common forms of mercury--elemental mercury, inorganic
salts, and organic mercury compounds—all exhibit toxicological
properties. Alkyl mercury compounds in the organic group appear
to be the most hazardous. Methyl mercury can be formed from any
of the three categories of mercury by microorganisms found in
the bottom muds of aquatic environments.
S
The high toxicity of mercury has led to stringent regulations
concerning mercury contamination; however, since its applications
and environmental sources are diverse, mercury continues to
enter the environment.
This report presents information detailing sources of mercury
contamination, potential health effects, control technology, and
regulatory actions. A brief description of the mercury produc-
tion process is given along with the amount of mercury available
from primary production, secondary production, and imported
metal.
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SECTION 2
SUMMARY
Major consumptive uses of mercury have included the manufacture
of electrical apparatus, industrial control instruments, and
mercury-based pesticides. The amount of mercury available for
domestic use is approximately 1,900 metric tons/yr.a Mercury is
obtained from primary processing of ore, secondary production
from scrap, and imports.
Mercury and its compounds are generally toxic. Mercuric salts
are fatal to man when taken internally at a dose of 20 mg to
3 g. Alkyl mercury compounds exhibit a high toxicity in man,
causing death from injestion of several milligrams.
Major sources of mercury pollution include copper smelting, coal
combustion, chloralkali production, control instrument manufac-
turing, and paint and battery consumption. Total mercury lost
to the environment from all manmade sources was estimated at
1,525 metric tons/yr.
Control of mercury emissions in the primary smelting industry is
accomplished by mist eliminators and wet-scrubbers. Secondary
process industries control mercury emissions by direct and
indirect condensation, chemical scrubbing, and adsorption.
Wastewaters and sludges containing mercury have been controlled
in the chloralkali industry by sulfide precipitation and by
high-temperature roasting, respectively,
Mercury has been classified as a priority pollutant for study
under the Federal Water Pollution Control Act. The U.S. Food
and Drug Administration (FDA) has established a guideline for
mercury in edible fish of 0.5 mg/kg.
Table 1 summarizes information on the sources and amounts of
mercury contamination in the environment, its uses, and present
control technology.
ai metric ton equals 106 grams; conversion factors and metric
system prefixes are presented in the prefatory material.
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TABLE 1. SOURCES OF MERCURY, THEIR MAGNITUDE, AND CONTROL
Mercury losses,
metric tons/yr
Source
Mercury mining and smelting
Other mining and smelting:
Copper mining
Zinc and lead mining
Copper smelting
Zinc smelting
Cement processing '
Lime processing
Unregulated sources:
Livestock
Fuel oil consumption
Refineries
Tars and asphalt
Coke ovens
Coal combustion
Utilities, oil, and natural gas
Natural gas consumption
utilities, coal
Manufacturing and processing:-
Caustic
Catalyst manufacture
Paint manufacture
Pesticide manufacture
Pharmaceuticals manufacture
Chloralkali
Textiles
Paint formulation
Control instrument manufacture
Catalyst usage
Tubes/switches manufacture
Lamp manufacture
Battery manufacture
Other
Commercial and industrial consumption:
Urethane
Nonagricultural pesticide use
Agricultural pesticide use
Control instrument use
Tubes, switches use
Lamp use
Laboratory usage
Consumer goods consumption:
Pharmaceuticals
Paint
Batteries
Dental applications
Air
7.85
0.02
0
40.77
4.59
0.5
0.08
0
16.94
1.15
1.1
7.16
9.97
11.99
15.46
40.71
0
0
0.01
0
0
14.84
0
0.29
0
0.05
0
0.4
0.13
10.28
0.12
4.39
0
16.54
7.53
6.07
2.28
1.04
173.61
69.71
0.93
Water
0
0.01
0
2.26
0.25
0.25
0.04
0
0
0
1.67
0.51
0
0
0
0
7.61
0.02
0.2
0.06
0.2
2.93
0.15
0.35
0
0.1
10.23
0
0
0.05
0
17.56
2.83
0
0
0
5.92
17.77
0
0
16.65
Land
0.45
0.08
0.01
45.29
5.09
2.51
0.41
17.7
0.02
1.15
14.99
2.56
1.11
0.01
0.01
4.52
1.9
0
0.05
0
0
226.83
7.63
0
1.97
18.85
8.7
1.57
1.34
2.49
2.22
21.95
16.02
107.5
46.26
37.31
1.59
2.09
9.14
403.3
0
Control technology
Mist eliminators and wet scrub-
bers control mercury in pri-
mary mining and smelting;
Secondary metal processing
industries use direct and in-
direct condensation, chemical
scrubbing, and adsorption.
Combustion sources control
particulates containing mer-
cury with electrostatic pre-
cipitators, wet scrubbers, and
baghouses .
Sulfide precipitation is used to
treat wastewater from chlor-
alkali plants. Sludges are
treated by high-temperature
roasting.
Regulatory action
Mercury ore process-
ing 2.3 kg/24-hr
period.
A 0.05 mg/m3 threshold
limit value (TLV) has
been established for
mercury in workroom
air.
