United SMw
Environmental Protection
Agwcy
Industrial Environmental Research EPA 600 2-79 210b
Laboratory December 1979
Cincinnati OH 45268
Research and Development
Status
Assessment of
Toxic Chemicals
Arsenic
-------
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
-------
EPA-600/2-79-2l0b
December 1979
STATUS ASSESSMENT OF TOXIC CHEMICALS:
ARSENIC
by
S. R. Archer
T. R. Blackwood
Monsanto Research Corporation
Dayton, Ohio 45407
and
T. K. Corwin
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
-------
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.
ii
-------
FOREWORD
When energy and material resources are extracted, processed,
converted, and used, the related pol'.utional 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
(IERL-Ci) assists in developing and demonstrating new and
improved methodologies that will meet these needs both effi-
ciently and economically.
This report contains a status assessment of the air
emissions. water pollution, health effects, and environmental
significance of arsenic, 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 IERL-Ci to communi-
cate 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
indicative rather than exhaustive.
Industrial
David G. Stephan
Director
Environmental Research
Cincinnati
Laboratory
111
-------
ABSTRACT
Arsenic, which is found naturally in metal ore deposits, is pro-
duced commercially as a byproduct during the processing of
nonferrous metal ores. Estimated 1974 consumption of arsenic
in the United States was 22,300 metric tons with the sole U.S.
producer, the ASARCO copper smelter in Tacoma, Washington, sup-
plying approximately 8,700 metric tons (as arsenic trioxide).
In addition to arsenic trioxide and arsenic metal, there are at
least 45 other arsenic compounds of commercial significance pro-
duced in the U.S. The largest use of arsenic is in the produc-
tion of agricultural pesticides, which includes herbicides,
insecticides, desiccants, wood preservatives, and feed additives.
It is recognized that atmospheric emissions of arsenic from
smelting operations constitute a major pollutant source. Sub-
stantial amounts of arsenic escape to the atmosphere from pyro-
metallurgical copper operations. An estimated 4,500 metric tons
of arsenic were released to the atmosphere in 1976 by primary
nonferrous smelters; nearly 90% of this total was a result of
copper production. Other emission sources include lead and zinc
smelters, glass production plants, coal burning facilities,
arsenical compound production plants, and pesticide application.
Evidence indicates that disposal of high arsenic-containing
wastewater and solid wastes has a potential impact greater than
that of air emissions. One veterinary pharmaceuticals plant has
been measured with a raw waste loading of 10,000 g/m3 arsenic
and 50 g/m3 to 60 g/m3 after treatment.
Since arsenic is a suspected carcinogen, regulations have been
or are being established for human exposure in air and water.
Two arsenical pesticides have recently had their registrations
cancelled. Based upon the information presented in this report,
several items should be considered in future studies. Control
methods are needed for arsenic fume and fugitive emissions from
pyrometallurgical smelter operations, and treatment methods are
needed for discharge of high arsenic-containing wastewaters.
Production statistics and process information is needed to
better understand the production of arsenicals, and fixation and
disposal of high arsenic-containing solid wastes should be
studied including leaching from existing sites.
lV
-------
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.
v
-------
CONTENTS
Foreword.
Abstract.
Figures
Tables.
Conversion Factors
Acknowledgement.
and Metric Prefixes.
l.
2.
3.
Introduction
Summary.
Source Description
Production.
Process description
Uses.
Environmental Significance and Health
Environmental significance.
Health effects.
Control Technology
Regulatory Action.
4 .
5.
6.
References.
Bibliography.
Appendix.
vii
Effects.
iii
iv
. viii
. viii
ix
x
1
2
6
6
8
. 10
. 17
. 17
. 21
. 22
. 24
. 26
. 27
. 30
-------
Number
FIGURES
1
Primary United States nonferrous smelting and
refining locations.
Flowsheet showing basic steps for production of
arsenlC trioxide at a copper smelter.
2
3
Flowsheet of arsenic emissions from production to use.
TABLES
1
2
3
4
Arsenic.
Primary Copper, Lead, and Zinc Smelters
Arsenic Compounds
Arsenic Compounds not Currently Produced
Quantities in the United States
in Significant
5
6
7
Distribution of Arsenic at Copper Smelters.
Distribution of Arsenic at Primary Lead Smelters.
Distribution of Arsenic at Zinc Concentrators
Vlll
Page
8
10
18
3
7
11
15
20
20
20
-------
a
CONVERSION FACTORS AND METRIC PREFIXES
CONVERSION FACTORS
Multiply by
To convert from
To
Degree Celsius (OC)
Kilogram (kg)
Degree Fahrenheit
Pound-mass (pound-mass
avoirdupois)
Mile2
Foot3
Gallon (U.S. liquid)
Pound-mass
Torr (mm hg, O°C)
t; = 1.8 tc + 32
Kilometer2 (km2)
Meter3 (m3)
Meter3 (m3)
Metric ton
Pascal (Pa)
2.204
3.860 x 10-1
3.531 x 101
2.642 X 102
2.205 x 103
7.501 x 10-3
METRIC PREFIXES
Kilo
Milli
k
m
103
10-3
Example
1 kg = 1 x 103 grams
1 mm = 1 x 10-3 meter
Prefix
Symbol
Multiplication factor
aStandard 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.
lX
-------
ACKNOWLEDGEMENT
This report was assembled for EPA by PEDCo-Environmental, Inc.,
Cincinnati, OR, and Monsanto Research Corporation, Dayton, OR.
Mr. D. L. Becker served as EPA Project Officer, and Dr. C. E.
Frank, EPA Consultant, was principal advisor and reviewer.
x
-------
SECTION I
INTRODUCTION
Arsenic, a suspected human carcinogen, is ubiquitous in the
environment. It is produced commercially as a byproduct during
the processing of nonferrous metal ores and naturally occurs in
these metal ore deposits. There is a concern of adverse human
health effects from inorganic arsenic due to its suspected
carcinogenicity-
There is a need to define the various sources from which arsenic
may be mobilized in the environment, to establish the consequent
health and environmental effects, and to examine possible control
techniques and present regulatory actions. This report provides
a brief overview describing these items with emphasis on arsenic
sources and the resulting environmental significance. Producers,
production process, and uses of arsenic are also discussed.
1
-------
SECTION 2
SUMMARY
Arsenic is produced commercially as a byproduct during the pro-
cessing of nonferrous metal ores, with which it is associated in
natural deposits. The ASARCO copper smelter in Tacoma, Washington
is the sole domestic production site for arsenic metal and
arsenic trioxide, from which all other arsenic compounds are
produced. While production information at Tacoma is proprietary,
it is estimated that in 1974 approximately 8,700 metric tons of
arsenic (as arsenic trioxide) were produced. Estimated 1974
United States consumption was 22,300 metric tons, with the
balance of demand over domestic production met by imports.
The domestic recovery process for arsenic consists of placing
the concentrates and raw materials into a roaster, in which they
are heated to between 650°C and 700°C until the arsenic vaporizes.
Gases from the roaster are condensed in two series of brick cool-
ing chambers, yielding a product containing 90% to 95% arsenic
trioxide. Greater purity arsenic trioxide product is produced
by resublimation in a reverberatory furnace at approxmately 538°C,
followed by recondensation. Arsenic metal is occasionally pro-
duced at Tacoma by reducing the oxide with carbon in an oxygen
deficient atmosphere. Table 1 is a summary of highlighted in-
formation regarding arsenic presented in this report.
In addition to arsenic trioxide and arsenic metal, there are at
least 45 other arsenic compounds of commercial significance pro-
duced in the United States. The largest use of arsenic is in
the production of agricultural pesticides, which include herbi-
cides, insecticides, desiccants, wood preservatives, and feed
additives.
Substantial amounts of arsenic are escaping into the atmosphere
from pyrometallurgical copper operations. An estimated 4,500
metric tons of arsenic were released to the atmosphere in 1976
by primary nonferrous smelters; nearly 90% of this total resulted
from copper production. While it is recognized that the atmos-
pheric emissions of arsenic from smelting operations constitute
a major pollution source, evidence indicates that the disposal
of high arsenic-containing wastewater and solid waste has a
potential impact greater than that of air emissions. An inves-
tigation of a plant producing veterinary pharmaceuticals and
intermediate organic chemicals including arsenicals has been
2
-------
TABLE
1.
