c/EPA
United States
Environmental Protection
Agency
Off Ice of Water
Regulations and Standards (WH-553)
Washington DC 20460
September 1980
EPA-440/4-81-015
Water
An Exposure
and Risk Assessment
for Copper
-------
DISCLAIMER
This is a contractor's final report, which has been reviewed by the Monitoring and Data Support
Division, U.S. EPA. The contents do not 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.
-------
SO277- ifll
3EPORT DOCUMENTATION , 1- «win- so. I 2.
PAGE i I? A-440 74-31-013 j
1 4. Titta «nd *j«rit«
An Exposure and Risk Assessment for Copper
1 7. AM*.**) Perwak> J>; Bysshe, S.; Goyer, M. ; Nelken, L. ;
Scow, K. ; Walker, P.; and Wallace, D.
k Performing Orfanliatton Nam* and Addma
Arthur D. Little, Inc.
20 Acorn Park
Cambridge, MA 02140
12. Sponsoring Organization Nam* and Addma
Monitoring and Data Support Division
Office of Water Regulations and Standards
U.S. Environmental Protection Agency
Washington, D.C. 20460
3. 4«cioi*nf s ACCIHIOII No.
9. Report OaM
September 1980
6.
9. Performing Organisation Rapt. No.
10. Projoct/Taak/Work Unit No.
11. Contract(C) or Grant(Q) No.
«o 68-01-3857
(C)
IX Type of fteoort A Period Covered
Final
14.
IS. Suppl«m«' *•' a«*
21. No. af Ptgta
122 '
"si I*, oo
• ANSI-OS. 18) SM Instruction* jn ?»«n« OPTIONAL fOOM 272 (4-77)
(Fornwiy NTIS-J3)
-------
EPA-440/4-81-015
September 1980
AN EXPOSURE AND RISK ASSESSMENT
FOR COPPER
by
Joanne Perwak
Sara Bysshe, Muriel Goyer, Leslie Nelken, Kate Scow,
Pamela Walker, and Douglas Wallace
•-Arthur. D-. Little, -Inc..
and
Charles Delos
U.S. Environmental Protection Agency
EPA Contract 68-01-3857
Monitoring and Data Support Division (WH-553)
Office of Water Regulations and Standards
Washington, D.C. 20460
OFFICE OF WATER REGULATIONS AND STANDARDS
OFFICE OF WATER AND WASTE MANAGEMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
-------
FOREWORD
Effective regulatory action for toxic chemicals requires an
understanding of the human and environmental risks associated with the
manufacture, use, and disposal of the chemical. Assessment of risk
requires a scientific Judgment about the probability of harm to the
environment resulting from known or potential environmental concentra-
tions. The risk assessment process Integrates health effects data
(e.g., carcinogenicity, teratogenicity) with information on exposure.
The components of exposure include an evaluation of the sources of the
chemical, exposure pathways, ambient levels, and an identification of
exposed populations including humans and aquatic life.
This assessment was performed as part of a program to determine
the environmental risks associated with current use and disposal
patterns for 65 chemicals and classes of chemicals (expanded to 129
"priority pollutants") named in the 1977 Clean Water Act. It includes
an assessment of risk for humans and aquatic life and is intended to
serve as a technical basis for developing the most appropriate and
effective strategy for mitigating these risks.
This document is a contractors' final report. 7.t has been
extensively reviewed by the Individual contractors ?.nd by the EPA at
several stages of completion. Each chapter of the draft was reviewed
by members of the authoring contractor's senior technical staff (e.g.,
toxicologists, environmental scientists) who had not previously been
directly involved in the work. These individuals were selected by
management to be the technical peers of the chapter authors. The
chapters were comprehensively checked for uniformity in quality and
content by the contractor's editorial team, which also was responsible
for the production of the final report. The contractor's senior
project management subsequently reviewed the final report in its
entirety.
At EPA a senior staff member was responsible for guiding the
contractors, reviewing the manuscripts, and soliciting comments, where
appropriate, from related programs within EPA (e.g., Office of Toxic
Substances, Research and Development, Air Programs, Solid and
Hazardous Waste, etc.). A complete draft was summarized by the
assigned EPA staff member and reviewed for technical and policy
implications with the Office Director (formerly the Deputy Assistant
Administrator) of Water Regulations and Standards. Subsequent revi-
sions were included in the final report.
Michael W. Slimak, Chief
Exposure Assessment Section
Monitoring & Data Support Division (WH-553)
Office of Water Regulations and Standards
ii
-------
TABLE OF CONTENTS
LIST OF FIGURES
LIST OF TABLES
ACKNOWLEDGMENTS *
I. EXECUTIVE SUMMARY 1
II. INTRODUCTION 9
III. MATERIALS BALANCE 11
A. Introduction and Methodology 11
B. Materials Balance 11
1. Primary and Secondary Copper Production 11
2. Production in Which Copper is a Byproduct/Contaminant 19
3. Environmental Release of Copper During Consumptive Use 21
4. Other Sources 24
5. Copper Disposal 27
C. Summary 29
References 30
IV. DISTRIBUTION 'OF COPPER IN THE ENVIRONMENT 33
A. Monitoring Data 33
1. Copper in Water 33
2. Copper in Aquatic Organisms 37
3. Copper in Plants 37
4. Copper in Soil 39
5. Copper in Air 39
a. Work Environment 39
b. 'Non-Work Environment 39
B. Environmental Fate 39
1. Overview 39
a. Methodology 39
b. Major Environmental Pathways 40
c. Important Fate Processes 40
2. Physicochemical Pathways 44
a. General Face Discussion 44
b. Atmospheric Transport 51
c. Solid tfascas 56
-------
TABLE OF CONTENTS (continued)
Page
d. Aqueous Industrial Discharge 60
e. POTW 64
f. Copper Sulface Use 68
3. Biological Pathways 71
C. Summary • 76
1. Distribution 76
2. General Fate 77
3. Specific Pathways 77
a. Air 77
b. Solid Waste 78
c. Industrial Wastewater 78
d. POTW's 78
e. Copper Sulfate Use 78
4. Biological Pathways 78
References 79
V. EFFECTS OF AND EXPOSURE TO COPPER—AQUATIC ORGANISMS 87
A. Effects of Copper ' 87
1. Introduction 87
2. Freshwater Organisms 88
a. Chronic/Sublethal Toxicity 88
b. Acute Toxicity 92
3. Marine Organisms 92
4. Other Studies ' 95
5. Factors Affecting the Toxicity of Copper 95
6. Conclusions 100
B. Exposure of Biota to Copper 101
1. Introduction 101
2. Monitoring Data 102
3. Ingestion 103
4. Fish Kills 103
5. Conclusions 103
References 106
VI. EFFECTS OF AND EXPOSURE TO COPPER—HUMANS 111
A. Human Toxicity 111
1. Introduction 111
a. Copper Deficiency 111
2. Metabolism and Bioaccumulation 112
3. Animal Studies 113
a. Carcinogenic!ty 113
b. Mutagenesis 115
-------
TABLE OF CONTENTS (continued)
c. Adverse Reproductive Effaces 116
d. Other Toxicological Effects 119
e. Copper-Metal Interactions 119
4. Human Studies 121
a. Ingescion 121
b. Inhalation 122
c. Dermal Exposure 122
d. Copper Intraut'erine Devices (lUD's) 123
5. Overview 123
Human Exposure 125
1. Introduction 125
2. Ingestion 125
a. Food 125
b. Drinking Water 126
3. Inhalation 126
4. Medical Exposure 128
5. Conclusions . 128
References • 129
VII. RISK CONSIDERATIONS 137
A. Biota 137
B. Humans 146
C. Conclusions 149
References 150
APPENDIX FOUR CASE STUDIES—COPPER RISK TO AQUATIC ORGANISMS 153
-------
LIST OF FIGURES
Figure
No. Page
1 Materials Balance of Copper 14
2 Typical Process Flowsheet for Copper Extraction
and Refining 16
3 Locations of Major Copper Mines in the United
States 17
4 Wood Processing Regions of the United States 22
5 Distribution of Total Copper in U.S. River Basins 34
6 Major Environmental Pathways of Copper Releases 42
7 Schematic Diagram of Major Pathways of Anthropogenic
Copper Released to the Environment in the United
States 44
8 Solubility Diagram of Cu(II) in Equilibrium with
Malachite, Azurite, and Tenorite from pH 0-14 46
9 Adsorption of Heavy Metals in Oxidizing Fresh Waters
(pH - 7, pE • 12, pC02 - 10~3-5 acm. pCT - 4.16)
As a Function of Surface Area of Si02 46
10 Adsorpfion of Heavy Metals on Soil Minerals and
Oxides 51
11 Aerodynamic Particle Size Distribution of Copper in
Industrial Stack Effluent 51
12 Monthly Deposition of Particulate Copper in New York
City 55
13 The pH in Kerber Creek 59
14 Bicarbonate Concentrations in Kerber Creek 59
15 Dissolved Copper Concentration in Kerber Creek 59
16 Total Copper in Sewage at Grand Rapids, Michigan
Before and After Prscreatment of Industrial
Discharges to a. ?OTW 67
-------
LIST OF FIGURES (continued)
Figure
No. Pag;