Chloralkali plants are
allowed 2.3 kg/24-hr
period (mercury emis-
sions) . Mercury has
been designated as a
priority pollutant
under the Federal
Water Pollution Con-
trol Act.
A 0.05 mg/m3 threshold
limit value (TLV) has
been established for
mercury in workroom
air.
A 0.05 mg/m3 threshold
limit value (TLV) has
been established for
mercury in workroom
air.
Food and Drug Adminis-
tration has estab-
lished a limit for
mercury in edible
fish of 0.5 mg/kg.
471.26 87.7 966.11
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Based on the data presented in this report, the following informa-
tion needs to be obtained in future studies:
• Potential population exposed to mercury compounds from
sources shown in Table 1.
• Concentrations of mercury in air, water, and land caused
by anthropogenic sources.
• Efficiencies and costs of control technology for mercury
pollutants.
It is recommended that further pollution assessment studies be
implemented concerning copper smelting, coal combustion and
paint manufacture and use since these operations contribute
approximately 51% of the total mercury emitted from all known
man-made sources. Approximately 85% of the total mercury lost
to land areas results from copper smelting, chloralkali opera-
tions, and consumption of batteries, control instruments and
tubes. The ultimate fate of this mercury is unknown and there-
fore requires further study.
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SECTION 3
SOURCE DESCRIPTION
Although mercury is mined and produced in the United States, most
of it is imported for use. It has unique properties which make
its use very important to industry and science. Production and
use are discussed in this section along with various chemical
processes and properties.
PHYSICAL AND CHEMICAL PROPERTIES
Mercury is a heavy metal which is liquid at normal temperatures.
Table 2 describes some of the physical and chemical properties
of mercury and various mercury compounds (1).
PRODUCTION
Principal sources of mercury include primary production from
domestic ore, secondary mercury production from scrap materials,
and imports. Primary production of mercury in the United States
totalled 59 metric tons in 1974. This was a 20% decrease in
primary production from 1973 when production totalled 73 metric
tons (2) .
Table 3 shows mercury mining operations and their location in
the United States (3).
Production of mercury from scrap materials was 267 metric tons
in 1973, while imports of mercury metal accounted for 1,576
metric tons during the same year (3).
(1) Stokinger, H. E. The Metals (Excluding Lead). In: Indus-
trial Hygiene and Toxicology, Chapter 27, D. W. Fassett and
D. D. Irish, eds. Interscience Publishers, New York, New
York, 1962. 1090-1104 pp.
(2) Non-Ferrous Metal Data 1974. American Bureau of Metal
Statistics, Inc., New York, New York, 1975. 143 pp.
(3) VanHorn, W. Materials Balance and Technology Assessment of
Mercury and Its Compounds on National and Regional Bases.
EPA-560/3-75-007, U.S. Environmental Protection Agency,
Washington, D.C., October 1975. 433 pp.
5
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TABLE 2. PHYSICAL AND CHEMICAL PROPERTIES OF
MERCURY AND SOME OF ITS COMPOUNDS (1)
Chemical
Atomic or Melting Boiling
Chemical molecular Specific point, point,
symbol weight gravity °C *C
Solubility (temperature, °C)
Mercury
Mercuric
oxide
(montroy-
dite)
Mercuric
sulfide
(cinnabar)
Hg
HgO
HgS
Mercuric HgCl2
chloride
Mercurous Hg2SOi,
sulfate
Mercuric
acetate
Mercuric Hg(NCO)2
fulminate
Dimethyl Hg(CH3)2
mercury
Ethyl C2H5HgCl
mercuric
chloride
200.61 13.546 -38.87
216.61 11.14 Decomposes 500
232.68 8.10
271.52 5.44
497.29
318.7
284.65
230.68
265.13
Phenyl C6H5HgO2C2H3 336.75
mercuric
acetate
7.56
3.27
Sublimes 583.5
276
Decomposes
Decomposes
4.42 Explodes
3.069
3.482 193
149
356.58 Insoluble hot or cold water dilute,
hydrochloric acid, hydrogen
bromide, hydrogen iodide.
52 mg/m3
395 mg/m3 (100)
Soluble acids
Insoluble alcohol, ether, acetone,
alkalies, ammonia
10 mg/m3 (18)
Soluble sodium sulfide, aqua regia
Insoluble nitric acid, alcohol
302 36 kg/m3 (0)
69 kg/m3 (20)
613 kg/m3 (100)
330 kg/m3 alcohol
250 kg/m3 ether
Soluble acetic acid, pyridine
Decomposes 600 g/m3
900 g/m3 (100)
Soluble sulfuric acid, nitric acid
250 kg/m3 (10)
1,000 kg/m3 (100)
Soluble alcohol, acetic acid
Slightly soluble cold water
Soluble hot water, alcohol,
ammonium hydroxide
96
Soluble alcohol, ether
Insoluble cold water
Very soluble hot alcohol
Slightly soluble ether
Slightly soluble hot or cold water
Soluble glacial acetic acid,
benzene, alcohol
'unless otherwise stated, solubility is in water at 25°c.
Note.—Blanks indicate data not available.