ARSENIC
Emission source
Requlatorv action
Production:
Off-gas from primary copper,
lead, and zinc smelting
Arsenic trioxide
(8,700 metric tons, 1974)
Arsenic metal
Transportation:
Cleaning of transport
vehicles
Leachate landfill
w
Industrial use:
(Consumption, 1974 -
22,300 metric tons,
for all uses)
Arsenic metal:
Metallurgical additives (3%)
Arsenic compounds:
Insecticides (22%)
Herbicides (23%)
Desiccants and
defoliants (~15%)
Soil sterilizers (17%)
Glass additives (10%)
Miscellaneous (10%)
Consumer use of end products:
Application of arsenical
pesticides
Public exposure due to use
of products
Emission quantity
4,500 metric tons/yr
(90%, 5%, and 5% from
copper, lead and zinc
smelting, respectively).
Air and water emissions
occur - quantities
unknown.
Waste water from ASARCO.
Tacoma has been measured
at 310 g/m3 arsenic.
Unknown.
The amount is expected
to be quite large.
A veterinary pharmaceu-
ticals plant has been
measured with a raw waste
loading of 10,000 g/m3
arsenic and 50 - 60 g/m3
after treatment.
Unknown.
Unknown.
Population exposed
Some smelters are near
population centers.
Produced only at
Tacoma, Washington.
Produced only at
Tacoma, Washington.
Unknown.
Problem centers lie
in watersheds on or
near landfill sites.
No data available.
Unknown.
Unknown.
Control method
Mechanical collectors, heat
exchangers, electrostatic
precipitators (all are
relatively inefficient
8 - 26%).
Neutralization, precipitation,
pond sealing, sludge dis-
posal (landfill).
No data available.
Neutralization, precipitation,
pond sealing, sludge dis-
posal (landfill).
Unknown.
Standard waste treatment
methods are assumed, but
may not be adequate.
Workplace exposure limit of
4 ~g/m3 at 8 hr (Occupational
Safety and Health Administra-
tion). (This may be reduced).
10 ppm in effluent under EPA
effluent guidelines (Best
Practicable Technology). Office
of Air Quality Planning and
Standards is considering an
ambient air standard for arsenic
in 1978.
possible regulation may occur
under the Safe Drinking Water
Act.
Basic copper arsenate and copper
acetoarsenite have been can-
celled for pesticide usage
under Federal Insecticide,
Fungicide, and Rodenticide Act.
Arsenic is also a priority pollut-
ant for study under the Federal
Water Pollutant Control Act.
Possible regulation under Federal
Insecticide, Fungicide, and
Rodenticide Act.
-------
conducted by the EPA. The plant produces two major wastewater
streams, one which contains about 10,000 g/m3 total arsenic and
6,000 gjm3 organics at a flow rate of 75.7 m3/day- The treated
stream contains 50 gjm3 arsenic and it is clarified, neutralized,
settled, and then routed to the city sewer where sludges are
landfilled. Also, there is increasing evidence to indicate that
there may be serious environmental problems by the production of
arsenical pesticides. Since arsenic is a suspected carcinogen,
epidemiological analyses should be conducted to support previous
findings of high incidences of lung cancer in smelter workers
and high arsenic in the urine of both workers and children living
near smelters.
The Environmental Protection Agency (EPA) is considering the
development of regulations under the Clean Air Act. The Office
of Air Quality Planning and Standards has tentative plans for
promulgating an arsenic standard in 1978. Two registered arseni-
cal pesticides have recently had their registrations cancelled.
The Occupational Safety and Health Administration (OSHA) has set
a workplace exposure limit of 4 ~gjm3, which may be downgraded
in the near future. Arsenic is a consent decree compound and is
thus destined for regulation under that agreement. Best Practi-
cable Technology (BPT), as established by the Effluent Guidelines
Division (EGO) of EPA, for the nonferrous metals industry lists
an average effluent concentration of 10 ppm. Finally, regulation
of arsenic under the Safe Drinking Water Act is anticipated.
Based upon the information presented in this report, the follow-
ing items need to be considered in future studies:
.
Methods for control of arsenic fume and fugitive emissions
from pyrometallurgical smelter operations, including assess-
ments of the adequacy of commercially-available control de-
vices, new control technology options, and the ultimate
fate of arsenic with the various control technology options.
. Treatment methods for high-arsenic wastewater discharged
from both smelters and plants producing arsenic compounds.
. Fixation and disposal of high-arsenic solid wastes including
leaching from existing disposal sites.
. Improved understanding of the production of arsenicals--pro-
duction processes, waste streams, control technologies, and
end uses. visits to production facilities in the industry
could provide much of this understanding. Highest priority
would be assigned to those companies with a varied product
slate of arsenicals. However, representative smaller produ-
cers should not be overlooked, as any production process
involving arsenic compounds can result in fugitive emissions
and wastes with serious environmental consequences.
4
-------
.
Environmental behavior of arsenic and arsenic compounds.
. Production statistics, locations and present waste treatment
configurations for the many end use arsenicals.
. Epidemiological analyses investigating high incidences of
lung cancer in smelter workers and high arsenic in the
urine of both workers and children living near smelters.
5
-------
SECTION 3
SOURCE DESCRIPTION
Arsenic is produced commercially as a byproduct during the pro-
cessing of nonferrous metal ores, with which it is associated in
natural deposits. Arsenic occurs primarily as inorganic com-
pounds; it occurs very infrequently in the elemental state. It
also forms a variety of organic compounds; i.e., compounds con-
taining an arsenic-carbon bond. Both organic and inorganic arse-
nic compounds can be toxic to man, and inorganic arsenic compounds
have been associated with lung cancer in worker populations (1).
PRODUCTION
Table 2 lists the 29 domestic primary nonferrous smelters,
indicating the principal likely sources of atmospheric arsenic
emissions for each. Arsenic sublimes at temperatures lower than
the operating temperatures of most existing particulate control
devices, so most arsenic in the concentrate is driven off during
the first high-temperature contact. Figure 1 (2) locates these
facilities.
The ASARCO copper smelter in Tacoma, Washington, is the sole
domestic production site for arsenic metal and arsenic trioxide,
from which all other arsenic compounds are produced. The feed
to Tacoma includes concentrates containing a high proportion of
arsenic (3% to 15%), as well as intermediate products such as
flue dusts, speisses, and other high-arsenic residues °(5% to 30%
arsenic) from other nonferrous smelters. Since the supply of
domestic arsenic exceeds its demand, only a portion of the high-
arsenic residues are shipped to Tacoma; the rest are disposed of
or stored at the smelters. Production information at Tacoma is
proprietary, but the estimated 1974 production of arsenic (as
(1) Arsenic Sources and Control Technology Review. Contract No.
68-01-2984, U.S. Environmental Protection Agency, Cincinnati,
Ohio, July 1976.
(2) Davis, W. E., et ale National Inventory of Sources and Emis-
sions-1968. Contract No. CPA 70-128 (PB 220 619), U.S. En-
vironmental Protection Agency, Durham, North Carolina, May
1971. 60 pp.
6
-------
TABLE
Company
Arnax, Inc.
Arnax - Homestake
Tollers
The Anaconda Co.
Asarco, Inc.
Lead
The Bunker Hill Co.
~
Cities Services Co.
Copper Range Co.
Inspiration Consolidated
Copper Co.
Kennecott Copper Corp.
Magma Copper Co.
National Zinc Co.
New Jersey Zinc Co.
Phelps Dodge Corp.
St. Joe Minerals Corp.
2.
PRIMARY COPPER,
LEAD, AND ZINC SMELTERS
Location
East St. Louis, IL
Boss, MO
Anaconda, MT
Tacoma, WA
El Paso, TX
Hayden, AZ
East Helena, MT
Glover, MO
Corpus Christi, TX
Columbus, OH
Kellogg, ID
Copperhill, TN
White Pine, MI
Miami, AZ
Garfield, UT
Hurley, NM
Hayden, AZ
McGill, NV
San Manuel, AZ
Bartlesville, OK
Palmerton, PA
Morenci, AZ
Douglas, AZ
Hidalgo, NM
Ajo, AZ
Herculaneurn, MO
Monaca, PA
Principal
product
metal
Zinc
Lead
Copper
Copper
Copper
Lead
Copper
Lead
Lead
Zinc
Zinc oxide
Lead
Zinc
Copper
Copper
Copper
Copper
Copper
Copper
Copper
Copper
Zinc
Zinc
Copper
Copper
Copper
Copper
Lead
Zinc
Capacity
metric
tons/yr
76,000
127,000
180,000
91,000
104,000
109,000
163,000
109,000
100,000
98,000
20,000
118,000
98,000
20,000
82,000
64,000
254,000
73,000
73,000
45,000
181,000
45,000
103,000
161,000
115,000
91,000
64,000
204,000
227,000
Roasting
furnaces
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
Likely sources of
arsenic emissions
Sinter Blast
machines furnaces
x
x
Smelting
furnaces
x
x
x
x
x
x
x
xa
x
x
x
x
x
x
x
x
x
x
x
x
x
x
aThe Kennecott-Garfield 'smelter is converted to the Noranda process, in which a single furnace combines
most of the functions of roasting, smelting, and converting.
x
x
x
x
x
x
x
-------
Figure 1.