17 Copper Concentration in Reservoir Sediment vs.
Sediment Depth 71
13 Calculated Copper Speciation in a Relatively Hard
Fresh Water Where Concentration of Inorganic
Carbon = 10~2-% and Calcium = 10~2-6M(a) in the
Absence of Organic Chelation and (6) in Presence
of Excess OTA ([MTAl total »[Cu] total) 141
vii
-------
LIST OF TABLES
Table
No. Page
1 Summary of U.S. Copper Supply and Demand, 1976 12
2 Summary of Environmental Releases of Copper 13
3 Copper Releases from Mining and Milling Activities,
1978 ' 18
4 Potential Environmental Release of Elemental
Copper Related to Agriculture, 1976 20
5 Reported Copper Concentrations in POTW Influent 26
6 Summary of POTW Copper Budget 28
7 Total Copper in Ambient Waters by Region 35
8 Total Copper in Sediments in U.S. Regions,
1970-1979 36
9 Residues of Copper in Aquatic Organisms 38
10 Average Distribution of Copper in Three River
Waters 46
11 Copper Concentrations as a Function of Water Hardness
and Urbanization—Tributaries of Lake Cayuga, New
York 47
12 Copper Concentration in Water and Sediments after
Exposure to Zinc Outcrop 48
13 Bioconcentration Factors for Algae and Aquatic
Invertebrates 72
14 . Bioconcentration Ratios in Fish 74
15 Sublethal Effects of Copper on Freshwater Fish 89
16 Acute Toxicities of Copper for Freshwater Fishes 93
17 Chronic/Sublethal Effects of Copper on Marine
Invertebrates 96
13 Recor.ad Results from CSPEX Studies 97
Vlll
-------
LIST OF TABLES (continued)
Table
Mo. Page
19 Observed Copper Concentrations in U.S. Minor
River Basins, 1973 104
20 Data for Copper-Related Fish Kills, 1971-1977' 105
21 Effect of Copper Salts on Embryonic Development
in the Hamster 113
22 Acute Toxicity of Copper Compounds 120
23 Outcome of Pregnancies with Copper lUD's Followed
to Termination • 124
24 Dietary Copper Intakes Reported in the Literature 127
25 River Basins with Factors Contributing to Risk For
Aquatic Organisms 133
26 . Distribution of Levels of Dissolved and Total
Copper from STORET Monitoring Data 139
27 Adverse Effects of Copper on Mammals 147
28 Human Exposure to Copper 143
-------
ACKNOWLEDGMENTS
The Arthur D. Little, Inc., task manager for this study was Joanne
Perwak. Other major contributors were Muriel Goyer (human effects),
Leslie Nelken (environmental fate), Gerald Schimke (materials balance),
Kate Scow (biological fate), Pamela Walker (materials balance), Douglas
Wallace (biota effects and exposure and monitoring data), Melba Wood
(monitoring data), Sara Bysshe (aquatic effects and exposure), and
Alfred Wechsler (technical review).
-------
SECTION I.
EXECUTIVE SUMMARY
INTRODUCTION
The Monicoring and Data Support Division, Office of Water Planning
and Standards, U.S. Environmental Protection Agency is conducting an
ongoing program to identify the -sources of and evaluate the exposure to
the 129 priority pollutants. This report assesses the exposure to and
risk associated with copper. The summary is organized somewhat
differently than the report, focusing on the risk consideration first
since this section presents the major conclusions of the study.
AQUATIC RISK CONSIDERATIONS
A consideration of the risk to aquatic organisms on the basis of
laboratory bioassay data and ambient monitoring data implies risk in
numerous locations in the United States. However, it is apparent that
numerous factors influence the toxicity of copper in the field. The
impact of these factors can only be evaluated on a case-by-case basis.
Examination of four such locations indicated risk to aquatic organisms
in three of them, although not as severe or widespread as would be pre-
dicted from laboratory data. In addition, this risk was not necessarily
related solely to copper. Actual fish kills that have been reported in
the past are commonly associated with mining areas and copper sulfate use
and indicate a high potential for risk to aquatic organisms in these
situations.
Toxicity; Toxicity data developed in the laboratory indicate that
adverse effects are observed in salmonids at copper levels of 10 yg/L in
soft water. Fathead minnow are affected at slightly higher concen-
trations. Numerous species experience lethal or sublethal effects at
concentrations of 6 to 60 ug/L in the laboratory, generally in soft or
moderately hard water. The fact that these levels (as total copper) are
exceeded in numerous locations in the United States (55% of STORET
observations), suggests that potential risk to fish and invertebrates is
widespread.
Exposure: An analysis of monitoring data from STORET showed that
mean concentrations were greater than 50 ug/L total copper in numerous
minor river basins in 1978. These locations were primarily in the South-
east, the Ohio River Basin, the Lower Mississippi, and the Gila, Spokane,
and Sacramento Rivers. In addition, some observations of greater than
120 ug/L were found in many of these locations. Further, examination of
STORET data for individual stations in three of these minor river basins
showed that elevated concentrations were generally limited to a Saw
locations within each minor river basin. Thus, the mean of 50 ug/L is not
representative of typical ambient conditions. In addition, soft waters
generally were found in the Southeast, the Lower Mississippi, che Sabine
-------
and Neches Rivers, Che Spokane River, and Che Sacramenco River, chus
furcher increasing Che pocencial risk in Chese areas.
Faecors Influencing Risk: Numerous faccors, however, complicace
Che direcc comparison of monicoring daca and laboracory coxicicy daca.
Firsc, only some chemical species of copper appear Co be responsible for
the observed effeccs. The cupric ion has been implicated and perhaps
ocher soluble inorganic complexes as well. Copper in che form of organic
complexes and adsorbed co parciculaces does noc appear co be available co
aquacic organisms.
The chemistry of copper can be very different in laboracory waters
as compared with field situations. In the laboratory, concentrations of
organic and suspended copper are generally low, making the relative
presence of soluble inorganic species greater. In the field, free copper
often comprises a very small portion of total measured copper (in some
situations less than 1%) as compared with suspended and complexed
copper. Thus, an overestimation of risk can result when monitoring data
are assessed on the basis of laboratory toxicity daca. Although
locacions with high copper concentrations have been identified, che
extent to which Chese potentially toxic levels in specific areas are
mitigated by complexation and adsorption is unknown.
Four areas with high reported copper levels were selected as case
studies Co examine specific sources of copper releases and the actual
risk to aquatic biota in the vicinity: Che Upper Sacramenco River in
California, che Coeur D'Alene River in Idaho, the Gila River in Arizona,
and the Delaware River. Several conclusions can be drawn from this
analysis:
• The use of major or minor river basin summaries from STORET,
which are necessary when there are a large number of obser-
vations, can be misleading. In Che examples cited, high con-
centrations are commonly limiced Co very localized condicions,
usually one or cwo stations. In addition, a large amount of
existing data is not yet included in the STORET system.
• Toxic effects as indicated by reduced populations of aquatic
organisms have been observed in very localized areas during some
periods. However, releases of copper appear to be rapidly
diluted, precipitated, or adsorbed onto sediment. Despite
occasionally high levels of copper, sensitive species have been
observed during at least some parts of the year in these
locacions. Thus seasonal variations in pH, flow, etc., appear
to affect greatly the level of exposure and, therefore, the risk
to aquatic organisms.
• The sources of copper in the Gila, che Coeur D'Alene, and che
Sacramenco River 3asins appear co be primarily siining activi-
ties, especially abandoned sites. The low on of che surfaca
wacars in these areas aakas che high copper levels aven nora
significant since che cupric ion would be acre prevalent.
-------
• Levels of copper in Che Delaware may well be lower Chan evidenced
by STORE! due Co dececcion limics of some of Che analyses.
Further, Che imporcance of copper as a. concaminanc of concern,
in most areas, appears Co far less Chan chac of other con-
taminants in Chac drainage basin.
• In all cases, copper was noc Che only concaminanc of concern.
Zinc, cadmium, and/or iron were also considered co be problems
in Che mining areas. A large number of organic and inorganic
concaminancs exist in Che Delaware River.
The case studies confirmed chac aquatic organisms are at risk, at
lease in Che Coeur D'Alene, Sacramenco, and Gila Rivers. This risk,
however, cannoc be encirely ascribed co Che effeccs of copper. The risk
due Co copper in Che Delaware River could noc be established.
HUMAN RISK CONSIDERATIONS
Copper does not appear to represent a significant risk to humans.
Ic has noc been shown Co be carcinogenic, mucagenic, or ceracogenic, even
when its use in lUD's is considered. Thus Che effeccs expected due Co
copper are primarily related to acute exposures, with Che lowest oral
lethal dose being 50 mg/kg. Since the maximum ingescion exposure is
estimated Co be 0.3 mg/kg/day (24 mg/day for a 70-kg person), a
considerable margin of safety appears co exisc. The only exposure route
with a potential for toxic effects is renal dialysis. However, no
problems with this type of exposure have been reported in the last few
years.
Toxicity: Copper is an essential trace element in human and animal
nutrition, and the total body content of the average adult ranges from
100 mg to 150 mg. Copper deficiency is a recognized problem and its symp-
toms are well known.
The net absorption efficiency of ingested copper is about 5%.
Absorption through Che skin is minimal. AbsorpCion through the lungs is
gradual and depends upon the solubility of the specific salt involved.
Homeostatic mechanisms regulate copper levels in Che human body quite
effectively.
No experimencal evidence exiscs Co suggesc thac copper is tumor-
genie in man or experimental animals. In fact, administration of copper
may inhibit chemically induced tumors in laboratory animal. The use of
copper lUD's has been investigated for dysplastic lesions of the cervix
or precancerous lesions. Although dysplasia cases have been reported,
no progression to cancer has been found, although further study is
underway.
No clear evidence of autagenicity exists, although enhanced crans-
foraation of hamster embryo cells by a simian adenovirus has been
observed, and increased Lachal mutations noted in Drosophila, buc only
-------
ac high concentrations? The results of bacterial assays have been
negative or show tnutagenic activity only at concentrations that are
toxic to the bacterium. Further work is needed to clarify the mutagenic
potential of copper.
Copper lUD's have been investigated for evidence of adverse re-
productive effects. There ara no data to suggest that intrautarine
copper has teratogenic effects on the fetus, although an increase in
spontaneous abortion has been observed in involuntary pregnancies with a
copper IUD in'utero in a relatively small sample.
As.far as other toxicological effects are concerned, there is a wide
margin of safety between copper deficiency and copper toxicosis in
mammalian species. The lowest reported lethal oral dose for humans is 50
mg/kg (copper sulfate). Survival after consumption of as much as 3 g
copper sulfate has been reported. Acute copper poisoning produces
tachycardia, hypotension, hemolytic anemia, oliguria, uremia, coma,
cardiovascular collapse and death.
Exposure: Although further investigation is needed in some areas
(i.e., the possibility of mutagenicity, and the potential for cervical
cancer related to the use of copper lUD's), it appears that copper has a
low order of toxicity to humans. Thus, worst case situations have been
considered for copper exposure. The maximum reported intake of copper in
food is 7.6 mg/day from diets containing liver, which is high in copper.
The maximum likely intake from drinking water is 16.7 mg/day, primarily
resulting from the use of copper in the water distribution system. Thus
a total maximum exposure via ingestion would be approximately 24 mg/day.
However, only an extremely small subpopulation would be exposed to this
level; a more typical exposure through ingestion would be 1 to 4 mg/day.