TABLE 3. PRODUCTION OF U.S. MERCURY MINES IN 1973
Mine
New Almaden
Guadalupe
Chilino Valley
Corona
Oat Hill
Manhattan-One-Shot
Mount Jackson
Culver-Baer
Abbott
Cardero
Ruja
Study Butte
Alice and Bessie
TOTAL
County/state
Santa Clara, CA
Santa Clara, CA
Marin, CA
Napa, CA
Napa, CA
Napa, CA
Sonoma , CA
Sonoma , CA
Lake, CA
Humboldt, NV
Humboldt , NV
Brewster , TX
Kuskokwim, AK
Estimated
production
metric tons/yr
•25
3
4
9
2
23
6
2
74
Note.—Blanks indicate data not available.
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PROCESS DESCRIPTIONS
The primary mercury industry is very small in the United States.
The ore of economic importance is cinnabar mercury sulfide. The
typical smelter industry practice is to feed mined mercury ore
directly into kilns for recovery of mercury by roasting. Ore
flotation is practiced for the beneficiation of low-grade ores.
Currently, most mercury is produced through a directly heated
pyrometallurgical process. Mechanical furnaces or retorts are
used to roast mercury-bearing materials (4). Mercury vapors
resulting from the roasting operation are drawn off and condensed
to yield metallic mercury.
The secondary mercury production industry consists of approxi-
mately 300 small facilities utilizing a variety of mercury-bear-
ing wastes as raw material sources. Wastes used in secondary
processing include spent catalysts, batteries and industrial con-
trols. Mercury from these sources is distilled off and condensed
to form the product.
In both processes, two or three distillations are sometimes
applied to give various degrees of mercury purity.
USES
Of the total 1975 domestic mercury consumption of 1,964 metric
tons, about 70% was from imports. New domestic capacity should
reduce imports to about 50%. Secondary smelting currently
accounts for 61% of domestic capacity. In 1973, consumption was
1,871 metric tons, as shown in Figure 1 (3).
Individual markets for mercury consumption are listed in Fig-
ure 1. Of these electrical apparatus manufacturing, electrolytic
preparation of chlorine, and caustic soda account for 50% of the
total mercury consumed in 1973. The cytotoxic properties of
mercury compounds have given them a widespread usage as germi-
cides and pesticides added to Pharmaceuticals, plastics, paints,
and other products. Methyl mercury and ethyl mercury have been
banned for use in seed treatment due to their high toxicity.
Methoxyethyl mercury (MEM) compounds have replaced the alkyl-
mercury compounds in seed treatment. Phenylmercury acetate (PMA)
has been extensively used as a fungicide and algaecide in paints,
plastics, and other products. Under the conditions in which they
are used, both types of compounds, PMA and MEM, are unstable and
slowly release inorganic mercury. Table 4 presents a listing of
41 other mercury compounds produced by 13 companies.
(4) Kirk-Othmer Encyclopedia of Chemical Technology, Second
Edition, Volume 13. John Wiley & Sons, Inc., New York,
New York, 1967. 218-235 pp.
7
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00
560
METERS
PUMPS
MISCELLANEOUS
100
^^™
—
—
PAINT
261
AGRICULTURE
50
PHARMA-
CEUTICALS
17
CATALYSTS
17
I—
L
P-
—
1—
TURF
SEED TREAT-
ELASTOMERS,
ETC.
VINYL
CHLORIDE
SYNTHESIS
MISCELLA-
NEOUS
35
15
3
VAT DYES
12
1
PRESERVATIVES
ADHESIVES
MISCELLANEOUS
PIGMENTS
STABILIZERS
MISCELLANEOUS
Figure 1.
Sources of mercury and industrial and commercial
usage in the United States, 1973 (metric tons/yr) (3)
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TABLE 4. PRODUCERS OF MERCURY COMPOUNDS
Chemical
Company
Location
Di(phenylmercury) dodecenyl
succinate
Chloromethoxypropylmercuric
acetate
Merbromin
Mercurial turf fungicides
Mercuric salicylate
Mercurous chloride
Mercury ammoniated
Mercury bichloride
Mercury bromate
Mercury bromide
Tenneco Chemicals, Inc.
Troy Chemical Corp.
Becton, Dickinson, Inc.
Mallinckrodt, Inc./Industrial Chemicals
Mallinckrodt, Inc./Drug and Cosmetic Chemicals
Merck & Co., Inc./Chemical Manufacturing Division
Mallinckrodt, Inc./Industrial Chemicals
Mallinckrodt, Inc./Drug and Cosmetic Chemicals
Mallincrodt, Inc./Industrial Chemicals
Merck & Co. Inc./Chemical Manufacturing Division
Troy Chemical Corp
City Chemical Corp.
City Chemical Corp.
Merck & Co., Inc./Chemical Manufacturing Division
Mercury chloride (mercurous) Mallinckrodt, Inc./Industrial Chemicals
Mercury cyanide
Mercury ethyl sulfate
Mercury fluoride (mercuric)
Mercury fluoride (mercurous)
Troy Chemical Corp.
Mallinckrodt, Inc./Drug and Cosmetic Chemicals
City Chemical Corp.
City Chemical Corp.
Pennwalt Corp./Ozark-Mahoning
City Chemical Corp.