Primary United States nonferrous
smelting locations (2).
arsenic trioxide) was 8,700 metric tons. a Estimated 1974 United
States consumption was 22,300 metric tons, with the balance of
demand over domestic production met by imports due to economic
and purity considerations. Demand is expected to increase at
0.3%jyr through 1980. Sweden and Mexico, which together account
for over half of world arsenic trioxide production, are the
principal source of imports. Arsenic trioxide enters the United
States duty-free. There are also minor imports of arsenic metal,
on which there is a 2.69jkg duty. The United States holds about
one-fourth of estimated world arsenic reserves.
PROCESS DESCRIPTION
Since most of the arsenic produced is in the form of arsenic tri-
oxide (AS203) as a byproduct of the smelting of other metals, the
production of arsenic is closely associated with the recovery and
treatment of arsenic-bearing flue dusts. As arsenic trioxide is
volatilized during the smelting of copper, lead, zinc, and other
metals, it is concentrated in this dust. The crude flue dust
al metric ton = 106 grams; conversion factors and metric system
prefixes are presented in the prefatory pages of this report.
8
-------
carrying up to 30% arsenic trioxide may also contain oxides of
copper or lead, and other metals such as antimony, zinc, and
cadmium (2).
The crude flue dust recovered during the smelting operation is
further refined by mixing it with a small quantity of pyrite or
galena concentrate prior to roasting. The pyrite or galena pre-
vents the formation of arsenites during roasting, and produces a
clinkered residue suitable for return to the process for recovery
of other metals. The gases from roasting are passed through a
series of brick chambers or kitchens, in which the temperature
varies from 221°C in the first, to 99°C or less in the last. As
the gases cool, arsenic trioxide condenses as a crude white
powder, 90% to 95% pure. Much of the product is used in this
form without further refinement (2).
If higher purity is required, the refining is usually carried
out in a reverberatory furnace at a roasting temperature of about
538°C. The vapors first pass through a settling chamber and then
through a series of kitchens. In the settling chamber, the tem-
perature is maintained above the condensation temperature of the
trioxide. In the kitchens near the furnace a black, amorphous
mass is condensed which contains about 95% arsenic trioxide.
This product is reprocessed. The bulk of the trioxide is con-
densed in the other kitchens at temperatures ranging from 121°C
to 182°C, and most of the dust which exits from the kitchens is
caught in a baghouse. Some of the arsenic escapes, all that is
in the vapor phase, plus a relatively small amount of the dust.
Figure 2 shows the basic steps for production of arsenic trioxide.
In addition to arsenic metal and arsenic trioxide, there are at
least 45 other arsenic compounds of commercial significance pro-
duced in the united States, all of which are made from arsenic
trioxide. Table 3 presents a listing of 45 known commercial
arsenic products, their end uses, producing companies, and pro-
duction sites. These products are manufactured by 28 companies
with production either in excess of 0.45 metric tons/yr or an
annual value of at least $1,000. Seven of these facilities are
in New Jersey, four in California, and three each in New York,
Illinois, Texas, and Oklahoma. Information on production tech-
nologies and site-specific production stastistics is considered
proprietary by the manufacturers; however, this information can
be made available for regulatory purposes. Table 3 is not an
exhaustive listing of all arsenicals; there may be other arsenic
products that are made only occasionally in small batches and
are, therefore, not generally considered commercial arsenic
compounds. Table 4 lists 31 arsenic compounds that have been
manufactured in the past but that are not believed to be in
current commercial production; however, if any of these are
produced occasionally in small lots, it is likely to be by com-
panies listed in Table 3.
9
-------
DUST-LADEN
VAPOR & GASES
LOW ARSENI C
AND
VALUABLE
RES I DUE
EXPANSION
CHAMBER
WASTE HEAT
BOI LER
FUMES
AND DUST
HIGH
ARSENI C
FUMES
VALUABLE
RES I DUE
PRECI PITATOR
S02
( TO BE CONVERTED TO H2S04 )
AND WASTE GASES TO STACK
WHITE ARSENIC
FOR MARKET
Figure 2.
Flowsheet showing basic steps for production
of arsenic trioxide at a copper smelter (2).
USES
The largest use of arsenic is in the production of agricultural
pesticides, which includes herbicides, insecticides, desiccants,
wood preservatives, and feed additives. Arsenic trioxide was
the raw material for the older inorganic pesticides, including
lead arsenate, calcium arsenate, and sodium arsenite. The newer
major organic arsenical pesticides include three herbicides,
monosodium and disodium methanearsonate (MSMA and DSMA) and cac-
odylic acid, and four feed additives that are substituted phenyl-
arsonic acids. The organoarsenical segment of the pesticides
industry produced approximately 15 products totaling 1.9 x 104
metric tons in 1973. This was an increase of almost 4.5 x 103
metric tons over 1972 production. Arsenic metal has several
minor uses, primarily as an additive in metallurgic applications,
10
-------
TABLE
3.
ARSENIC COMPOUNDS
Chemical
Uses
Amine methanearsonate
(AMA)
Antimony arsenate
Arsambide (N-carbamoylar-
sonilic acid)
Arsanilic acid
Arsaphen (acetarsone)
Arsenic
f-'
f-'
Arsenic acid
Arsenic iodide
Arsenic pentafluoride
Arsenic trifluoride
Company
W. A. Cleary Corp.
Vineland Chemical Co., Inc.
City Chemical Corp.
Eli Lilly & Co./Tippecanoe Labs
Polychemical Labs, Inc.
Rohm & Haas Co./Whitmayer Labs
R.S.A. Corp.
Abbott Labs/Agri. & Vet. Prods.
Fleming Labs, Inc.
Sterling Drug, Inc./Winthrop Labs
ASARCO, Inc.
Los Angeles Chern. Co.
Osmose Wood Preserving Co.
Pennwalt Corp./Inorganic Chemical
Woolfolk Chern. Works, Inc.
City Chern. Corp.
Pennwalt Corp./Ozark-Mahoning Co.
Pennwalt Corp./Ozark-Mahoning Co.
Location
Somerset, NJ
Vineland, NJ
Jersey City, NJ
Lafayette, IN
Bronx, NY
Myerstown, PA
Ardsley, NY
North Chicago, IL
Charlotte, NC
Rensselaer, NY
Tacoma, WA
South Gate, CA
Memphis, TN
Bryan, TX
Fort Valley, GA
Jersey City, NJ
Tulsa, OK
Tulsa, OK
Herbicide.
Medicinal.
Arsanilates; mfg. of arsenical
medicinal chemicals, veterinary
medicine.
Medicinal.
Metallic form: alloying additive
for metals, especially lead and
copper (shot, battery grids,
cable sheaths, boiler tubes).
High-purity (semiconductor)
grade: used to make gallium
arsenide for dipoles and other
electronic devices; doping agent.
in germanium and silicon solid
state products; special solders
medicine.
Mfg. of arsenates; glass making
wood treating process; defoli-
ant desiccant for cotton;
soil sterilant.
Analytical chemistry, medicine.
(continued)
-------
TABLE
3
(con tin ued)
Location
Chemical
Uses
Arsenic trioxide
Arsine
f-'
N
1,2-BiS(diphenylarsino)
ethane
Bis(2-diphenylarsinoethyl)
phenyl phosphine
1,2-Bis(diphenylarsino)
methane
Cacodylic acid (dimethyl-
arsinic acid)
Cacodylic acid, sodium salt
Calcium arsenate
Calcium arsenite
CAMA (calcium acid methyl
arsenate)
Cobalt arsenate
Company
ASARCO, Inc.
Mallinckrodt Inc./Industrial Chern.
Airco, Inc./Airco Industrial Gases
G. D. Searle & Co./Matheson Gas
Pressure Chemical Co.
Pressure Chemical Co.
Pressure Chemical Co.
The Ansul Co./Chem. Group
Vineland Chern. Co., Inc.