Since absorption via ingestion is about 57,, the actual absorbed dose
would be considerably lower.
Inhalation exposures, even in worst case situations (for example,
near smelters) are considerably lower than ingestion exposures, on the
order of 0.04 mg/day.
Certain medical procedures may result in human exosure to copper.
For example, copper sulfate used in the treatment of burned skin has been
reported to result in symptoms of copper toxicosis though this type of
incident appears to be rare.
Persons receiving kidney dialysis have also been exposed to high
levels of copper, primarily due to source water or to equipment problems.
Exposures of 5 mg have been reported, and the potential for a 240-rag
exposure per dialysis has been calculated. Incidents of such exposures
have not been reported recently, and it is probable that dialysis
equipment has been improved in order co reduce axposura.
A Large subpopuiacion of human famai.es is exposed co copper chrough
Che use of copper IUD' 3. Such devices can release up co 50 ug copper/day,
-------
abouc one-half of which amount is lose in menstrual blood. The resulcanc
exposure of 0.025 nig/day is available for absorption, whereas only 5% of
ingested copper is absorbed.
SOURCES OF COPPER RELEASES TO THE ENVIRONMENT
In 1976, the total U.S. industrial demand for copper was 2.4 million
metric tons (MT). Approximately 34% of this supply resulted from
domestic mine production, 17% from industry stocks, 15% from scrap
recylcing, and 14% from imports. This supply went largely into the
production of copper wire and other electrical components C56%), with
24% being used for brass production. Thus these two industries accounted
for the consumption of 80% of the industrial supply.
Of the total identified releases of copper to the environment, 97%
went to land, 2.4% went to water, 0.3% went to POTW's, and 0.04% went to
air. It should be pointed out that the uncertainties in this type of
analysis are great, and the distribution of specific releases to
specific environmental compartments is often based on very limited
information. In addition, the transfer between compartments may be
rapid. However, it is clear that the land receives by far the largest
portion of copper release.
The major-contributors of copper to land (97%) are the mines and
mills in the form of tailings, overburden, etc. Disposal occurs pri-
marily in the states of Arizona, Nevada, New Mexico, Utah, Tennessee,
Michigan, and Montana.
Agricultural applications contribute about 2% of the pollutant
loading to land, primarily in the Southeast, Pacific, Cornbelt and
Appalachian regions. Other sources of copper to land include POTW's,
municipal refuse, electroplaters, and iron and steel producers. There
are numerous unquantified releases to land. These losses are primarily
from copper-containing products during use, such as plumbing, gutters,
roofing, radiators, etc.
Of the identified releases of copper to water (28,848 MT for 1976),
the transport of eroded copper-containing soils is the most significant,
representing about 68% of the total. This source, however, is widely
distributed throughout the United States. Copper sulfate use represents
about 13% of the identified releases to water, while urban runoff
represents about 2%. Sources to urban runoff include exposed con-
struction elements and transportation and industrial applications
(plumbing, chrome, brass, etc.).
In addition, POTW's contribute about 8% of the total releases co
water. While this represents a contribution by point sources, there are
numerous locations where che releases occur. Sources of copper co POTW's
include domestic wastes, which account for about 25% of che cocal copper
entering wacer from POTW's; escimaced known industrial releases account
for an additional 20%. The remainder can probably be accri'oucad to
concribucions from additional induscrial and natural sources.
-------
The remaining 9% of the direct releases Co water is comprised of
releases from electroplating (400 MT) , abandoned mines (314 MT) , iron or
steel (656 MT) and various other industrial processes. Copper wire and
brass production, although utilizing about 80% of the copper supply,
release relatively low amounts to the aquatic environment, 134 and 151
MT, respectively.
Known releases of copper to the atmosphere (434 MT) include pri-
marily emissions from smelting (41%), copper wire production (34%), and
incineration of refuse (21%). Smaller amounts are released from brass
production and iron and steel production.
. The largest areas of uncertainties in this analysis are the esti-
mated loadings of copper associated with suspended sediment, from
abandoned metal mines, in urban runoff, and to POTW1 s . The releases from
mining and other industrial operations are better defined. In addition,
releases during the use of copper-containing products could be sub-
stantial, but these have not been specifically estimated. However, the
reported contribution of copper in urban runoff may already contain some
copper from these sources.
FATE AND DISTRIBUTION OF COPPER IN THE ENVIRONMENT
Monitoring Data: Copper is widely distributed in the environment
since it is naturally occurring. Levels of total copper in the aquatic
environment generally range from 1 Mg/L to 100 ug/L, although higher
concentrations are found near sources and more generally in New England,
the Western Gulf, and the Lower Colorado River. Sediments generally con-
tain levels between 1 mg/kg and 1000 mg/kg copper. Levels of copper in
fish tissues are generally in the range of 1 mg/kg to 100 mg/kg.
Molluscs, especially oysters, have accumulated levels as high as 1000
mg/kg. Copper is an essential micronutrient for plants and is found at
levels of 1 mg/kg to 150 mg/kg. Copper deficiency is a common problem in
crops .
Levels of copper in air range from 0.01 ug/m^ to 0 . 3 ug/m^ , although
levels near smelters can be 1 ug/m^ to 2
Fate and Pathways Analysis: Since the largest portion of copper
reaches the soil, it is important to consider the fate of copper in this
compartment. In general, the behavior of copper in soils is dependent
upon the adsorptive properties of the soil, as well as the pH and redox
potential of the soil solution. At a pH of 5 or 6, adsorption is the
principal means of limiting copper mobility. Above this pH, chemical
precipitation becomes the more dominant fate process.
Specifically, the greatest portion of copper releases co land
originate from solid waste and tailings from copper tnining and milling.
Currently, tailings ara left to settle in Lagoons following creacraenc
with Lime co raise ths 3ti and aracioicace heaw aecals. Controlled
-------
conditions for chase sites reduce the mobility of copper. However,
former disposal sites are more subject to leaching and runoff and the
resulting acid mine drainage affects both groundwaters and surface
waters. The immediate effect on receiving waters is a drop in pH and
bicarbonate concentration, as well as an increase in the concentration
of copper and other metals. Stream recovery is a function of the
distance downstream from the source as the copper concentration is
rapidly reduced due to-precipitation, adsorption and dilution.
A large, but not well quantified amount of copper is disposed of in
municipal landfills. Although copper is the "least generally mobile" of
the metals and is strongly adsorbed onto soil, it has been found in
landfill leachate at levels of 0.1 mg/L to 1.0 mg/L.
The direct releases of copper to water are small relative to those
going to land; however, resulting exposure may be important. In general,
copper reaching the aquatic environment will be rapidly adsorbed on to
suspended solids or bottom sediment. The form of the dissolved copper is
highly dependent on the receiving water. Below a pH of about 7, the free
ion will be important, whereas above this, the carbonate and hydroxy
complexes will predominate. If organic complexing agents are present in
sufficient amounts, organic complexes of copper will predominate over
the entire pH range. Copper in the sediment may be associated with iron
and manganese oxides, organic matter, clays and perhaps sulfides. It
does not appear to be readily exchangeable or soluble in natural,
alkaline, waters.
Copper reaching the aquatic environment as a result 'of runoff is
probably already adsorbed onto soil particles. The fate of this copper
depends upon the fate of the suspended material.
Copper is also discharged as a constituent of wastewater effluents
from electroplating, brass manufacture, etc. The concentration of
copper in aqueous industrial discharges can be lowered by pretreatment.
Once released, the copper is rapidly adsorbed and, in some cases,
precipitated.
Copper is directly applied to the aquatic environment through its
use as an algicide (CuSO^,). When added at levels of 0.4 g Cu^"1" per m^,
levels in water are returned to baseline values within 24 hours. Copper
is strongly adsorbed onto the sediment where it accumulates.
A small portion of copper releases reach the atmosphere. The forms
of copper released due to thermal processes are the oxide, elemental
copper as the vapor, and copper adsorbed to particulates; copper sulfide
as the dust is the result of entrainment from coal pits.
Once copper has been released into the atmosphere, ics residence
cirne and discsnca traveled are dependenc upon particle size, as well as
meteorological factors. Copper from combustion sources (smelting, coal
combuscion, incineration) cends co be associated with sub-micron par-
-------
ticulate matter. Such copper can be deposited via rainout or dry
fallout. The residence cime in che troposphere has been estimated as 7
to 30 days. Thus, while most deposition will occur in the vicinity of the
source, some particulates may be carried considerable distances.
Copper deposited on pavements can contribute to urban runoff and
represent a significant source to surface waters. Copper deposited on
soils or surface waters is subject to the same factors, which affect
direct releases to those compartments, primarily adsorption.
Copper entering POTW's is largely concentrated in the sludge, with
about 25% to 75% being removed by treatment. The efficiency is dependent
upon treatment method and influent concentration, with less removal
occurring at higher concentrations in influent. Industrial pretreatment
can reduce the concentration in the effluent and in the sludge from
POTW's. Copper in effluents is subject to the factors affecting other
releases to the water compartment; it appears to be rapidly diluted and
adsorbed.
Sludge may go to a sanitary landfill or be spread for the purpose of
amending soil. Although the form of copper in the sludge is not known,
it does not appear to be readily translocated when applied to soil.
Concentrations in leachate from sludge amended soils were less than
12 ug/L.
Copper reaching both the water and soil compartments can be taken up
by biota. In aquatic environments, uptake depends on such factors as pH
and water hardness. Molluscs, especially oysters, appear able to con-
centrate copper up to 30,000 times water concentrations. Field studies
have shown that fish accumulate copper at concentrations one to two
orders of magnitude over water concentrations. Uptake of copper from
soil can also occur, although terrestrial plants are commonly deficient
in this nutrient. However, concentrations of copper are increased in
some plants cultivated on soil amended with sewage sludge.
-------
SECTION II.
INTRODUCTION
The Office of Water Planning and Standards, Monitoring and Data
Support Division of the Environmental Protection Agency is conducting
a program to evaluate the exposure to and risk of 129 priority pollutants
in the nation's environment. The risks to be evaluated included poten-
tial harm to human beings and deleterious effects on fish and other
biota. The goal of the task under which this report has been prepared
is to integrate information on cultural and environmental flows of
specific priority pollutants and estimate the risk based on receptor
exposure to these substances. The results are intended to serve as a
basis for developing suitable regulatory strategy for reducing the
risk, if such action is indicated.