Elizabeth, NJ
Newark, NJ
Baltimore, MD
St. Louis, MO
St. Louis, MO
Hawthorne, NJ
St. Louis, MO
Jersey City, NJ
Jersey City, NJ
St. Louis, MO
Hawthorne, NJ
Newark, NJ
Jersey City, NJ
Jersey City, NJ
Hawthorne, NJ
Jersey City, NJ
St. Louis, MO
Newark, NJ
Jersey City, NJ
Jersey City, NJ
Jersey City, NJ
Tulsa, OK
Jersey City, NJ
(continued)
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TABLE 4 (continued)
Chemical
Company
Location
Mercury iodate
Mercury iodide (mercuric)
Mercury lactate
Mercury naphthenate
Mercury nitrate (mercuric)
Mercury oxalate (mercuric)
Mercury oxalate (mercurous)
Mercury oxide, red
Mercury oxide, yellow
Mercury oxyfluoride
Mercury phosphate
Mercury stearate
Mercury succinate
Mercury succinimide
Mercury sulfate (mercuric
sulfate)
City Chemical Corp.
Mallinckrodt, Inc./Drug and Cosmetic Chemicals
City Chemical Corp.
Troy Chemical Corp.
City Chemical Corp.
Mallinckrodt, Inc./Industrial Chemicals
City Chemical Corp.
City Chemical Corp.
Mallinckrodt, Inc./Industrial Chemicals
Merck & Co., Inc./Chemical Manufacturing Division
Troy Chemical Corp.
Mallinckrodt, Inc./Industrial Chemicals
Merck & Co., Inc./Chemical Manufacturing Division
Troy Chemical Corp.
City Chemical Corp.
City Chemical Corp.
City Chemical Corp.
City Chemical Corp.
City Chemical Corp.
Jersey City, NJ
Jersey City, NJ
Jersey City, NJ
Newark, NJ
Jersey City, NJ
Jersey City, NJ
Jersey City, NJ
Jersey City, NJ
Jersey City, NJ
Hawthorne, NJ
Newark, NJ
Jersey City, NJ
Hawthorne, NJ
Newark, NJ
Jersey City, NJ
Jersey City, NJ
Jersey City, NJ
Jersey City, NJ
Jersey City, NJ
Mallinckrodt, Inc./Industrial Chemicals Division Jersey City, NJ
Merck & Co., Inc./Merck Chemical Manufacturing Division Hawthorne, NJ
G. Frederick Smith Chemical Co. Columbus, OH
(continued)
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TABLE 4 (continued)
Chemical
Company
Location
Mercury sulfocyanide
(Mercuric sulfocyanide)
(Mercury thiocyanate)
(Mercuric thiocyanate)
Methylmercuric chloride
2-(Phenylmercuriamino)
ethyl acetate
Phenylmercuric acetate (PMA)
PhenyImercuric ammonium
acetate (PMAA)
Phenylmerciric lactate
Phenylmercuric oleate
Phenylmercury borate
Phenylmercury hydroxide
Phenylmercury nitrate
Phenylmercury propionate
TolyImercuric chloride
Tris (2-hydroxyethyl)
(Phenylmercuric) ammonium
lactate
R.S.A. Corp.
Strem Chemicals, Inc.
W. A. Cleary Corp.
W. A. Cleary Corp.
Cosan Chemical Co.
Merck & Co., Inc./Chemical Manufacturing Division
Tenneco Chemicals, Inc.
Troy Chemical Corp.
Troy Chemical Corp.
Troy Chemical Corp.
W. A. Cleary Corp.
Cosan Chemical Co.
Merck & Co., Inc./Chemical Manufacturing Division
Tenneco Chemicals, Inc.
Troy Chemical Corp.
Cosan Chemical Co.
Troy Chemical Corp.
Merck & Co., Inc./Chemical Manufacturing Division
Troy Chemical Corp.
Merck & Co., Inc./Chemical Manufacturing Division
Eastman Kodak/Organic Chemicals Division
W. A. Cleary Corp.
Ardsley, NY
Danvers, MA
Somerset, NJ
Somerset, NJ
Clifton, NJ
Hawthorne, NJ
Elizabeth, NJ
Newark, NJ
Newark, NJ
Newark, NJ
Somerset, NJ
Clifton, NJ
Hawthorne, NJ
Elizabeth, NJ
Newark, NJ
Clifton, NJ
Newark, NJ
Hawthorne, NJ
Newark, NJ
Hawthorne, NJ
Rochester, NY
Somerset, NJ
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SECTION 4
ENVIRONMENTAL SIGNIFICANCE AND HEALTH EFFECTS
ENVIRONMENTAL SIGNIFICANCE
Mercury is circulated in the biosphere; approximately 1,200
metric tons are released annually to the atmosphere by degassing
from the earth's crust and oceans (3). In nature, mainly in the
aquatic environment, methyl mercury is produced from inorganic
mercury by microbial activity.
Table 5 presents the sources and extent of mercury contamination
in the environment. From this table, the source that accounts
for 45% of the total mercury released (694 metric tons) is from
final consumption of consumer goods. This includes consumer use
of Pharmaceuticals, paint, and batteries (3).