Vineland Chern. Co., Inc.
Los Angeles Chemical Co.
Woolfolk Chern. Works, Inc.
Los Angeles Chemical Co.
Vine 1 and Chern. Co., Inc.
City Chemical Corp.
Tacoma, WA
St. Louis, MO
Santa Clara, CA
Cucamonga, CA
E. Rutherford, NJ
Gloucester, MA
Joliet, IL
La Porte, TX
Morrow, GA
Newark, CA
Ardsley, NY
Ardsley, NY
Ardsley, NY
Marietta, WI
Vineland, NJ
Vineland, NJ
South Gate, CA
Fort Valley GA
South Gate, CA
Vineland, NJ
Jersey City, NJ
Pigments, ceramic enamels, ani-
line colors; decolorizing agent
in glass; insecticide; rodenti-
cide; herbicide; sheep and
cattle dip; hide preservative;
wood preservative; preparation
of other arsenic compounds.
Organic synthesis; military
poison gas; electronics.
Herbicide.
Herbicide, medicine.
Insecticide, germicide.
Insecticide, germicide.
Herbicide.
Painting on glass; coloring
glass.
(continued)
-------
TABLE
3
(continued)
Chemical
Uses
Company
Location
Copper acetoarsenite
Copper arsenate
Diphenylarsine
l-Diphenylphosphine-2-di-
phenylarsino ethane
DSMA (disodium methyl
arsenate)
Gallium arsenide
I--'
w
Gallium arsenide phosphide
Hexafluoro arsenic acid
Indium arsenide
Lead arsenate
Lithium arsenate, primary
Methylarsine oxide
Methylarsine sulfide
MSMA (monosodium methyl
arsenate)
Los Angeles Chemical Co.
City Chemical Corp.
Pressure Chemical Co.
Pressure Chemical Co.
The Ansul Co./Chem. Group
W. A. Cleary Corp.
Diamond Shamrock/Biosciences
and Metals
Vineland Chern. Co., Inc.
Apache Chems., Inc.
Eagle-Picher Ind./Electronic Div.
Monsanto Co./Electronics Div.
Monsanto Co./Electronics Div.
Pennwalt Corp./Ozark-Mahoning
Monsanto Co./Electronics Div.
Dimensional Pigments, Inc.
Los Angeles Chemical Co.
Rona Pearl, Inc.
Woolfolk Chemical Works, Inc.
City Chemicals Corp.
Vine land Chem. Co., Inc.
Vine land Chern. Co., Inc.
The Ansul Corp./Chem. Group
Diamond Shamrock/Biosciences and
Metals
Vine land Chern. Co., Inc.
South Gate, CA
Jersey City, NJ
Ardsley, NY
Ardsley, NY
Marietta, WI
Somerset, NJ
Greens Bayon, TX
Vine land, NJ
Rockford, IL
Miami, OK
Quapaw, OK
St. Peters, MO
St. Peters, MO
Tulsa, OK
St. Peters, MO
Bayonne, NJ
South Gate, CA
Bayonne, NJ
Jersey City, NJ
Vineland, NJ
Vineland, NJ
Marietta, WI
Greens Bayon, TX
Vineland, NJ
Wood preservative; larvicide.
Insecticide; fungicide.
Herbicide, pharmaceutical.
Semiconductor in light-emitting
diodes injection lasers;
solar cells; magento-resistent
devices; thermistors; micro-
wave generation.
Semiconductors.
Semiconductors; injection laser.
Insecticide, herbicide.
Fungicide.
Fungicide.
Herbicide.
(continued)
-------
TABLE
3
(continued)
Chemical
Uses
Company
Location
3-Nitro-4-hydroxyphenylar-
sonic acid
4-Nitrophenylarsonic acid
Potassium arsenate
Potassium hexafluoroarsenate
Silver arsenate
Silver arsenite
f-'
.f::>
Sodium arsanilate
Sodium arsenite
Strychnine arsenate
Triphenylarsine
Zinc arsenate
Salsbury Laboratories
Salsbury Laboratories
City Chemical Corp.
Pennwalt Corp./Ozark-Mahoning
City Chemical Corp.
City Chemical Corp.
Abbott Labs/Agri. & Vet. Prod.
Rohm & Haas/Whitmoyer Labs
Blue Spruce Co.
Los Angeles Chemical Co.
Pennwalt Corp./Inorganic Chern. Co.
Woolfolk Chemical Works, Inc.
City Chemical Corp.
Pressure Chemical Co.
City Chemical Corp.
Charles City, IA
Charles City, IA
Jersey City, NJ
Tulsa, OK
Jersey City, NJ
Jersey City, NJ
North Chicago, IL
Myerstown, PA
Bound Brook, NJ
South Gate, CA
Tacoma, WA
Fort Valley, GA
Jersey City, NJ
Ardsley, NY
Jersey City, NJ
Pharmaceutical.
Pharmaceutical.
Flypaper; insecticide; labora-
tory reagent preserving hides;
printing textiles.
Medicine.
medicine;
Medicine; veterinary
organic synthesis.
Manufacturing
Manufacturer of arsenical soaps
for taxidermists; antiseptic;
dying insecticides; hide pre-
servation herbicide
Insecticide; wood preservation.
-------
TABLE 4.
ARSENIC COMPOUNDS NOT CURRENTLY PRODUCED IN
SIGNIFICANT QUANTITIES IN THE UNITED STATES
Compound
Use
Arsacetin
Arsenic disulfide
Arsenic pentasulfide
Arsenic pentoxide
Arsenic thioarsenate
Arsenic tribromide
Arsenic trichloride
Arsenic trisulfide
Arsphenamine
Arethinol
Ferric arsenate
Ferric arsenite
Ferrous arsenate
Magnesium arsenate
Mercuric arsnilate
Mercuric arsenate
Potassium arsenite
Silver arsphenamine
Silver methylarsenate
Sodium arsenate
Sodium arsphenamine
Strontium arsenite
Tryparsamide
Tetraarsenic tetrasulfide
Arsenic pentasulfide
Methanarsenic acid
Methyldihydroxyarsine
Dimethylhydroxyarsine
Trimethylarsine
Trimethylarsineoxide
Arsonic acids
Medicine.
Depilatory agent; paints; rodenticides; glass.
Pigments; blue fire.
Insecticide; dyeing and printing.
Thermal protectant.
Analytical chemistry, medicine.
Intermediate for organic arsenicals.
Pigment; glass.
Medicine.
Medicine.
Insecticide.
Medicine.
Medicine, insecticide.
Insecticide.
Medicine.
Medicine; paints.
Medicine; mirrors.
Medicine.
Algicides.
Medicine; insecticides; germicide, textiles.
Medicine.
Medicine.
Medicine.
Unknown.
Unknown.
Unknown.
Unknown.
Unknown.
Unknown.
Unknown.
Unknown.
in glass production, as a catalyst in several manufacturing pro-
cesses, and in medicine. Arsenical drugs are still used in
treating tropical diseases, such as African sleeping sickness
and amebic dysentery, and are used in veterinary medicine to
treat parasitic diseases, such as heartworm (filariasis) in dogs
and blackhead in turkeys and chickens.
To summarize the end use information presented in Table 3, the
1974 demand for arsenic broke down as follows:
15
-------
Percent
Arsenic metal:
Metallurgical additives
Arsenic compounds:
Insecticides
Herbicides
Desiccant and defoliants
Soil sterilizers
Wood preservatives
Animal food additives
Glass additives
Miscellaneous
3
22
23
15
17
6
2
10
2
Although no single use dominates the market, the general category
of pesticides includes 83% of the total. The production of
arsenic metal has increased since 1974 when research indicated
that it can impart strength to cast ferrous alloys. Chlorinated
hydrocarbons are potential substitutes for arsenates in some
applications, but restrictions on their use may inhibit extensive
substitution.
16
-------
SECTION 4
ENVIRONMENTAL SIGNIFICANCE AND HEALTH EFFECTS
ENVIRONMENTAL SIGNIFICANCE
Arsenic is not an abundant element, but it can be found in trace
quantities almost everywhere since it is widely distributed in the
earth's crust. It is present in sea water, in coal deposits, and
in virgin soils as well as in ores. The most extensive occurrence
is with copper, lead, cobalt, nickel, iron, gold, and silver (2).