This report is intended to provide a brief, but comprehensive,
summary of the production, use, distribution, fate, effects, exposure,
and potential risks of copper. There are a number of problems with
attempting such an analysis for this metal. Since the purpose of this
report is to provide a basis for regulation, it is important to identify
sources. However, copper is an element commonly found in the earth's
crust and natural sources to waterways can be significant. Thus in any
analysis of discharges or runoff, it is important to distinguish back-
ground concentrations or natural sources from anthropogenic sources.
We have attempted to do this to the extent possible, but in discharges
from Publicly Owned Treatment Works (POTW) facilities, for example, it
is difficult to trace back to the sources, natural or anthropogenic.
In addition, the aquatic chemistry of copper is complex. Other
metals are commonly found with copper, making 'this situation more com-
plicated due to possible interactions. We have used information avail-
able on the aquatic chemistry of copper to draw conclusions regarding
specific fate pathways as related to sources.
Finally, copper is a nutritional requirement, and copper deficiency
could be considered a risk. However, for the purposes of this risk
assessment we have discussed copper deficiency cursorily to establish
a range of acceptable doses. We have concentrated on assessing the
risks due to exposure to high levels of copper.
This report is organized as follows:
• Section III contains information on the production, discharge
(point and non-point) and disposal of copper.
• Section IV describes available monitoring data and a consider-
:he face of copper in five specific pathways.
-------
• Section V considers effects and exposure of biota to copper.
• Section VI discusses effects of copper on humans and describes
exposure scenarios.
• Section VII discusses risk consideration for various subpopulations
of humans and aquatic organisms, as a result of estimated exposure
to copper.
10
-------
SECTION III.
MATERIALS BALANCE
A. INTRODUCTION AND METHODOLOGY
In- this section, a materials balance is developed for copper.
The materials balance considers copper as it flows from, the cultural
environment to its first point of entry into the natural environment.
Potential sources of copper releases were identified by a review of
activities in which the material participates from its extraction and
refining through processing, use, and disposal. Thus the materials
balance encompasses all sources of pollutant release from the point at
which copper enters the cultural environment until it has returned to
the natural environment.
For each source of pollutant release,, the amount of material
released was estimated, and the environmental compartments (air, land,
and water) initially receiving and transporting the element were
identified, as were the locations at which the pollutant loadings take
place. There 'are many uncertainties inherent in this type of analysis:
not all current releases have been identified, past releases are not
well documented, and future releases are difficult to predict. Never-
theless, sufficient information is available to indicate in general
terms the nature, magnitude, locations, and time dependence of pollutant
loading of the environment with .copper.
*
B. MATERIALS BALANCE
In 1976, total U.S. industrial demand was 2.4 million metric tons
(MT). Primary production of copper is expected to grow at an annual
rate of 3% and secondary production at a rate of 5%. Table 1 summarizes
the commercial sources and uses of copper.
Environmental releases during production and occurring due to
various consumptive uses are presented in Table 2 and Figure 1. Copper
is consumed primarily as the metal or alloys by industry. A remaining 0.5%
is used forming copper compounds, largely copper sulfate (Versar, 1978).
Of the industrially consumed metal, the majority is used by electrical
and electronic equipment manufacturers; the construction, machinery and
transportation industries are major consumers as well. Significant
discharges to the environment occur during production and beneficiation
processes. Discharges to water from Publicly Owned Treatment Works
(POTW's) are also substantial.
1. Primary and Secondary Copper Production
Copper is mined and allied in seven scatas within Che continental
United Scatas, and this provides a significant source of ralaasas co che
Li
-------
TABLE 1. SUMMARY OF U.S. COPPER SUPPLY AND DEMAND, 1976
Source/Consumer
Domestic mine production and
beneficiation
Refined Scrap
Unrefined Scrap
Imports (refined)
Imports (ores-concentrates)
Industry Stocks,. 1 January 1976
Copper Wire Mills
Brass Production
Other
Industry Stocks, 31 December 1976
Total
Supply
(MT)
1,287,940
204,080
149,660
235,810
99,770
419,940
Consumption
(MT)
2,397,200
1,349,288
567,092
39,110
441.710
2,397,200
Note: The above figures are for one year (1976). There is considerable
statistical variation from year to year; consequently, these do not
not reflect average values.
Source: Versar,' 1978.
12
-------
TABLE 2. SUMMARY OF ENVIRONMENTAL RELEASES OF COPPER
(Estimated 1976)
Release (MT/yr)
Source
Air
d
2002
&
A
1641,2
31,2
17* '2
A
_
_
-
A
-
-
*
-
—
1002
„,
484
Direct
Acuatic
13. 42
Unknown
0.33
343
1341
151]
656J
1811'2
110 3
43
1743
151*
4003
723
9
314.
3,600"
44lf
18,400
- .
2.0739
26,909
POTW
73
—
1.4841
294 l
_
_
_
-
_
1,4003
-
-
* 2
84
—
-
_
3,269*
Land
1,073,2902
Unknown
A
Unknown
d
421.2
8961'2
_
_
_
-
_
920 3
-
-»
19,1951+, 5,6
*
—
1.9002
9,6803
1,110,923
Primary Production
Smelting
Secondary Production
Metallic Ore Mining
& Related Activities
Copper Wire Mills
Brass Production
Iron & Steel Production
Coal Mining**
Pulp, Paper & Paperboard
Inorganic Chemicals
Steam Electric Industry
Machinery Mfgr.
Electroplating
Miscellaneous Sources
Area Sources:
Abandoned Metal Mines
Agricultural Applications
Urban Runoff
Suspended Sediment
Incineration/Refuse
POTW
Total
Insignificant
*These emissions are directly applied to the category in which they are
reported; however, often during or shortly following release, they enter
other environmental media.
**Coal combustion is known to release some copper; insufficient data is
available to substantiate this quantity,. ----- ^
^Ihe total estimated POTW influent is ^X800/MT/yr (see Table 6). Thus,
only a portion of the sources have been" identified.
^Versar, 1978.
Arthur D. Little Estimate.
•^Effluent Guidelines Monitoring Data, analyzed by Versar, EPA, 1979.
^U.S. Department of Agriculture, 1974.
5SRI, 1979.
E?A, 1977.
3Tabia 5.
Martin and Mills (1975).
-------
Erosion-
Suspended
Sediment
18,400 MT
ENVIRONMENTAL
COMPARTMENTS
INDUSTRY
Electroplating
(27.200 MT)
Brass Prod.
(567,092 MT)
Primary Production
(1,287.340 MT)
Copper Wire Mills
(1,349,288 MT)
CONSUMPTIVI
RELEASES
Urban Runori
525 MT
MT
Other
Air
484 MT
Water
26,909 MT
POTW
3,269 MT
) Copper Use
Includes smelting
Industrial releases in which copper exists as a trace element. Sources include iron and steel production,
coal mining, pulp and paperboard manufacture, steam electricity generation, other ore mining, and
abandoned mines.
^POTW affluent includes contributions from human and other unknown sources.
Note: Boundaries between receiving meaium are often undefined and/or changing: Copper aoparenrly
released :o one camoarrment can result in another.
Source: Arthur 0. Little, Inc.. based on 1975 estimates.
FIGURE 1. MATERIALS 3ALANCS OF COPPER
-------
environment, particularly to land. A typical flowsheet for the copper
production process is presented in Figure 2.
The general practice for sulfide ores (from which 88% of the copper
is produced) is to mine the ore, then concentrate it in a milling plant
to produce a concentrate for smelting and refining. Nine companies
operate 17 smelters and 19 companies operate 23 refineries and electro-
winning plants (Arthur D. Little, Inc., estimates, 1979). The other major
process is the acid leaching of oxide ore and recovery from solution by
cementation or electrolysis. Figure 3 shows the .location of major
copper mines.
Following extraction, the ore is crushed and concentrated by a
flotation process involving organic reagents and water (milling). For
a grade of ore of between 0.6% and 0.8% copper, the resulting concentrate
is from 15% to 35% copper (NIOSH, 1975). The copper is then roasted in
a reverbatory furnace and formed into a matte for smelting.
The major releases to land and water from mining and milling are
presented by state in Table 3. The copper content in tailings represents
that portion of the mineral that could not be recovered. Most of it is
in the form of silicates and sulfides, which are relatively insoluble.
Tailing ponds are contained by control structures that permit only rare
opportunities for discharge. Large quantities of mine tailings that
have accumulated from past mining practices constitute a source of copper
as shown in Table 2.
Waterborne discharges of copper from active copper mines result
from the concentrating process, the grinding process at the mill, and
the thickening and settlement processes. For copper mining and milling
operations situated in the Vest and Southwest, water is a scarce
commodity, which is most often recycled rather than discharged. Of the
21 copper mining and milling operations in Arizona, only two
discharge effluent. None of the operations in Nevada and New Mexico
discharge any water at all (Arthur D. Little, Inc., estimates, 1979).
Thus, in total,water discharges of copper from these processes are
small.
Airborne releases of copper from the mining and milling processes
are also insignificant. Economic as well as environmental factors pro-
vide incentives for maintaining an efficient recovery mechanism (e.g.,
bag houses). The relatively high price of copper on the current market
makes it economically attractive to capture copper otherwise released
to the atmosphere. The same situation exists in sheltering and other
copper refining processes.
Seventeen primary copper smelters in the United States are operated
by nine companies. All but two (in Tennessee and Michigan) are Located
in the western states of Arizona, Texas, Nevada, New Mexico, Montana and
-------
Overburden
from
Ooen Pics
Mines
Open Pics and
Underaround
Sulfide
_Wat.er
+ Recycle '
! it
Ores
Oxide
r
Ores
Solution_
Recycle
A
I
Milling
(concentracion)
Leaching
(Vats-Heaps)
Waste
1' Concentrate
I
Solution
Tailing?