One source of environmental contamination by mercury is the
burning of coal and petroleum. Analyses of fly ash from coal-
fired boilers show 10% or less of the original mercury remains
from the coal. The major portion of mercury in coal is thus
released to the air. Coal has been reported to contain between
0.012 parts per million (ppm) and 33 ppm of mercury.
The chloralkali industry is an example of a manufacturing process
where mercury contamination is evident. Atmospheric emissions
from the B. F. Goodrich plant in Calvert City, KY were reported
to be 110 kg/day, far exceeding the National Air Emissions
Standard of 1.3 kg/day. Of mercury losses, brine sludge repre-
sented about 60% of the total. Furthermore, a survey of Diamond
Shamrock, Muscles Shoals, AL, showed that mercury lo.sses were
atmospheric emissions, principly from the mercury cell in chlor-
ine manufacture. An investigation of mercury losses from Pennwalt
in Calvert City, KY, revealed that most losses emanated from
cellroom ventilation. Emissions from these plants, however,
have been reduced due to the use of control technology. Water
contamination from the chloralkali industry, once a dominant
source, also has been greatly reduced through improved wastewater
treatment.
In the primary lead industry, the major air emission is hot
mercury-laden gas from the furnace. A typical condenser stack
gas emission factor of 0.12 kg Hg per metric ton of lead ore
processed has been reported. The concentration in the gas is
12
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TABLE 5. TOTAL MERCURY LOSSES IN 1971 FOR THE UNITED
STATES BY SECTOR AND SIC CATEGORY (3)
(metric tons)
Source
Mercury mining and smelting:
Mercury mining
Mercury processing
(including secondary)
Subtotals
Other mining:
Copper mining
Zinc and lead mining
Copper smelting
Zinc smelting
Cement processing
Lime processing
Lead smelting
Subtotals
Unregulated sources :
Livestock
Fuel oil--residential, commercial,
and industrial
Refineries
Tars and asphalt
Coke ovens
Coal--Residential, commercial, and
industrial
Utilities--oil and natural gas
Total
Air
0.01
7.84
7.85
(1.7%)
0.02
0.00
40.77
4.59
0.50
0.08
4.75
50.71
(10.8%)
0.00
16.94
1.15
1.10
7.16
9.97
11.99
losses
Water
0.00
0.00
0.00
(0.0%)
0.01
0.00
2.26
0.25
0.25
0.04
0.26
3.07
(3.5%)
0.0
0.00
0.00
1.67
0.51
0.00
0.00
to
Land
0.01
0.41
0.42
(0.0%)
0.08
0.01
2.26
0.25
1.76
0.29
0.26
4.91
(0.5%)
17.70
0.02
1.15
14.99
2.56
1.11
0.01
Total
mercury
lost
0.02
8.25
8.27
(0.5%)
0.11
0.01
45.29
5.09
2.51
0.41
5.27
58.69
(3.8%)
17.70
16.96
2.30
17.76
10.23
11.08
12.00
Total
recycled
0.00
0.00
0.00
(0.0%)
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
(0.0%)
0.00
0.00
0.00
0.00
0.00
0.00
0.00
(continued)
-------
TABLE 5 (continued)
Source
Unregulated sources — continued
Natural gas--residential, commer-
cial, and industrial
Utilities — coal
Subtotals
Manufacturing and processing:
Caustic
Catalyst manufacture
Paint manufacture
Pesticide manufacture
Pharmaceuticals manufacture
Chloralkali
Textiles
Paint formulation
Control instrument manufacture
Catalyst usage
Other
Tubes/switches manufacture
Lamp manufacture
Battery manufacture
Subtotals
'Final consumption:
Commercial and industrial:
Urethane and miscellaneous
Nonagricultural pesticide use
Agricultural pesticide use
Total
Air
15.46
40.71
104.48
(22.2%)
0.00
0.00
0.01
0.00
0.00
14.84
0.00
0.29
0.00
0.05
10.28
0.00
0.40
0.13
26.00
(5.5%)
0.12
4.39
0.00
losses
Water
0.00
0.00
2.18
(2.5%)
7.61
0.02
0.20
0.06
0.02
2.93
0.15
0.35
0.00
0.10
10.23
0.00
0.00
0.05
21.72
(24.8%)
0.00
17.56
2.83
to
Land
0.01
4.52
42.07
(4.4%)
1.90
0.00
0.05
0.00
0.00
226.83
7.63
0.00
1.97
18.85
8.70
1.57
1.34
2.49
271.33
(28.1%)
2.22
21.95
16.02
Total
mercury
lost
15.47
45.23
148.73
(9.8%)
9.51
0.02
0.26
0.06
0.02
244.60
7.78
0.64
1.97
19.00
29.21
1.57
1.74
2.67
319.05
(21.0%)
2.34
43.90
18.85
Total
recycled
0.00
0.00
0.00
(0.00%)
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.97
0.00
20.66
0.00
0.00
0.00
20.66
(14.1%)
0.00
0.00
0.00
(continued)
-------
TABLE 5 (continued)
Source
Commercial and industrial — continued
Control instrument consumption
Tubes/switches consumption
Lamp consumption
Laboratory usage
Subtotals
Consumer goods:
Pharmaceuticals consumption
Paint consumption
Battery consumption
Dental applications
Subtotals
TOTAL
Final disposal:
Sewage
Urban runoff
Natural sources:
Degassing 1,
Runoff and groundwater
Total
Air
16.54
7.53
6.07
2.28
36.93
(7.8%)
1.04
173.61
69.71
0.93
245.29
(52.0%)
471.26
4.01
0.00
018.70
0.00
losses
Water
0.00
0.00
0.00
5.92
26.31
(30.0%)
17. 77
0.00
0.00
16.65
34.42
(39.2%)
87.70
19.92
11.70
0.00
188.30
to
Land
107.50
46.26
37.31
1.59
232.85
(24.1%)
2.00
9.14
403.30
0.00
414.53
(42.9%)
966.11
22.88
0.00
0.00
0.00
Total
mercury
lost
124.04
53.79
43.38
9.79
296.09
(19.4%)
20.90
182.75
473.01
17.58
694.24
(45.5%)
1,525.07
46.80
11.70
1,018.70
188.30
Total
recycled
82.69
0.00
0.00
12.98
95.67
(65.2%)
0.00
0.00
24.89
5.55
30.44
(20.7%)
146.77
-------
7.86 mg/mg3. The amount of mercury discharged to wastewaters
from primary lead production is insignificant.