Arsenic is generally regarded as a contaminant in ore and must
be removed during smelting and refining in order to improve the
quality of the metal; thus, arsenic emissions can occur during
metallurgical processing. Figure 3 shows the sources of arsenic
emissions incidental to processing nonferrous ores, from produc-
tion of arsenic and arsenic compounds, and from the use of arsen-
ical compounds. Figure 3 also indicates the media to which the
arsenic is emitted.
Inorganic arsenic is emitted to the air from several sources,
including copper, lead, and zinc smelters, glass production
plants, coal-burning facilities, cotton gins, arsenical-compound
(including pesticides) production plants, and pesticide applica-
tion. Organic arsenic discharges are associated with the manu-
facture and use of pesticides. Trivalent arsenic which is a
common contaminant of ores, occurs naturally and is the major
component of arsenic emissions from smelters (3).
An environmental assessment of the primary copper, lead, and zinc
industries concluded that substantial amounts of arsenic are
escaping into the atmosphere from pyrometallurgical copper opera-
tions (4). Emissions are less significant in other copper pro-
cessing steps or during lead and zinc smelting. An estimated
4,500 metric tons of arsenic were released to the atmosphere in
1976 by primary nonferrous smelters; nearly 90% of this total
(3) Summary Characteristics of Selected Chemicals of Near-Term
Interest. EPA-560/4-76-004 (PB 225 817), u.S. Environmental
Protection Agency, Washington, D.C., April 1976. 50 pp.
(4) Environmental Assessment of Primary Copper, Lead and Zinc
Industries, pedCo draft reports on Contract No. 68-02-1321
and 68-02-2535, u.S. Environmental Protection Agency,
Cincinnati, Ohio, 1978.
17
-------
ARSENIC INPUTS I
I
EMISSIONS FROM PROCESSING NONFERROUS ORES
IMPORTS
FERRO ALLOYS
RECYCLED MET AL
COPPER ORES
I
I
I
I
I
COPPER
SMELTER
TO AIR.
IN PRODUCT
SLAG S TO LAND.
SLUDGES TO LAND.
f-'
CO
I
I
I
I
IMPORTED DUSTS I
AND CONCENTRATES
FLUE DUSTS
CONTROL D EV ICE
COLLECTED DUST
TO LAND.
LEACH RESIDUES
TO LAND.
TO WATER 0
IN PRODUCT
I TO AI R.
I FLUE DU STS
LEAD ORES I LEAD SM ELTER CONTROL DEVICE COLLECTED DUSTS
I SLAGS TO LAND.
I
I SLUDGES TO LAND.
I
I
I I N PRODUCT
I
ZINC ORES I ZINC SMELTER
I RESIDUES
TO AIR. TO LAND.
FLUE OUSTS COLLECTED DUSTS t
CONTROL D EV I CE
TO WATER 0
Figure
EMISSIONS FROM ARSENIC AND ARSENIC COMPOUND PRODUCTION I EMISSIONS FROM USE
I
CONTROL DEVI CE COLLECTED DU ST I
FLUE OUSTS
TO AI R. I
I I N PRODUCT
FLUE DUSTS.
ARS IC LEAD ALLOY
METAL PRODUCTION
SLAG S TO LAND.
COPPER ALLOY
PRODUCTION I N PRODUCT
TO WATER 0 I
ARSENIC I
PESTICIDES I
RECOVERY, PRODUCTION TO AI R .
TACOMA I
TO LAND.
PESTICIDES I
I TO AIR.
FEED ADDITIVES TO AI R. I
PRODUCTION I
FEED ADDITIVES TO LAND.
ARSENIC I
TROX IDE WOOD PRESERVATIVES
PRODUCTION IN PRODUCT
GLASS TO AIR.
PRODUCTION
IN PRODUCT
MISCELLANEOUS USES IN PRODUCT
TO WATER 0
KEY
. AIR EMISSION
. LAND EMI SSION
o WATER EMISSION
arsenlC
emissions
use.
Flowsheet of
3.
from production
to
-------
was a result of copper production. Land-destined wastes con-
taining arsenic include flue dusts and residues from smelters,
slags from steelmaking, and fly ash from coal combustion, as well
as other minor sources. There is serious potential for environ-
mental degradation by the leaching of these wastes into water
supplies. Direct sources of arsenic into water include sulfuric
acid plant blowdown and wastewater from various hydrometallurg-
ical smelter processes. It is difficult to treat arsenic waste-
water streams because of its solubility- The waste streams from
arsenic recovery at A8ARCO-Tacoma include the process ~as str~am
(C02' H20, 802, arsenic fume), washdown water (310 glm arsenlc),
and fugitive dusts from materials handling. In many cases at non-
ferrous smelters, solid residues such as slags and dusts from gas
cleaning operations are recycled. However, this practice can lead
to the build-up of arsenic and other trace metals to unacceptable
levels in the system, requiring the use of purge streams. These
materials present a difficult disposal problem to prevent fugi-
tive emissions or leaching into underground or surface waters.
An environmental assessment of the primary copper, lead, and
zinc industries analyzes these industries as a series of inter-
related production processes--45 for copper, 22 for lead, and 17
for zinc (4). Certain of these process steps for each industry
involve the release of arsenic to various media. Each process
is examined in terms of its function, input materials, operating
conditions, utility consumption, waste streams, and control tech-
nology. The appendix is an example of a process description
indicating the types of information presented.
While it is recognized that the atmospheric emissions of arsenic
from smelting operations constitute a major pollutant source,
evidence indicates that the disposal of high arsenic wastewater
and solid waste has a potential impact of greater than that of
the air emissions. Tables 5, 6, and 7 detail the magnitude and
sources of arsenic discharged during nonferrous ore smelting (1).
Proprietary limitations make it difficult to obtain detailed in-
formation regarding production processes and waste treatment
configurations, not only in the nonferrous industry, but in end
use of arsenicals as well. Characterization of waste streams in
the end use industry is generally lacking, as most arsenicals are
produced in batch lots at plants with many other products, and
the effluents are often mixed prior to treatment and disposal.
There is increasing evidence to indicate that there may be
serious environmental problems created by the production of
arsenical pesticides. In one case, a pesticide manufacturer in
Virginia sprayed high-arsenic wastes onto its property, which
was in close proximity to the Potomac River. An analysis of the
soil during a subsequent sale of the property revealed massive
levels of arsenic contamination. At the request of the city,
the soil was excavated, stored in sealed drums, and landfilled.
The effects from the leaching of this material into the river
are not known.
19
-------
TABLE 5.
DISTRIBUTION OF ARSENIC AT COPPER SMELTERS (1)
Arsenic containing source
Metric tonsjyr
Lake copper product
Fire-refined copper product
Electrolytic copper product
Slags to land disposal
Sludges to land disposal
Flue dusts to land disposal
Lead residues dissipated to
Treated wastewaters
Air emissions
Commercial white arsenic
land
30
6
7
1,900
1,500
9,600
8,800
32
4,800
8,300
35,000
TOTAL
TABLE 6.
DISTRIBUTION OF ARSENIC AT PRIMARY LEAD SMELTERS (1)
Arsenic containing source
Metric tonsjyr
Air emissions
Retained in refined lead
Land-destined solid wastes
TOTAL
240
20
800
1,060
TABLE 7.
DISTRIBUTION OF ARSENIC AT ZINC CONCENTRATORS (1)
Arsenic containing source
Metric tonsjyr
Air emissions
Retained in zinc products
Land-destined solid wastes
Wastewater effluents
Residues shipped to lead smelters
TOTAL
190
5
240
0.4
210
525
An investigation of a plant that produces veterinary pharmaceu-
ticals and intermediate organic chemicals including arsenicals
has been conducted by the U.S. EPA. The plant produces two
major wastewater streams, one of which contains about 10,000 gjm3
total arsenic and 6,000 gjm3 organics at a flow rate of
75.7 m3jday. This stream is treated by 2-stage batch precipita-
tion using high-lime and manganous sulfate as precipitants. The
treated wastewater, which contains 50 gjm3 to 60 gjm3 arsenic,
20
-------
is clarified, neutralized, settled, and then routed to the city
sewer where the sludges are landfilled. High concentrations of
arsenic have been found in the municipal wastewater. A more
extensive sampling and analysis program is scheduled, preliminary
to the design of acceptable treatment methods.
The two preceding examples of arsenical production plants give
some indication of the nature of the environmental problems that
can arise at such facilities. Although little information is
available, it is possible that many of the other production sites
listed in Table 3 are creating similar problems.