Smelting
Cementation
Electrolysis
Solvent Extract^
Waste to Dumps
or Left in Pil
*
Some Discharge
Refining
Refining
Copper
Copper
7IGURE 2. TYPICAL PROCESS FLOWSHEET TOR COPPER EXTRACTION AND REFINING
J.O
-------
I-*
--1
v ACIIWO ixjppor Minos
O Active Zinc-t-eaU-Lead/Zinc Minos
A Inactive Oro and Mineral Minus
(Martin and Mills 1976)
'•': !-! '''\e& ' > " "T" ^ --1;/" vv /-A
.., \ ...... _ -.,,..^ ,,^ ^^ \ ^ \"-.l.vi \ 7;.v,.-... .;:/IIM {.f^..*
^U r/'?^/..\7'::5<-
- ^V •• * M ' V- •- $ I ^ ^ \
A , y / V ' ' / ft u '*
FIGURE 3. LOCATION OF ACTIVE AND INACTIVE MINES IN THE UNITED STATES
-------
TABLE 3. ESTIMATED COPPER RELEASES FROM MINING AND MILLING ACTIVITIES. 1978
Ore Mined
Concentrate
Produced
SLate
Arizona
Nevada
New Mexico
III ah
Tennessee
Michigan
MonLana
(1000 MT/yr)
159,769
16,362
21,323
32,208
1,836
3,281
15,419
(1000 MT/yr]
2.1791
253 !
421 l
753
853
125
327
To La I
250,198
4,911+
Copper Deposited as
Solid Wastes from Milling
(MT/yr)
126,310
21,420
21,600
21,980
1.000
1,280
15.100
208,690
Copper Deposited as
Solid Wastes from Mining
(MT/yr)
399,900
63,750
122,700
169,050
negligible
negligible
114.200
869,600
'indicates that certain mills have not published production of concentrate; therefore, the above
quantities are less than actual concentrate production.
Source: Arthur I). Little, Inc., estimates, 1979, based on EPA Nl'DES data.
-------
Washington (EPA, 1977b). The smelting process applies sufficient heat
to the copper ore/concentrate to convert the gangue into a slag (waste
product) and simultaneously to concentrate the copper into a high grade
material. It involves the processes of roasting, reverbatory smelting,
converting and fire refining. The copper is formed as a matte containing
30% to 70% copper (NIOSH, 1975). The matte is oxidized to remove iron
and sulfur by streams of hot air forced through the molten mass.
Studies of the atmosphere surrounding copper smelters in Utah,
Arizona, and Montana revealed moderate to high concentrations of copper
(NIOSH, 1975). Quantification of the material released in terms of bulk
discharge per unit production is difficult, however, because these
studies were conducted to determine human exposure levels rather than
rates of emission. As with mines and mills, western smelters must
operate within constraints of a limited water supply and are likely to
recycle water used. Even including releases from the two non-western"
smelters, aquatic discharges from smelters are expected to be
negligible.
Secondary copper production involves the direct electrowinning and
refining from scrap metal. Data (for 1976) obtained from effluent guide-
lines monitoring at EPA (Versar, 1979) indicate that 0.3 MI are discharged
directly to water annually and 7 MT to POTW's annually. It is thought
that atmospheric emissions of copper from secondary production are small
(Arthur D. Little, Inc., estimates).
2. Production in Which Copper is a Byproduct/Contaminant
In addition to the copper mines, relatively small quantities of
copper are found in the effluents of lead-zinc mines. The majority of
these are located in the five states of Missouri, Tennessee, Idaho,
New York, and Colorado. The amount of copper released from this
source is estimated to be 5.7 MI annually (Arthur D. Little, Inc.,
estimates). Copper is also present in the effluents from various other
ore mines, and is estimated to amount to a release of 1.9 MT annually.
Copper appears in the ash of most coals in trace amounts;
consequently coal combustion should provide a release of copper to the
atmosphere. Reliable documentation quantifying this emission is not
readily available; however, for a 99.5% recovery of coal ash and given
the extremely low concentrations of copper in coal, this release is not
expected to be significant.
Copper also appears as an impurity in materials used in the production
of iron and steel and subsequently 17 MT annually is emitted to the
atmosphere and 896 MT is disposed of on land. This approximation is
determined by the efficiencies of pollution controls on iron and steel
production processes (Arthur D. Little, Inc.,estimate ).
19
-------
TABLE 4. POTENTIAL ENVIRONMENTAL RELEASE OF ELEMENTAL
COPPER RELATED TO AGRICULTURE, 1976
Discharge of Copper
Through Impurities
Fungicides
Copper/Sulfate
Hug lua1 (MT/yr)
tluitliuuut 78
Appalachian 1,157
Southeast 3,471
Lake liiaiua
Cum Hull
Null In: rn I'lalna
DC 1 l.i !iiai>:u
Suuilicru I'lalus
35
Central 1'fl71
9
South
Central _
Hu.ua.li,
rac lilt 2.070
luial 8.700
Fungicides
Other Coppers2
' (MT/yr)
31
253
-
143
-
-
-
-
573
1.000
Algtcldes Wood Preservatives
Copper Sulfate Other Coppers'
(MT/yr) (MT/yr)
(Hoc Available by 5OO
Keglon)
3.500
you
1.100
600
000
3.600 8.000
and Adjuvants In
Fertilizers
(MT/yr)
(Not Available by
tteglou)
1.336 - 1,654
ltural production regluns apply except for wood processing regions; botli are defined In Figure 3.
uitychlurlde sulfate, cupper hydroxide, cuprous oxide, copper oleate, copper, chromated copper
lt;, and acid copper clironate.
USIM (1974); EPA (1974); SKI (1979).
-------
Probably as a naturally occurring constituent, copper has been
detected in discharge waters from the pulp and paper industry and the
steam electric industry. These two sources discharge 110 MT and 1.74 MT,
respectively,each year directly to waters (EPA, 1979).
3. Environmental Release of Copper .During Manufacturing Processes and
Consumptive Use
Of the 2.4 million MT consumed in the U.S. in 1976, over 99% was
used in the pure metallic form or in alloys that are predominantly
copper (Versar, 1978). Manufacturing uses of copper include the wire
mills and brass mills.
Based upon EPA monitoring data, it has been determined that wire
mills contribute 164 MT to air and 1618 MT to water (POTW and direct
aquatic) annually- (Versar, 1978).
Brasses are alloys of copper and zinc. The Bureau of Mines estimated
that 567,000 MT of copper was consumed by this use in 1976. Based upon
EPA monitoring data, it is estimated that 445 MT of copper are discharged
to water (direct and POTW) annually, 42 MT is disposed of as solid waste
annually and 3 MT is emitted to the atmosphere annually (Versar, 1979).
The largest consumer of copper is the electrical industry, which
uses it in wiring, communications equipment, electronic components,
lighting equipment and in generators. Because of its superior qualities
of high conductive capacity and relatively low corrodibility, copper
is used in the manufacture of electrical components that ate intentionally
shielded from environmental interference to ensure efficient operation.
Consequently, pathways to the environment, if any, involve a slow process,
and environmental release from this consumptive use is negligible.
Copper is used in the electroplating industry in a modest amount
relative to other metals, e.g., nickel. The process by which it is
consumed discharges some copper to water. Estimated consumption by
the industry is about 27,200 MT of copper a year (Schroeder, 1979).
Conservatively, it is estimated that no more than 10% is released to
the environment (Schroeder, 1979; Arthur D. Little, Inc., estimates,
1979). EPA reports that 52% of electroplating operations discharge
to POTW's (EPA, 1979). From the remainder, approximately 70% of
waste is treated and discharged as sludge, and the other 30% is
effluent released directly to water (Arthur D. Little, Inc. ,
estimates, 1979).
The construction industry is a significant consumer of copper; its
uses include roofing materials, heat exchangers, plumbing, tubing,
valves and process equipment. Copper exposed to the atmosphere •—
such as in roofing, drainage gutters, and exterior trim — is naturally
susceptible to acid rains and oxidation and, consequently, erodes more
rapidly. Copper used in plumbing, valves and tubing is routinely
21
-------
NORTHERN PLAINS
NORTHEAST
SOUTH CENTRAL
PACIFIC
Key:
MOUNTAIN
SOUTHEAST
Farm Production Regions
A - Pacific F - Corn Dell
b — Mountain
C - Northern Plains
O - Lake States
E - Northeast
G - Appalachian
H - Southern Plains
I - Delta States
J - Southeast
Source: Arthur D. Little, Inc. from USDA 1974; SRI. 1979.
FIGURE 4. WOOD PROCESSING REGIONS OF THE UNITED STATES
(Data Excludes Alaska and Hawaii)
-------
exposed to moisture and is likely to be released to the aquatic
environment. Although the nature and quantities of these industrial
applications are fairly well defined, consequent release to the
surrounding environment is less predictable.
Copper is consumed in the machinery industry in the production of
mining machinery, conveyors, bushings, bearings, and miscellaneous
tools. The transportation industry uses copper in radiators, carburetors,
tubes, and brakes. This latter application contributes an unquantified
amount of copper to roadways and thus is potentially a source of copper
in urban runoff.
There are several other industries in which copper was detected but
all discharged minor amounts ( < 10 MT annually). These include: printing
and publishing, ore mining, textiles, non-ferrous metals, rubber,
petroleum refining, leather tanning, gum and wood chemicals, inorganic
chemicals, and paint and ink. Automatic and other laundries discharged
82 m per year to POTW. (EPA, 1979).
Copper sulfate is a chemical compound that has long been used in
agriculture. The U.S. Department of Agriculture (USDA) recommends copper
sulfate as the safest, most effective, inexpensive, and extensively used
algicide (EPA, 1974); this copper enters the aquatic environment directly.
Other agricultural uses include in fungicides, feeds, and fertilizers on
citrus fruits, deciduous fruits, and vegetables. Copper sulfate is also
used in industry to froth flotation agents and supplement wood preservatives.
Table 4 and Figure 4 summarize agricultural consumption of copper sulfate
by regions, where available, based on 1971 and 1974 data from USDA and in
a study for EPA by SRI (1979). Most of these uses have, by definition,
entered the environment (the soil compartment) upon their use. The use of
copper as a wood preservative does not reach the environment immediately,
although it would eventually reach the soil compartment. We have assumed
that the use of this product has been similar in the past, and thus releases
have achieved equilibrium. Chroraated copper arsenate is used as a wood
preservative to treat lumber and timbers, primarily Douglas Fir and
Southern Pine (SRI, 1979).
Copper exists as an impurity in phosphate rock from which phosphatic
fertilizers, are produced. In a study of agriculture-related releases of
copper (1979), SRI determined that between 136 MT and 454 MT of elemental
copper are discharged annually. Because of the nutritional requirements
of plants and animals for copper, copper is used as an adjuvant in
fertilizers. In the above study, SRI determined that approximately
1200 MT of copper are used each year for this purpose.
23
-------
4. Other Sources
The iron and steel industry represents a major source of copper,
especially to the aquatic environment. Versar (1980) has estimated that
this industry releases 656 MT to water annually, based on data from
Effluent Guidelines Division.