The largest source of solid waste is the furnace or retort resi-
due, amounting to some 207 kg/kg of metallic mercury produced.
This calcined waste can vary widely in mercury content, with an
estimated average of 100 ppm and 250 ppm for retorts and fur-
naces, respectively. These furnace residues together with mine
rock and tailings are judged to have potential impacts on the
environment.
The secondary mercury production industry consists of approxi-
mately 300 small facilities utilizing a variety of mercury-
bearing wastes as raw material sources. An evaluation of the
industry indicates that the estimated atmospheric mercury emis-
sions are 2 kg/100 kg Hg processed. This amounts to 5.3 metric
tons/yr of mercury emitted from the 267 metric tons produced
annually by secondary processing.
HEALTH EFFECTS
Human exposure to mercury may occur in its mining and recovery or
in any industry where mercury is being used. Mercury enters the
body through the skin, gastrointestinal tract, or respiratory
tract (4). Early symptoms of mercury poisoning include general
weakness, exhaustion, mouth inflamation, loosening of teeth,
excessive salivation, emotional instability, and body tremors
(4). Chronic poisoning can develop rapidly and without warning.
Various mercury compounds differ in their toxicity to man. Mer-
curic salts have a fatal oral dose in man of 20 mg to 3 g (5).
Alkyl mercury compounds exhibit high toxicity in man, causing
death from injestion of several milligrams (5).
(5) Quality Criteria for Water. EPA-440/9-76-023, U.S. Environ-
mental Protection Agency, Washington, D.C., October 1975.
501 pp.
16
-------
SECTION 5
CONTROL TECHNOLOGY
In the primary smelting industry, attention is focused on air
emissions control. Mist eliminators and wet-scrubbers are the
major control devices. Available data indicate that 50% to 70%
of the mercury emitted from the stacks of primary extraction
facilities is particulate. In the secondary production industry,
emission controls include direct and indirect condensation,
chemical scrubbing, and adsorption.
In an experimental study of a chloralkai plants, wastewater
ranged from 3 ppm to 18 ppm mercury, while brine sludge was
150 ppm to 1,500 ppm mercury. The most effective control tech-
niques were sulfide precipitation for the water treatment and
high temperature roasting for the treatment of sludge. Effluent
mercury levels ranged from 10 parts per billion (ppb) to 125 ppb,
with an average removal efficiency of 96.8%.
AIR EMISSIONS
Various processes have been developed for removing mercury vapor
from air and other gases (6). One process achieves mercury
removal from gases by impregnating materials (including metal
such as gold, silver, cadmium, indium, thallium, aluminum, lead,
gallium, and copper) on activated carbon. These products will
rapidly and quantitatively remove mercury vapor from air as well
as from other gases, including hydrogen, carbon dioxide, nitrogen,
and oxygen. The high surface area of the activated carbon,
which is impregnated with the mercury reactant, appears to be ,
partially responsible for the greatly improved adsorption of the
mercury vapor; the carbon appears to activate the metal thus
enabling the mercury to be adsorbed by the impregnating material
(metal).
Another process involves removing mercury from a gas stream by
washing the gas with alkaline hypochlorite containing added
alkali metal or calcium chloride. The alkaline hypochlorite
solution can be sodium hypochlorite. Sodium hypochlorite solu-
tions are well known in commerce and normally contain sodium
hypochlorite and sodium chloride of approximately equimolar pro-
portions. When mercury vapor is reacted with such solutions or
(6) Sittig, M. Pollutant Handbook. Noyes Data Corporation,
Park Ridge, New Jersey, 1973. 286-308 pp.
17
-------
with solutions prepared by diluting the commercial solutions with
water, a precipitate of insoluble mercury compounds is formed.