Several arsenic cycles have been proposed to interrelate the
sources, emissions, movement, distribution, and sinks of various
forms of arsenic in the environment. Arsenic is continuously
cycling in the environment, due to oxidation, reduction, and
methylation reactions. The methylation process is a true detox-
ification, as methanearsonates and cacodylates are only one
two-hundreth as toxic as sodium arsenite.
HEALTH EFFECTS
A health effects study of the primary copper, lead, and zinc
industries was initiated recently by IERL-Ci. A comprehensive
health effects literature search was followed by a retrospective
epidemiological analysis comparing disease-specific mortality
parameters for counties that have contained smelters for over
35 years to those for all surrounding counties. The results of
this study indicate an observed incidence of various types of
cancer in the counties with smelters that was higher than in the
surrounding counties or the national average. Smelting zinc ore
concentrates with high levels of arsenic was clearly associated
with significantly elevated rates of cancer of the trachea, lung,
and bronchus. The fact that arsenic is a suspected carcinogen
would indicate that more definite studies of this nature should
be undertaken. These data also support similar conclusions from
a previous study that showed a high incidence of lung cancer in
smelter workers and high arsenic in the urine of both the workers
and children living near the smelter.
21
-------
SECTION 5
CONTROL TECHNOLOGY
The method of treatment of the off-gases from high-temperature
operations at nonferrous smelters varies, but the general pat-
terns are the same. The gas is first passed through mechanical
collectors and heat exchangers to remove large particles and
reduce its temperature. Expansion chambers, balloon flues,
cyclones, and waste heat boilers are all in use at primary copper
smelters. Dust is finally collected in electrostatic precipi-
tators; however, these devices are only partially effective for
arsenic removal because their operating temperatures are above
those necessary to effectively condense the arsenic fumes. Tests
of a hot electrostatic precipitator on the reverberatory furnace
at an Arizona copper smelter have indicated that only from 8%
to 26% of the arsenic present in the concentrate fed to the fur-
nace is being captured in this particular type of control device.
At the ASARCO-Tacoma smelter, the process gas from the arsenic
plant is cleaned with an electrostatic precipitator, currently
being replaced by a fabric filter. Fugitive emissions are con-
trolled by fabric filters on the ventilation air. The controls
in use at plants producing arsenic compounds are not known.
Fabric filters have higher efficiency that electrostatic pre-
cipitators, but they require 2 to 3 times the power and are also
more expensive to purchase and install. They can be expected,
however, to receive wider use as more complete arsenic control
is required. High-pressure-drop venturi scrubbers are capable
of effective removal of arsenic from a gas stream. They are now
used at smelters to remove arsenic and other impurities in the
gas which is fed to sulfuric acid manufacture equipment to pre-
vent damage to the acid-producing catalyst. However, their use
creates a water disposal problem. A copper smelter in Sweden
achieves 98% arsenic removal from the combined gas stream from
a roaster and electric smelting furnace in a 2-stage electro-
static precipitator with an intermediate cooling tower. Temper-
ature control is critical, and the second stage operates at 130°C
to l40°C to precipitate the majority of the sublimed arsenic.
A 2-stage system using an electrostatic precipitator and fabric
filter with intermediate cooling is also reported to be operating
successfully at a Canadian smelter.
22
-------
When considering the control of high-arsenic waste streams, it
must be kept in mind that effective collection may create a
waste disposal problem in another media. For example, because
there is already an oversupply of arsenic, a disposal problem is
created by collection of high-arsenic dusts in particulate con-
trol devices. Due to their slight solubility, these dusts can
leach into streams and ground water supplies unless stored in
weatherproof, siftproof silos, or in hopper cars. A major
research program at Montana College of Mineral Science and Tech-
nology being conducted for IERL-Ci is investigating the fixation
of arsenic wastes to permit their safe disposal.
As has been previously indicated, little is known about the con-
trol technologies in use at the plants producing the various
arsenic compounds from arsenic trioxide. However, based on the
available evidence, conventional wastewater treatment methods
such as neutralization and precipitation and solid waste disposal
such as landfills are clearly inadequate for high-arsenic wastes.
Careful treatment must be provided to prevent fugitive emissions,
discharge into waterways, or leaching into water supplies. A
review of wastewater treatments is contained in Patterson and
Minear's publication for the state of Illinois (5).
(5) Patterson, J. W. and Minear, R. A., Wastewater Treatment
Technology, Second Edition, State of Illinois, Institute of
Environmental Quality, January 1973.
23
-------
SECTION 6
REGULATORY ACTION
The following list of regulatory actions, control options,
attendant impacts, and personnel contacts has been prepared to
show present Federal activities concerning arsenic (6):
. Air Pollution Assessment--An assessment of arsenic as
an air contaminant includes a summary of the analysis
of the National Air Sampling Network samples and other
air samples around nine smelters. The final report
deadline was mid-1976. Josephine Cooper, OAQPS, (919)
688-8146, X-SOl.
.
Effluent Guidelines--The revision of best available
technology limitations will include considerations of
arsenic. A broad examination is being directed to the
best approach for controlling arsenic. Guidelines for
some industrial categories can be expected within the
next two years. Ernst Hall, OWPS, (202) 426-2576.
. Hazardous Material Spills--Arsenic is included in the
preliminary listing of hazardous chemicals under Section
311 of FWPCA. Mandatory reporting of any spill and
clean-up and civil penalties are contemplated. Promul-
gation of the final regulation has been considered for
late 1976. Allen Jennings, OWPS, (202) 245-0607.
. Interim Drinking Water Standards--A maximum permissible
concentration of 0.05 g/m3 for arsenic in drinking water
has been promulgated. This concentration is currently
being reviewed in connection with the development of
additional standards in 1977. Joseph Cotruvo, OWS, (202)
766-5643.
. New Source Performance Standards--Arsenic data are being
collected from process sources at primary copper, zinc,
and lead smelters. Whether standards are set under Section
(6 )
Identification of Selected Federal Activities Directed to
Chemicals of Near-term Concern. EPA-560j4-76-006, U.S.
Environmental Protection Agency, Washington, D.C., July
1976. 36 pp.
24
-------
111 of the Clean Air Act is contingent on these data and
the air pollution assessment. The overall study will take
two years. Alfred Vervaert, OAQPS, (919) 549-8411, X-301.
. Review of Arsenical Pesticides--Arsenic is a candidate
for rebuttable presumption proceeding under Section 3 of
FIFRA. The determination deadline under this proceeding
was May 1977- Ronald Dreer, OPP, (202) 755-5687.
. Water Quality Criteria--A concentration of 50 mg/m3 has
been proposed for total arsenic as a water quality
criterion. David Critchfield, OWPS, (202) 245-3042.
. Workplace Standards--Revised arsenic workplace standards
were proposed in January 1975. The final review of the
inflationary impact statement is being completed. After
this review and hearings, the final standard may be pro-
mulgated. Gerald Weinstein, OSHA, (202) 523-7186.
Arsenic is designated a priority pollutant under the Federal
Water Pollution Control Act.
25
-------
REFERENCES
1.
Arsenic Sources and Control Technology Review. Contract No.
68-01-2984, u.S. Environmental Protection Agency, Cincinnati,
Ohio, July 1976.
2.
Davis, W. E., et ale National Inventory
sions-1968. Contract No. CPA 70-128 (PB
Environmental Protection Agency, Durham,
May 1971. 60 pp.
of Sources and Emis-
220 619), u. S.
North Carolina,
3.
Summary Characteristics of Selected Chemicals of Near-Term
Interest. EPA-560j4-76-004 (PB 225 817), u.S. Environmental
Protection Agency, Washington, D.C., April 1976. 50 pp.
4.
Environmental Assessment of Primary Copper, Lead and Zinc
Industries, PedCO draft reports on Contract No. 68-02-1321
and 68-02-2535, u.S. Environmental Protection Agency,
Cincinnati, Ohio, 1978.
5.
Patterson, J. W. and Minear, R. A., Wastewater Treatment
Technology, Second Edition, State of Illinois, Institue of
Environmental Quality, January 1973.
6.
Identification of Selected Federal Activities Directed to
Chemicals of Near-term Concern. EPA-560j4-76-006, U.S.
Environmental Protection Agency, Washington, D.C., July
197 6 . 3 6 pp.
26
-------
BIBLIOGRAPHY
Arsenic, National Academy of Sciences, EPA Contract No. 68-02-
1226, 1977.
Assessment of Industrial Waste Practices in the Metal Smelting
and Refining Industry, Volume II, Primary and Secondary
Nonferrous Smelting and Refining. Calspan Corporation,
Draft, April 1975.