Copper is a natural constituent of the soil at concentrations
ranging from 1 mg/kg to 50 mg/kg. Consequently, copper resulting from
soil runoff is transported in streams and water bodies throughout the
United States. The average annual total suspended load of the United
States has been estimated by Wischmeier (1976) as 3.6 billion MT, 25%
of which enters the major streams. If a copper concentration of 20 mg/kg
is assumed, approximately 18,000 MT of copper is discharged to water via
this route. Obviously, a large part of this is a result of cultural
activities, such as agriculture and construction. However, some of it
is due to natural background weathering.
Urban runoff receives a substantial quantity of copper from a
variety of identifiable sources. Possible sources of copper release in
the urban/industry environment include exposed construction elements
(roofing, gutters and trim), transportation (radiators, carburetors,
brakes, etc.) and industrial applications (plumbing, tubing, valves,
etc.), as discussed above. Assuming a concentration of 25 ug/1 in urban
runoff (EPA 1980) and a volume of 21 x 1012 1/yr (EPA 1977c), a release
of 525 MT/yr can be estimated. The major portion (441 MT) flows to
separate storm sewers (41%) (point sources) and to unsewered areas (43%)
(non-point sources). Combined sewers contribute the remaining 16%
(84 MT) to POTW's. As shown in Table 2, total urban runoff must be
considered one of the major sources of pollutant loading.
Environmental release of copper during its production processes is
partially regulated by EPA guidelines. Mining operations dispose of
tailings at controlled land areas at or near the mine site. The copper
is locked in silicate compounds or other insoluble forms, and this
decreases the likelihood of leaching. Release of copper to the air and
water is minimized by two significant factors. First, the relatively
high cost of copper in the current industrial market makes it
economically attractive to recover the maximum amount of the metal in
bag houses and other related mechanisms; this provides the primary
incentive for reducing air emissions of copper. Second, most copper
mining operations are located in the Midwest and Southwest portions of
the United States. These areas are characteristically dry regions in
which water is at a premium; consequently, there is little if any discharge
of waters from the operations. Four exceptions exist; they are located
in Michigan, Montana, Tennessee and Utah. However, abandoned mines and
past disposal practices can result in significant discharges to the
environment. Figure 3 shows the numerous locations where such
situations exist, although the map includes all abandoned mines. Martin
and Mills (1976) have estimated that 314 MT reach the aquatic environment
annually as a result of abandoned mines.
POTW's also represent a significant source of copper to the
environment. Influents and effluents indicate an abnormally high
24
-------
concentration of copper in streams located near industrial areas
(EPA, 1979). Because no other apparent source of copper release exists,
these copper concentrations must be attributable to urban runoff,
industrial discharge, and domestic and commercial areas.
In this study, the available data have been examined and an
estimate made on the basis of a flow-weighted mean concentration of
copper in POTW influent and on mean removal efficiencies of primary
and secondary treatment plants.
A substantial number of studies addressing the composition of POTW
influent and effluent have been accomplished in recent years. Many of
the individual studies are of a single POTW and there is considerable
variability in the nature'of the study, the quality of the reporting,
and the indicated range of values for copper concentration. Several
studies present data and conclusions based on groups of POTW's that
were investigated. Table 5 indicates the range of results reported.
Of the studies examined, none presents data from a truly representative
cross section of POTW's in the United States. However, one (Sverdrup
and Parcel, 1977) presents a relatively consistent data set on 103
POTW's clustered mainly in the Midwest, with some additional plants
in California, New Jersey, New York, and elsewhere in the Southeast.
The authors of the Sverdrup and Parcel study concluded that their data
describe "typical" POTW's with regard to heavy metals. Since the
study emphasized secondary treatment plants, only a small number of
primary plants are represented in the sample. With data presented in
the study, a flow-weighted mean concentration, C, for copper concentra-
tion in the influent of the 103 POTW's was calculated by the following
formula:
r!03c TT
C = L Vi = 250 ug/1
EVi
Where:
C = concentration of iC POTW
V± = flow volume of ith POTW
The Sverdrup and Parcel report concluded that POTW's meeting
secondary treatment standards removed an average of 82% (range from 55%
to 90%) of the copper in the influent. This conclusion is drawn from
data on 22 of the 103 plants that met these standards and for which
sufficient data existed on all parameters of interest.
25
-------
TABLE 5. REPORTED COPPER CONCENTRATIONS IN POTW INFLUENT
POTW's
12 - New York City1
99 - New York, New
Jersey &
Connecticut2
Land Use
Residential
Mixed
10 - Southern Ontario3 Mixed
103 - United States'*
12 - New York City5
6 - New York City
Sewers5
Mixed
Mixed
Residential
Values Reported (mg/1)
Mean =0.21
50% below 0.10
95% below 0.85
100% below 9.60
50% below 0.15
90% below 0.35
100% below 1.20
Median =0.12
Range = 0.01 - 1.968
X - 0.238 (0.13 - 0.43)
X - 0.202 (0.11 - 0.33)
:Davis and Jacknow, 1975.
2Mytelka _et _al., 1973
301iver and Cosgrove, 1975.
^Sverdrup and Parcel Associates, 1977 draft.
5Klein et al., 1972.
-------
Sverdrup and Parcel (1977) noted that while influent concentrations
reported elsewhere in the literature agreed with their data, the removal
efficiencies reported elsewhere tended to be lower. They suggested that
the explanation could be that other analyses included some POTW's not
meeting secondary treatment standards. In any event, 82% was both the
median and flow-weighted mean of the removal efficiencies for the 22
plants. Data were presented on removal efficiency for 10 primary treat-
ment facilities in addition to the 22 secondary plants. The median
value of removal efficiency for the primary plants was 37% while the
flow-weighted mean was 31%. The latter was used in the above calculations
to estimate partitioning between sludge and release to the aquatic
environment.
Data on improved metals removal during advanced treatment are
sparse. However, it was assumed that an improvement of 3% over
secondary treatment could be achieved. Therefore, advanced treatment
was assumed to be capable of removing 85% of the copper in the influent.
The total amount of treated effluent from POTW's in the United
States and outlying territories is estimated to be 34,031 MGD on the
basis of the 1976 needs survey as reported by SRI International
(R. A. Marshall, 1978 a,b). It is also estimated from this report
that less than 2% of the flow is from primary treatment plants, while
nearly 64% undergoes secondary treatment, and nearly 35% undergoes
advanced treatment.
Table 6 summarizes the POTW copper budget on the basis of the
above assumptions and shows that 2073 MT of copper is discharged by
POTW's to the aquatic environment, while 9680 MT is discharged to land.
Identifying the source(s) of copper observed in POTW's remains
problematic. Only 2341 kkg of copper released to POTW's are accounted
for in Table 2. Recent studies (Arthur D. Little, Inc., 1979) have
shown that residential areas are significant sources of copper in the
sewer systems of Cincinnati and St. Louis. Data from these two cities
suggest that copper loadings of 26.3 - 57.7 mg/day/person may be
generated by residential areas. For an average of 42 mg/day/person,
the total copper loading to POTW's from all residential area sources
would be 3066 MT, leaving 6347 MT of the POTW's loading to be accounted
for by industrial and natural discharges.
5. Copper Disposal
Little information is available on levels of copper in refuse.
However, it is likely that copper does comprise some small portion of
municipal solid waste, about 5% of which is incinerated. Some portion
(probably much less than one-half) of the copper in the incinerated
waste would be released to air, while the remainder would to go ash and
be discharged to land. If 0.001% of the 1979 municipal solid waste
load of 200 million MT in the United States is assumed to be copper,
27
-------
TABLE 6. SUMMARY OF POTW COPPER BUDGET
CD
1976 Needs Survey
Primary Treatment
Secondary Treatment
Advanced Treatment
Total
Flow not included in
Needs Survey
Total flow treated by
POTW in U.S. and out-
lying territories
Flow (MDG)
336
16,019
8,711
Copper Load ing (L)
to POTW (kkg)1
116
5,533
3,008
Treatment
Removal
Efficiency
.312
.822
.853
POTW
Discharge
(kkg)
To Sludge To
36
4,537
2,557
Water
80
996
451
25,066
8,965
34,031
8,657
3,097
11,754
7,130
2,550
9,680
1,527
546
2,073
^(kkg/yr) = flow (MGD) x 250 (10~6g/l) x 3.785 (1/gal) x 365 (day/yr) x
O
= 0.3454 x flow.
2Flow-weighted mean value calculated from Sverdrup and Parcel Associates data, February 1977.
3Assume advanced treatment removes Cu proportionately to TSS — estimated 3% increment from SRI,
September 20, 1978.
Source: Derived from 1976 Needs Survey, reported by SRI International (1978 a,b).
-------
Chen 2,000 MT of copper would be in the wasce (Arthur D. Little, Inc.,
estimate). Incineration would release a maximum of 100 MT to the air and
the remaining 1,900 MI would be disposed of on land, either directly
with the municipal solid waste or as ash remaining after incineration.
Most of this waste would be in metallic form.
A study published on the subject of municipal wastes reports copper
occurring at concentrations as high as 0.16% in solid waste (NAS, 1975).
Assuming the above waste load, this would signify 320,000 MT of copper in
this source, of which 16,000 MI goes to air by incineration and the
remaining 304,000 MI is deposited to land. This estimation is presented
as an alternative though we feel that it may be unreasonably high.
The state of knowledge in the area of municipal waste is currently poorly
documented and considerable further work is needed.
C. Summary
Copper is released to all environmental compartments as illustrated
in Table 2. The most significant receptor is land, to which jLn situ
mining operations, agricultural activities, and POTW sludge disposal
are the three largest contributors. Mining contributes by far che
largest quantity in the form of mining and milling wastes. The copper
in these wastes is in a chemically bound form with little, if any,
potential for further release to the environment. Agricultural prepara-
tions containing copper are distributed at recommended concentrations
designed to fulfill functions as pesticides, nutrients, etc. POTW
sludge accounts for less than one-half of the amount used in agricultural
applications.