This is inconvenient because it tends to settle out in vessels
and pipelines and the like and makes the recovery of the mercury
more difficult. It has been discovered, however, that if addi-
tional alkali metal chloride or calcium chloride is added to the
alkaline hypochlorite solution, the mercury remains in solution,
possibly in the form of a complex anion. The amount of addi-
tional sodium or calcium chloride to prevent mercury compounds
precipitating depends upon the composition of the solution, par-
ticularly with respect to pH.
Washing the mercury-containing gas streams may be carried out in
any gas-liquid contacting device; for example, a column packed
with Raschig rings or on diffuser plates. It may be carried out
in ambient temperature or at any other convenient temperature.
Mercury may then be recovered from the solution either chemically
or electrolytically. A suitable electrolytic cell for recovering
the mercury contains a graphite or platinized titanium anode and
a mercury cathode. The mercury in solution is reduced at the
cathode. A preferred method of recovering mercury from the
absorbing solution is to blend it slowly into the feed brine
stream supplying one or more commercial mercury cells. The
mercury in solution is then recovered electrolytically at the
cathode.
WASTEWATER EFFLUENTS
A variety of processes for mercury removal from water have simi-
larly been developed (6). One process involves recovering mer-
cury from brine effluent from mercury cathode electrolytic cells.
The mercury cathode electrolytic cells are constructed with a
relatively small gap between a fixed anode and a steel plate or
other current-conducting material. In the operation of these
cells, saturated sodium chloride or potassium chloride brine and
mercury are passed through this gap during the electrolysis. The
mercury upon entering the cell spreads over the steel plate or
other conducting material and acts as a cathode for the cell.
In the process, saturated brine solutions are used. After pass-
ing the brine once through the cell, the brine discharged from
the cell is dechlorinated by air stripping or other means, resa-
turated, and recycled again through the cell. In passing through
the cell, the chloride concentration of the brine is seldom
reduced over 20%. Thus, the brine discharge from the cell is
still relatively saturated.
While mercury cathode cells have many advantages over other con-
ventional cells, a small but significant amount of mercury is
lost in the process. A major portion of the mercury loss results
from the chlorination of the mercury to a soluble salt which dis-
solves in the brine as it passes through the cell. This mercury
18
-------
which reacts with the chlorinated brine is often lost in the
resaturation step of the process. Thus, the brine leaving the
cell may contain as much as 50 parts of mercury per million parts
of brine.
An aqueous solution having a pH between 2 and 11 and containing
from 1 ppm to 500 ppm of dissolved mercury can be cleaved with a
reducing agent. This is done by bringing a substantially water-
stable solid metallic reducing agent having a greater solution
potential than mercury into contact with the solution; elemental
metallic mercury is liberated. The liberated mercury amalgamates
the surfaces of the reducing agent and also coalesces into drop-
lets on the surfaces.
Depending on the manner of carrying out the process, particles of
amalgam and mercury droplets are either allowed to fall from the
reducing agent and collected from time to time, or the amalgam
and mercury droplets are flushed from the surfaces of the reduc-
ing agent along with inert solid formed and recovered from the
flushing liquid by settling or filtration. Impure mercury recov-
ered in this manner is purified by standard methods, such as acid
washing or retorting or by a combination of methods. If desired,
mercury may also be recovered by removing the reducing agent from
the reaction zone periodically along with accumulated reaction
products and by.retorting the entire mass.
SLUDGES
A number of processes have also been developed for removal of
mercury from sediments and sludges (6). For example, one process
involves recovering mercury from sludge from a purification tank
for the purification of saturated alkali chloride solution
obtained in the production of caustic alkali and chlorine by the
electrolysis of alkali chloride solution in the so-called "mer-
cury process."
In the electrolysis of alkali chloride solution by the mercury
process, alkali chloride is usually dissolved in water to a con-
centration of about 0.3 g/m3 and this saturated alkali chloride
solution is introduced into an electrolytic cell fitted with a
mercury cathode. The electrolysis is then carried out, and
sodium amalgam is produced at the mercury cathode, while chlorine
gas is generated at the anode and subsequently collected.
According to the above electrolytic step, about 10% of the alkali
chloride in the influent alkali chloride solution is electrolyzed
after which it is exhausted from the electrolytic cell.
Additional alkali chloride is dissolved in this depleted brine
to produce again the saturated alkali chloride solution. The
saturated alkali chloride solution, from which impurities such as
calcium, magnesium, and sulfate mixed together with the
19
-------
additional alkali chloride are removed in a purification step, is
again circulated into the electrolytic cell.
The efficiencies of the control methods described for mercury
removal from air, water and solids are not known. The extent to
which these control techniques are applicable to specific
industries where mercury is present as a pollutant is unknown.
20
-------
SECTION 6
REGULATORY ACTION IN PROGRESS
Past regulations established by EPA concerning mercury are cited
in Table 6 (3). The FDA has established a guideline for mercury
in edible fish of 0.5 mg/kg (5). The American Conference of
Governmental Industrial Hygienists has established a threshold
limit value (TLV) of 0.05 mg/m3 for mercury in workroom air (7).
Mercury has been designated as a priority pollutant for study
under the Federal Water Pollution Control Act. Best available
technology and pretreatment primary standards are to be reviewed
in the near future.
(7) TLVs® Threshold Limit Values for Chemical Substances and
Physical Agents in the Workroom Environment with Intended
Changes for 1976. American Conference of Governmental Indus-
trial Hygienists, Cincinnati, Ohio, 1976. 94 pp.