Assessment of the Adequacy of Pollution Control Technology for
Energy Conserving Manufacturing Process Options. Industry
Assessment Report on the Primary Copper Industry.
Arthur D. Little, Inc., Draft, October 1974.
Background Information for New Source Performance Standards:
Primary Copper, Zinc, and Lead Smelters, Volume I, Proposed
Standards. EPA-450/2-74-002a, u.S. Environmental Protect-
ion Agency, Research Triangle Park, North Carolina,
October 1974.
Compilation and Analysis of Design and Operation Parameters for
Emission Control Studies. Pacific Environmental Services,
Inc. (Individual draft reports).
David, W. E. National Inventory of Sources and Emissions:
Copper, Selenium, and Zinc. PB 210 679, PB 210 678, and
PB 210 677. u.S. Environmental Protection Agency, Research
Triangle Park, North Carolina, May 1972.
Development Document for Interim Final Effluent Limitations
Guidelines and Proposed New Source Performance Standards
for the Primary Copper Smelting Subcategory and the
Primary Copper Refining Subcategory of the Copper Segment
of the Nonferrous Metals Manufacturing Point Source
Category. EPA 440/1-75-032-b, u.S. Environmental Protect-
ion Agency, February 1975.
Encyclopedia of Chemical Technology. Interscience Publishers,
a division of John Wiley & Sons, Inc., New York, New York,
1967.
27
-------
Fejer, M. E. and D. H. Larson. Study of Industrial Uses of
Energy Relative to Environmental Effects. U.S. Environ-
mental Protection Agency, Research Triangle Park, North
Carolina, July 1974.
Halley, J. H. and B. E. McNay. Current Smelting Systems and
Their Relation to Air Pollution. Arthur G. McKee & Company,
San Francisco, California, September 1970.
Hollowell, J. B., et al. Water Pollution Control in the Primary
Nonferrous Metals Industry, Volume I, Copper, Zinc, and
Lead Industries. EPA-R2-73-247a (PB 299-466-b), U.S.
Environmental Protection Agency, Washington, D.C.,
September 1973.
Jones, H. R. Pollution Control in the Nonferrous Metals
Industry. Noyes Data Corporation, Park Ridge, New Jersey,
1972.
Measurement of Sulfur Dioxide, particulate and Trace Elements in
Copper Smelter Converter and Roaster/Reverberatory Gas
Streams. EPA 650/2-74-111, U.S. Environmental Protection
Agency, Washington, D.C., October 1974.
Metallurgy Processing in 1974.
February 1975.
Mining Congress Journal,
Parsons, T. B., ed., and F. I. Honea. Industrial Process Pro-
files for Environwental Use: Chapter 8, Pesticides Indus-
try. EPA-600/2-77-023H (PE 266 225), U.S. Environmental
Protection Agency, Research Triangle Park, North Carolina,
January 1977. 240 pp.
Phillips, A. J. The World's Most Complex Metallurgy (Copper,
Lead, and Zinc). Transactions of the Metallurgical Society
of AIME, 224(issue H) :657-668, August 1962.
Reports on the Effects of Environmental Pollutants, Arsenic.
Oak Ridge National Laboratory, Draft, 1976.
Statnick, R. M. Measurement of Sulfur Dioxide, Particulate and
Trace Elements in Copper Smelter, Converter and Roaster/
Reverberatory Gas Streams. (PB 238 095), U.S. Environ-
mental Protection Agency, Research Triangle Park, North
Carolina, 1974.
Systems Study for Control of Emissions Primary Nonferrous Smelt-
ing Industry. Arthur G. McKee & Co. for U.S. Department
of Health, Education and Welfare, Washington, D.C.,
June 1969.
28
-------
Trace Pollutant Emissions from the Processing of Metallic Ores.
PEDCO-Environmental Specialists, Inc., August 1974.
Treilhard, D. G. Copper - State of the Art.
ing Journal, April 1975.
Chemical Engineer-
Vandergrift, A. E., L. J. Shannon, P- G. Gorman, E. W. Lawless,
E. E. Sallee, and M. Reichel. Particulate Pollutant System
Study, Mass Emissions, Volumes 1, 2, and 3. (PB 203 12B,
PB 203 522, and PB 203 521), u.S. Environmental Protection
Agency, Durham, North Carolina, May 1971.
29
-------
APPENDIX
PRIMARY COPPER PRODUCTION
REVERBERATORY SMELTING
Function
Copper smelting is the process of re~oving from a roasted or
dried ore concentrate much of its iron and some undesirable im-
purities, leaving a molten mixture that can be processed
efficiently by a copper converter. This is most often accom-
plished by other methods.
The reverberatory furnace is a large horizontal chamber into
which ore and various fluxing materials are charged. The furnace
is then heated by direct firing. As the temperature .of the
charge increases, a complex series of chemical reactions
takes place, and the charge separates into three fractions.
One fraction is S02 gas, which along with other volatiles, is
mixed with the combustion gases and is carried out of the
furnace. A second fraction is a molten slag containing much
of the iron, which is tapped from the furnace and discarded.
The third fraction, called the matte, becomes the charge to
the copper converter.
The charge to the reverberatory furnace is proportioned so that
the resulting matte typically contains 40% to 45% copper and
25% to 30% each of iron and sulfur. The matte contains most of
the heavy elements present in the charge, practically all the
gold and silver, and part of the arsenic and antimony.
Reverberatory smelting, the oldest of the copper smelting pro-
cesses now in use, is little different now than when it was
first practiced in 1879. It is in use at all but two of the
smelters in this country, in one of two modifications, described
as either "deep bath" or "dry hearth". Some reverberatory
furnaces are very large, capable of accepting as much as 1,800
metric tons of material per charge.
Input Materials
The primary input material is the roasted or dried concentrate,
whose composition is not much different from the concentrate
received from the mill. Slags from the converter and anode
30
-------
furnace also are added for reprocessing, as are flue dusts from
dust collection equipment throughout the smelter. Precipitates
from hydro-metallurgical operations or materials from refinery
processing may be added at this step.
Flux consists normally of sand high in silica content, and
usually limestone to make the slag more fluid. Sometimes "direct
smelting ore" is used, which adds both fluxing waterial and
additional copper.
Composition of one charge to a reverberatory furnace in Arizona
is reported as follows:
Ore concentrate
Converter slag
Precipitator
Flue dusts
Silica flux
Limestone flux
- 64%
2%
1%
1%
2%
6%
This charge produced molten materials of which 47% was matte
and 53% was slag.
Operating Conditions
When possible, the concentrate is charged into the furnace while
still hot from the roaster (400°C or more). Converter slag is
charged as a liquid (approximately 1,lOO°C). Other materials
are usually charged at ambient temperatures. The reverberatory
furnace usually heats the mixed charge to at least 1,OOO°C
before the matte forms and separates; temperatures up to 1,300°C
have been reported. All operations are at or near atmospheric
pressure.
utilities
It is estimated that 90% of the energy consumed in a smelting
operation is added into the reverberatory furnace. It is
reported that 6.48 x 1016 J of energy were used in domestic
copper smelters in 1973. Consumption of energy by this process
is very high; it is usually supplied by natural gas, but
pulverized coal or fuel oil can be used. It is estimated that
2.09 x 109 J of heat is required to smelt 1 metric ton of
concentrate if the charge is preheated by a roasting operation.
If the charge is not preheated, an addional 1.63 x 109 J are
required. These values give credit for steam generated by
waste heat boilers, which are almost always installed with a
reverberatory furnace. In itself, the reverberatory furnace is
thermally inefficient, using more than four times the heat
theoretically required.
31
-------
Noncontract cooling water is used by copper smelters, primarily
for the protection of equipment auxiliary to the roaster, con-
verter, and reverberatory furnace. Data that allocate this
cooling load specifically to each process are not available.
Reported data indicate that the total cooling water consumption
for smelting operations can vary from 4 m3 to 61 m3 per metric
ton of copper product.
Contact cooling water is used at four smelters to granulate the
slag from the reverberatory furnace. One smelter uses 1,700 m3
of water per day for this purpose.
Waste Streams
It is reported that 20% to 45% of the sulfur that enters with
the ore concentrate is emitted by the reverberatory furnace as
S02. Although most smelter operators have attempted to make
operational changes either to increase or reduce this quantity,
no recent data are available. The gas is released as a dilute
stream of variable composition, reported as from 0.5 to 2.5
weight percent S02- Other constituents in the exit gas are
shown in Table A-l, for unroasted and roasted concentrate feeds.