The water compartment receives most of its- copper initially from
three major sources: suspended sediment, poTW's, and agricultural
application. POTW loadings represent more localized releases, while
soil runoff and agricultural sources represent non-point sources. Vari-
ous industries also account for additional small direct contributions to
water but, as shown in Table 2, the identified industries account for
only 9% of the direct aquatic release. However, they may represent
important sources in local areas. In addition, abandoned mines repre-
sent a source of copper to the aquatic compartment. These sources may,
however, contribute s'ignificantly' to the copper levels in very local
environments.
Airborne releases are apparently very small and the major ones are
associated with copper wire mills and, hence, are very localized.
-------
REFERENCES
Arthur D. Liccla, lac. 1979. Sources of toxic pollutants found in
influents to sewage treatment plants. VI. Integrated Interpretation,
Part 1. Report on EPA Contract Mo. 68-01-3857.
Bureau of Mines. 1977. Minerals Yearbook 1977. Copper. Washington, D,C.
Council for Agricultural Science and Technology. 1976, Application of
sewage sludge to cropland-appraisal of potential hazards of heavy metals
to plants and animals. Ames, Iowa. (EPA #PB-264-015).
Davis, J. and J. Jacknow. 1975. Heavy metals in wastewater in three
urban areas. JWPCF 47(9) :2292.
Klein, L.A., M. Long, S. Nash and S.L. Kirschner. 1974. Sources of
metals in New York City wastewater. Metal Finishing. 34:5.
Martin, H.W. and W.R. Mills, Jr. 1976. Water pollution caused by
inactive ore and mineral mines - a national assessment. NTIS
# PB-264-936. Prepared for the Office of Research and Development,
EPA, Cincinnati, OH.
Mytelka, A., J.S. Crachoe, W.B. Guggino and H. Golub. 1973. Heavy
metals in wastewater and treatment plant effluents. JWPCF 45:1859-1864.
National Academy of Sciences. 1975. Mineral resources and the environ-
ment, supplementary report. Washington, D.C.
National Institute for Occupational Safety and Health (NIOSH). 1975.
Environmental conditions in U.S. copper smelters. Cincinnati, OH.
National Research Council. 1977. Zinc. National Academy of Science.
Baltimore: University Park Press.
Oliver, B.C. and E.G. Cosgrove. 1975. Metal concentrations in the
sewage effluents and sludges of some southern Ontario wastewater
treatment plants. Env. Letters 9^(1).
Schroeder, H.J. 1979. Bureau of Mines, Metals Section. Personal
communication.
Sittig, Marshall. 1975. Environmental Sources and Emissions Handbook.
Park Ridge, New Jersey: Noyes Data Corporation.
SRI International (Robert A. Marshall). 1978a. Toxic survey for
publicly owned craataent plants (draft final report) - Task 3 under
EPA Contract 63-01-3887.
30
-------
SRI International (Robert A. Marshall). 1978b. Statistical support for
analytical survey of publicly owned treatment plants (draft final
report, Part 1) - Task 4 under EPA Contract 68-01-3887.
SRI International (S.E. Casey). 1979. Agricultural sources of zinc.
Draft report to the Monitoring and Data Support Division, EPA.
Sverdrup & Parcel and Associates, Inc. 1977. Study of selected pollutant
parameters in publicly owned treatment works (draft) - Task Order No. 7
under EPA Contract 68-01-3289.
United States Department of Agriculture. 1974. Farmers' use- of pesticide
in 1971. Washington, D.C.
United States Environmental Protection Agency. 1972. AP-42 compilation
of. air pollutant emission factors. Washington, D.C.
United States Environmental Protection Agency. 1974. Production, distri-
bution, use and environmental•impact potential of selected pesticides.
Washington, D.C.
United States Environmental Protection Agency. 1977a. State and local
pretreatment programs (federal guidelines). Washington, D.C.
United States Environmental Protection Agency. 1977b. Heavy metal
pollution from spillage at ore smelters and mills. Washington, D.C.
United States Environmental Protection Agency. 1977c. Nationwide
evaluation of combined sewer overflows and urban stormwater discharges,
Volumes I and II. Washington, D.C.
United States Environmental Protection Agency. 1979. Effluent guidelines
data, as yet unpublished. Effluent guidelines division, Office of Water
Planning and Standards. Washington, D.C.
United States Environmental Protection Agency. 1980. Memo to Jody
Perwak, Urban Runoff Pollutants, Charles Delos, Monitoring and Data
Support Division. Jan. 11, 1980.
Versar, Inc. 1978. Materials balance: Copper. Draft report to the
Monitoring and Data Support Division, EPA.
Versar, Inc. 1979. Effluent guidelines monitoring data. Memo to
Monitoring and Data Support Division, EPA.
Versar, Inc. 1980. Effluent guidelines monitoring data. Memo co
Monitoring and Data Support Division, EPA.
Wischmeier, W.H. 1975. Cropland and erosion and sedimentation. Concrol
or Water Pollution from Cropland Vol. II. Agricultural Research Service,
USDA, Washington, D.C.
31
-------
SECTION IV.
DISTRIBUTION OF COPPER IN THE ENVIRONMENT
A. MONITORING DATA
1. Cooper in Water
STORET data provide the most complete survey of ambient concen-
trations of copper in freshwater. This discussion focuses on levels of
total, rather than dissolved copper primarily because dissolved copper
was infrequently measured.
The nationwide distribution of observations of total aqueous copper
is as follows:
• 4% of all samples are in the range of .1 ug/L to 1 ug/L;
• 41% are between 1 ug/L and 10 ug/L; and
• 44% fall into the 10 ug/L to 100 ug/L category;
• 10% are between 100 ug/L and 1,000 ug/L; and
• 1% exceed 1 mg/L.
This distribution is depicted graphically in the histogram in Figure 5.
Table 7 lists all of the major river basins and the distributions of
concentrations for each. The major river basins with the highest total
concentrations of aqueous copper (i.e., those with the greatest, percen-
tage of samples containing concentrations in excess of 100 ug/LJare the
New England, Western Gulf, and Lower Colorado River basins (see Table
26 in Section VII).
STORET data indicate that bottom sediments in rivers normally con-
tain between 1 mg/kg and 1,000 mg/kg of copper, which is two to four
orders of magnitude greater than concentrations found in river water.
The distribution of values is: 30% of observations between 1 mg/kg and
10 me/ka 60% between 10 mg/ks and 100 mg/kg; and 8% between 100 mg/kg
and 1,000 mg/L. The regions with the highest concentrations in sediment
are Hawaii, the Lower Colorado River basin, and Upper Mississippi
Valley, and the Great Lakes (see Table C and Section VII).
An extensive search of the literature for levels of copper in sea-
water was not conducted, however, most reports of copper concentrations
in seawatar ara in the range of 1-5 -Jg/1 (Friberg ec^'kl. , 1977).
-------
30%
20%
—
a.
-------
Region
New England
Mid Atlantic
Southeast
Great Lakes
Ohio
Tennessee
Upper Mississippi
Souris and Red of North
Missouri
Arkansas and Red
Western Gulf
Hawaii
Rio Grande and Pecos
Upper Colorado
Lower Colorado
Great Basin
Pacific Northwest
California
Alaska
United States
TABLE 7. TQTiL COPPER IN AMBIENT WATERS
BY REGION, 1970-1979 '
Percentage of Observations
: 100-1
ug/L
3
1
2
1
1
<1
<1
<1
<1
1
3
1
9
<1
2
<1
3
1
2
4
1-10
ug/L
40
38
43
45
44
32
33
36
44
45
47
58
43
57
23
48
55
38
48
41
10-100
ug/L
33
49
37
48
49
58
44
62
49
43
29
33
.34
35
39
44
35
52
44
44
100 u g/L-
1000 u'g/L
18
9
16
5
5
9
12
2
6
11
18
5
12
6
33
8
6
7
6
10
1000-10,01
Ug/L
4
1
1
<1
1
1
9
<1
<1 .
<1
<1
<1
2
1
2
<1
<1
2
<1
1
Source: U.S. EPA, 19/9c.
-------
Region
TABLE 8. TOTAL COPPER IN SEDIMENTS
IN U.S. REGIONS, 1970-1979
Percentage of Observations
New England .
Mid Atlantic
Southeast
Great Lakes
Ohio
Tennessee
Upper Mississippi
Lower Mississippi
Souris and Red of North
Missouri
Arkansas and Red
Western Gulf
Hawaii
Rio Grande and Pecos
Upper Colorado
Lower Colorado
Great Basin
Pacific Northwest
California
Alaska
1-10
33
31
41
14
24
20
23
24
24
54
57
37
<1
16
53
40
14
18
10-100
mg/k.g
50
53
56
65
73
69
58
72
41
39
43
59
33
84
46
40
81
75
100-1,000 1,000-10,000
15 1
15 <1
1 <1
17 2
4 <1
10 1
4 15
2 <1
<1 35
7 <1
<1 <1
2 <1
67 <1
<1 <1
1 <1
20 <1
5 <1
7 <1
United States
30
60
Sourca: U.S. EPA 19/9c.
-------
2. Copper in Aquatic Organism
The amount of copper in che tissues of aquatic organisms is de-
pendent upon both concentration in water and dietary intake.
The most comprehensive compilation of data on copper residues in
fish tissues is in STORET. Of 1,150 residue analyses performed through-
out the U.S. (mostly in freshwater organisms), 67% contained from 1 mg/kg
to 10 mg/kg copper, and 27% had concentrations between 10 mg/kg and
100 mg/kg. The regions in which the mean copper residues were highest
are Hawaii, Puerto Rico, and the Colorado River Basin. Fish in the
Western Gulf states also showed high residues, now ever, sampling was
limited.
NRG (1977) summarized a .number of studies reporting copper concen-
trations in the edible portions of marine fish, ranging from 1 mg/kg
for cod to 36 mg/kg for oysters. In one study, the Atlantic oyster
(Grassestrea virginica) had copper concentrations as high as 1,050 mg/
kg when exposed to water with 50 ug/L copper (Shuster and Pringle,
1969, as cited in Phillips and Russo, 1978). As a group, mollusks have
copper residues of 1.24-1,050 mg/kg. Various species of marine worms
have concentrations ranging from 5.96 mg/kg to 94.4 mg/kg copper. Ten
species of freshwater fish found in the Illinois River had copper resi-
dues of 0.05 mg/kg to 0.39 mg/kg. No significant differences in the
residues of omnivorous and carnivorous fish were apparent. These data
are listed with references in Table 9.