21
-------
TABLE 6. EPA MERCURY REGULATIONS (3)
Federal
Register
Date
Applicable to
Standard
to
to
38 FR 8820
38 FR 35388
(proposed)
(39 FR 10603
4/06/73
12/27/73
Mercury ore processing facilities 2.3 kg/24-hr period
and chloralkali plants.
Paper and allied products, oil
and gas extraction, industrial
organic or inorganic chemical,
alkalis and chlorine, ferrous
metal production, nonferrous
metal smelting and refining,
lumber and wood products,
bituminous coal and lignite
mining, storage or primary
battery manufacturing, or metal
mining facility discharging
into navigable water.
38 FR 28610
39 FR 38064
10/15/73 Ocean dumping.
10/25/74 Wastewater treatment plant sludge
incinerators.
Streams, lakes, or estuaries with flow
<0.28 m3/s or lakes <2.02 km2 — no
discharges.
Other streams and lakes—20 mg/m3/discharge
or l/10th this concentration when low flow
is <10 times the waste flow.
Other estuaries and all coastal waters—
100 mg/m3/discharge or l/10th this concen-
tration where low flow is <10 times the
waste flow.
Stream—not to exceed 0.005786 times flow in
m3/s or 0.73 kg/day.
Lake—not to exceed 0.004821 times flow in
m3/s or 0.61 kg/day.
Estuary—not to exceed 0.00027 times flow in
m3/s or 1.22 kg/day.
Coastal water—not to exceed 0.009642 times
flow in m3/s or 1.47 kg/day.
No mercury except as trace contaminants.
3.2 kg/24-hr period.
This table does not include regulations dealing with mercury-based pesticides. There have been and
continue to be many such regulations, all involving either cancellation or suspension of pesticide use.
Federal Register, 38:3820.
-------
REFERENCES
1. Stokinger, H. E. The Metals (Excluding Lead). In: Indus-
trial Hygiene and Toxicology, Chapter 27, D. W. Fassett and
D. D. Irish, eds. Interscience Publishers, New York,
New York, 1962. pp. 1090-1104.
2. Non-Ferrous Metal Data 1974. American Bureau of Metal
Statistics, Inc., New York, New York, 1975. 143 pp.
3. VanHorn, W. Materials Balance and Technology Assessment of
Mercury and Its Compounds on National and Regional Bases.
EPA-560/3-75-007, U.S. Environmental Protection Agency,
Washington, D.C., October 1975. 433 pp.
4. Kirk-Othmer Encyclopedia of Chemical Technology, Second
Edition, Volume 13. John Wiley & Sons, Inc., New York,
New York, 1967. pp. 218-235.
5. Quality Criteria for Water. EPA-440/9-76-023, U.S. Environ-
mental Protection Agency, Washington, B.C., October 1975.
501 pp.
6. Sittig, M. Pollutant Handbook. Noyes Data Corporation,
Park Ridge, New Jersey, 1973. pp. 286-308.
7. TLVs® Threshold Limit Values for Chemical Substances and
Physical Agents in the Workroom Environment with Intended
Changes for 1975. American Conference of Governmental
Industrial Hygienists, Cincinnati, Ohio, 1975. 94 pp.
23
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/2-79-210J
2.
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
5. REPORT DATE
December 1979 issuing date
Status Assessment of Toxic Chemicals: Mercury
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
T.R. Blackwood, D.R. Tierney
T.M. Briggs
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Monsanto Research Corp PEDCo Environmental, Inc
1515 Nichols Road 11*199 Chester Road
Dayton, Ohio 45*107 Cincinnati, Ohio 45246
10. PROGRAM ELEMENT NO.
1AB604
11. CONTRACT/GRANT NO.
68-03-2550
12. SPONSORING AGENCY NAME AND ADDRESS
Industrial Environmental Research Lat>»
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, OHio 45268
- Cinn, OH
13. TYPE OF REPORT AND PERIOD COVERED
Task Final 11/77 - 12/77
14. SPONSORING AGENCY CODE
EPA/600/12
15. SUPPLEMENTARY NOTES
IERL-Ci project leader for this report is Dr. Charles Frank,,513-684-4481
16. ABSTRACT
This report lists the properties, production sources, amounts, and
uses of mercury. Mercury pollution figures, sources, health effects,
environmental significance, and control technologies are cited. Areas
are listed where information is lacking or further study is required.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COS AT I Field/Group
mercury, metals, transition metals, cinna-
bar, mercury isotopes, mercury alloys, [
mercury amalgrams, mercury halides,
mercury inorganic compounds, mercury ore
deposits, metalliferous mineral deposits,
organic compounds, metal containing organi
poisoning, toxic diseases, mercury
smelting, mercury ore
refining, chloralkali
plant s
68D
68G
containing
nineral deposits, mercury
: compounds, mercury
alloys, mercury tellui
ides, Group 2B
compounds
13. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (ThisReport)
Unclassified
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20. SECURITY CLASS (Thispage)
' Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
* U.S. GOVERNMENT PRINTING OFFICE: 1980-657-146/5506
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