The volume of this gas is very large, since it consists
primarily of the combustion gases from the heating fuels. Temp-
erature of the exit gases may reach 1,150°C to 1,200°C.
TABLE A-i.
COMPOSITION OF REVERBERATORY FURNACE EXHAUST GASES
Green feed,
Calcined feed,
Component
Carbon dioxide
Nitrogen
Oxygen
Water
Sulfur dioxide
%
%
8.4
69.3
0.25 to 1.0
18.8
1.5 to 2.5
10.2
71. 0
0.25 to 1.0
17.7
0.6
Between 14 kg and 40 kg of particulate matter are emitted in
this gas stream per metric ton of copper matte produced. One
analysis of the particulates showed 24% copper and the following
concentrations of other elements:
Element
qjm3
44,000
310
100
45
35
2.5
zinc
Cadmium
Manganese
Chromium
Nickel
Mercury
32
-------
Other investigations indicate that most of the volatilized
arsenic, selenium, lead, antimony, cadmium, chromium, and zinc
emissions will be generated in the reverberatory furnace.
Fugitive dust is generated in this process as materials are
loaded into the furnace. No quantities are reported, but this
is probably one of the largest sources of dust in a smelting
operation.
The only liquid waste from this process is the run-off from
slag granulation. Three complete analyses are reported as
shown in Table A-2. Liquid waste is most often generated as the
overflow from a pond into which the molten slag is dumped.
Since the pond is an open body of usually hot wateri subject to
rainfall and evaporation, quantity and composition of the over-
flow may be highly variable.
TABLE A-2.
EFFLUENTS FROM SLAG GRANULATION
(g/m3 )
Parameter
pH
Total dissolved solids
Total suspend solids
Sulfate
Cyanide
Arsenic
Cadmium
Copper
Iron
Lead
Mercury
Nickel
Selenium
Tellurium
Zinc
Oil and grease
aNa data available.
Plant 103
7.7
140
6.8
62
0.005
3.7
0.001
0.12
0.04
0.04
0.0001
0.001
0.001
0.001
0.44
Plant 110
8.1
3,800
151
310
0.050
0.048
0.001
0.05
0.03
0.070
0.0001
0.06
0.54
0.023
0.0
Plant 102
6.4 to 7.6
_a
0.030
5.70
0.042
0.604
340
7.4
0.0001
0.16
0.040
0.100
36
0.02
One copper smelter is situated close to a market for the furnace
slag it produces; for all the others, the slag constituted a
large quantity of solid waste, as much as 3,000 kg/metric ton of
copper produced. Table A-3 gives an analysis of potentially
hazardous elements found in a reverberatory furnace slag. The
bulk of the slag is a mixture of iron silicates, with other
elements, also as shown in Table A-3.
33
-------
TABLE A-3.
GENERAL RANGE OF REVERBERATORY FURNACE
SLAG COMPOSITION
Compound or element
Composition, %
Iron oxide
Silicon dioxide
Calcium oxide
Magnesium oxide
Aluminum oxide
Copper
Sulfur
34 to 40
35 to 40
3 to 7
0.5 to 3
4.5 to 10
0.4 to 0.7
0.0 to 1.5
Trace elements
ppm
zinc
Maganese
Antimony
Lead
Chromium
Selenium
Nickel
Cadmium
Mercury
Arsenic
Tellurium
Cobalt
7,800
450
400
100
100
20
25
10
1.0
Trace
Trace
Trace
Control Technology
Gases from the reverberatory furnace pass through a waste heat
boiler and then through an electrostatic precipitator for par-
ticulate removal. The gases may pass through spray coolers or
balloon flues before entering the ESP units. The degree of
particulate removal ranges from 50% to 99.9%. Particulates
collected are recycled into the metallurgical process, normally
as part of the reverberatory furnace charge, but accumulations
of trace elements causes some flue dusts to be discharged or
processed separately. Quantities and their disposition are not
reported.
At present, there is virtually no control of the SO 2 emissions
from reverberatory smelters. Intensive studies are underway to
develop scrubbing techniques that can be applied to large vol-
umes of flue gas containing small concentrations of S02. These
represent the best available control technology. One smelter
absorbs the S02 from this stream in dimethyl aniline and re-
generates it as a concentrated stream for further processing.
34
-------
One Canadian smelter uses an ammonia absorption process on some
streams, but this system is not in use in this country. Other
scrubbing solutions, containing compounds of zinc and aluminum,
are used on smelter gases in Japan. Scrubbers using lime or
limestone, with and without magnesium addition, are being used
on sulfur-containing flue gases from coal-fired boilers in the
united States, and might be adopted for use in u.s. smelters,
as has been done in Japan. Another absorption process based on
sodium sulfite-bisulfite is under test. The only one of these
processes specific to the domestic copper industry is DMA
absorption.
Of the four smelters that practice slag granulation, one reports
no wastewater from this source, since the rate of evaporation at
this location necessitates a continuous water ITake-up to the
quenching pond. The other three smelters mix the water from
slag granulation with other wastes.
Granulated slag is usually a coarse-grained material of low to
medium density, usually discarded near the smelter. A small
amount may find a market for use as road fill or concrete aggre-
gate. Crushed slag that has not been granulated also finds a
small market for these same purposes. Most slag is not gran-
ulated, but is simply poured out and allowed to solidify- There
is no easy way to naturalize or reclaim the slag dumping areas,
and there are no published reports on how this could be done.
It is generally assumed that the potential of secondary water
pollution from slag dumps is less than that from mine spoil or
tailings beds.
35
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO. 12. 3. RECIPIENT'S ACCESSION NO.
EPA-600/2-79-210b
4. TITLE AND SUBTITLE 5. REPORT DATE
December 1979 issuing date
Status Assessment of Toxic Chemicals: Arsenic 6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S) 8. PERFORMING ORGANIZATION REPORT NO.
T.R. Blackwood, S.R. Archer
T.K. Corwin
9. PERFORMING ORGANIZATION NAME AND ADDRESS 10. PROGRAM ELEMENT NO.
Monsanto Research Corp. PEDCo - Environmental lAB604
1515 Nichols Road 11499 Chester Road 11. CONTRACT/GRANT NO.
Dayton, Ohio 45407 Cincinnati, Ohio 68-03-2550
4S246
12. SPONSORING AGENCY NAME AND ADDRESS 13. TYPE OF REPORT AND PERIOD COVERED
Industrial Environmental Research Lab. - Cinn, OH Task Final 1l/77 12/77
Office of Research and Development 14. SPONSORING AGENCY CODE
U.S. Environmental Protection Agency EPA/600/12
Cincinnati, Ohio 45268
15. SUPPLEMENTARY NOTES
IERL-Ci project leader for this report is Dr. Charles Frank, 513-684-4481
16. ABSTRACT
The production, consumption, and uses of arsenic are dealt with in this report.
Sources of environmental contamination by arsenic are identified and the
consequences of such pollution explained. Better control methods are needed for
both air emissions and discharge of arsenic-containing wastewaters. Present control
technologies are listed as well as areas in which further study is required.
17. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS b.IDENTIFIERS/OPEN ENDED TERMS c. COSATI Field/Group
Arsenic, metalloids, Arsenic Isotopes, Pesticides, Smelting, 68A
Arsenic Organic Acids, Arsenic Organic Copper 68D
Compounds, Arsine, Arsenides, Arsenic 68G
Oxides, Arsenic Inorganic Compounds,
Arsenic Halides, Arsenic Containing Alloys
Arsenic Chlorides, Arsenic Trioxide,
Arsenic Metal
18. DISTRIBUTION STATEMENT 19. SECURITY CLASS (This Report) 21. NO. OF PAGES
Unclassified 46
Release to Public 20. SECURITY CLASS (This page) 22. PRICE
Unclassified
EPA Form 2220-1 (Rev. 4-77)
PREVIOUS EDITION IS OBSOLETE
36
"; U 5 GOVERNMENT PRINTING OFFICE 1960 -6 57- 146/5508
-------
United Slates
Environmental Protection
Agency
Environmental Research Information
Center
Cincinnati OH 45268
EPA 335
Official Business
Penalty for Private Use, $300
Special Fourth-Class Rate
Book
Please make all necessary changes on the above label.
detach or copy, anil return t© the address in the upper
left-hand corner
If you do no! wish to receive these reports CHECK t+ERi D.
detach, or copy this cover, and return to th» address in the
upper Mt-hand corner
EPA-600/2-79-210b
------- |