3. Copper in Plants
Copper is an essential micronutrient for the normal growth and
development of green plants*. Although the quantitive requirements of
plants are lower than for any other nutrient except molybdenum, there
are many documented cases of naturally occurring copper deficiency.
Copp'er toxicosis, on the other hand, is rarely observed except on
tailing dumps or where fertilizers or fungicides high in copper have
been used extensively (NRG, 1977).
Copper concentrations in edible plants range from 1 mg/kg to 143
mg/kg (NRG, 1977). Allaway (1974) gives the range as 4-15 mg/kg on s.
dry weight basis. Crops with high copper requirements for optimal
productivity include wheat, barley, oats, corn, carrots, red beets,
onions, spinach, alfalfa, and cabbage (in decreasing order of importance).
Fink _et al. (1976) examined ten species of freshwater plants, and found
copper concentrations of 2.5-65.5 mg/kg.
Much of the copper in soils is not available for plant uptake except in
acidic soils. Lining soils to pH 7 or 8 reduces copper availability
and say be a factor in. some areas where Biases are capper-deficient
CIRC, 1977).
-------
TABLE 9. RESIDUES OF COPPER IN AQUATIC ORGANISMS
Species
Concentration
dug/kg)
Polychaete (Cirrlforaia_3airabrancha)
Squid (3 sp.)
Various taoHusks
Bloodworm (Glvcera dibranchiata)
Bristleworm (Neghthys sp.)
Clamworm (Nereis diversieolor)
Sandworm (Nereis virens)
Common Periwinkle (Littorina^ litcorina)
Blue Mussel (Mytilus edulis)
Sofc Shell Clam (Mya arenaria)
Clam (Macoma balehica)
Northern Pike (Esox lucius)
Largemouth bass (Microoterus salmoides)
(Morone chrysoosj
ShorcnoseGar (Leoisosteus platostomus)
Black Bass (Microoterus dolomieui)
Bigmouth Buffalofish (Ictiobus cyprinellu3)0.07-0.26
Gizzard Shad (Dorosoma cepedianum) 0.18-0.39
Redhorse (Moxostoma macrolepidotum) 0.16-0.20
Quilback Carpuckers (Caroiodes cvorinus) 0.10-0.30
Carp (Cvorinus car^io) 0.12-0.41
5.96-69.31
15,000 (max.)
1-10
10.1-28.0
8.9
0.8-84.4
12.1-15.6
54.6-68.0
3.9-8.5
8.4-21.5
88.1-171
0.05-0.. 08
0.08-0.13
0.17-0.24
0.13-0.20
0.14-0.16
Reference
Milanovich ec al. (1976)
Martin and Flegal (1975)1
Marks (1938)L
Flnk-et jl. (1976)
Fink e_t al. (1976)
Fink erjl. (1976)
Fink et al. (1976)
Fink et al. (1976)
Fink et al. (1976)
Fink et al. (1976)
Fink et al. (1976)
Mathis and Cummings (1973)
Mathis and Cummings (1973)
Mathis and Cummings (1973)
Mathis and Cummings (1973)
Mathis and Cummings (1973)
Mathis and Cummings (1973)
Mathis and Cummings (1973)
Mathis and Cummings (1973)
Mathis and Cummings (1973)
Mathis and Cummings (1973)
LAs ci:ac in Phillips and 3.usso (1973)
-------
4. Copper in Soil
Copper occurs naturally at a concentration of approximately 50 mg/
kg in the earth's crust, which includes both parent rock and soil. Of
the parent materials, biotite and pyroxene basalts have the highest cop-
per concentrations, averaging 140 mg/kg. Ranges in copper concentration
of 10-40 mg/kg are commonly found in sandstone, Copper is normally found only
in relatively low concentrations in coal. Copper tends co be concentrated
in clay mineral fractions, with some further enrichment in clays with
high organic carbon content. It is also concentrated in manganese oxides
where levels up to 0.1% have been found (NRC, 1977).
The rate at which parent rock is degraded into the derivative soil
depends upon the pH, the redox potential, the amount of organic matter
in existing soil, the mechanism of formation of the derivative soil, and
the degree of weathering. The pH is of particular concern in agriculture
because copper is more mobile (in dissolved form) under acid than under
alkaline conditions (NRC, 1977).
Ambient copper concentrations found in soils are approximately 20 mg/
kg. In agriculturally productive soils, copper occurs in a range of 1-50
mg/kg. Soils derived from mineralized parent material often have much
higher values (NRC, 1977).
5. Copper -in Air
a. Work Environment
-The OSHA standard for airborne copper in a work environment is 1.0
mg/m (a time-weighted average for 8-hr daily exposure to copper_ dust).
The standard for copper fume is 0.2 mg/m3, (NRC, 1977).
b. Non-work Environment
A range of 0.01-0.257 u-g/m was found in rural and urban communities
sampled by the National Air Sampling Network in 1966 (NRC, 1977). "Frac-
tional" airborne concentrations have been found near one copper smelter
with occasional weekly averages of 1-2 ug/m3. The validity or these data
has been questioned because of possible contamination of air samples by
the operation of conventional high-volume sampling equipment. Ambient
concentrations, therefore, may be lower Chan reported (NRC, 1977).
B. EJmRONMENTAL FATE
1. Overview
a. Methodology
In this section, "he environmental fate is considerad .for copper
ralsasad co the ativironment as a result of human activities. "or each
release of significant quantities co air, watar, or land, che fona of che
-------
copper in the discharge is identified, and the environmental pathway is
described. Biological pathways are considered separately from physico-
chemical and bulk transport pathways. A general overview of the environ-
mental chemistry of copper produced by Versar (1979a) has been used as the
basis for formulating judgments concerning the direction and rate of trans-
port of copper in any ecosystem. Other studies available in the literature
support the observations noted and are discussed within.
b. _ Major Environmental Pathways
The major pathways of physical transport are designated in Figure 6.
The rates at which the metal is transported are described in terms of
the relative speed at which the transport occurs.
Separate pathways for atmospheric releases (Pathway 1) are shown
for point source and dispersive emissions. Combustion processes, such as
incineration, smelting and coal combustion contribute to highly localized
pollution (la); dispersive (non-point) sources such as corrosion of copper
from chromeplated objects contribute to the concentration of copper found
in urban runoff (Ib). Pathway 2 follows the flow of copper originating
from solid waste disposal dumps and mine tailings. As environmental
controls restrain further discharges to air and water, the quantity of
copper disposed of upon land surfaces and following this pathway can be
expected to increase. Copper discharged with industrial process effluents
into local surface waters or (POTW's) follows Pathway 3. The fate of
copper in POTW's is described in Pathway 4. Deliberate releases of copper
as in agricultural uses and as in algicide, are covered in Pathway 5.
Figure 7 gives a general overview of all major environmental
pathways of anthropogenic copper. The figure also indicates the rela-
tive contributions of the copper industry and all other human activities
to the major environmental pathways. The major impact on the land com-
partment (mostly at specific disposal sites) and the underlying ground-
waters is to be noted. The migration of groundwaters containing copper
to nearby surface waters has not been shown in this figure since (1)
the process is very slow, and (2) the magnitude of the copper transported
via this pathway is not well documented. Also not represented here is
the high concentration of copper in sediments with respect to the overlying
water and in soils subject to contamination by airborne copper.
c. Important Fata Processes
Copper is concentrated in the sediments in aerobic waters, sorbed
primarily in hydrous iron and manganese oxides. Copper also sorbs to
clays and organic material. Copper transported in the water column is
in association with the dissolved or suspended solids. The primary com-
plexing speciies ara the organic agents _such_as. humic..acid; the aqueous
carbonate and hydroxide are the predominant inorganic dissolved species.
In anaerobic -w-acsrs, the solubility of copper decreases; copper vill sxisc
in che reduced phase as aecaliic copper or cuprous oxide, or pracioicaca
as'coooer suifide.
-------
t'AIIIWAV NO.
1*.
Atmospheric Emissions
(Major Point Sources)
CuO. CuS. Cu(in)
Cu Production
Siiioltinu
lion £ Sleul Production
Coal Combustion
Inciuuraliun
Atmospheric Emissions
(Non-point Sources)
CuO (paniculate). Others
Chrume & Brass Corrosion
Oil £ Lubricant Combustion
tit
Pathway #4
POTW
I
Sawari
Paveinani & Local
Road Soili
Solid Waste & Tailinos.
Coal Piles & Opun
Pit Mines
Primary Cu Production
Coal Mininu
Oiu Mining and Buneliciaiion
Surface Waters
Sediment
(Slow)
Dissolved Solids
Susp. Sediment
Groundwater
FIGURE 6. MAJOR ENVIRONMENTAL PATHWAYS OF COPPER'EMISSIONS
-------
J
4.
1
At|ueuui> Discharges
Ueuuliciaiion
Smelling
Cu I'lodiiction
POTW
lulluuitl
I
Primary
Treaimonl
j
Treatment
System
Ehluenl
\
Ha/ardous/
Solid Waste
Dump
Biological
Treatment
<
Slue
r
^*
i
J
e*
Elllueni
^~
POTW
Palltway H 4
(Surface Water
Sediments
Slow ^
Grouitdwalef
i
Surface Waters A
Sudimunis •
Ocean Dumping
Incin-
eration
Land- """
rill fc
Air
Soil
*" Oceans
K
^ Oceans
*> ^V
?
Groundwaief
r
JSIoww) *~ ' ' '
Aljicidu
Aijilciillniul
FIGURE 6. MAJOR ENVIRONMENTAL PATHWAYS OF COPPER RELEASES (Continued)
-------
Anthro-
pogenic Sourcej
ol Copper
Copper Mining
anU Production
Other Oie Mining
Runoll ami W«ifl Wttei
Viet and Oiy fallout
) Oceans
Suilacu Waleit aiul Sediments
Tailings Piles
Lagoons
Landfills
etc.
Gioundwatitr
Note: Quantities of copper moving in each pathway are roughly proportional to the thickness of each pathway shown.
Slow movement from groundwaters to surface waters not shown.
FIGURE 7. SCHEMATIC DIAGRAM OF MAJOR PATHWAYS OF ANTHROPOGENIC COPPER
RELEASED TO THE ENVIRONMENT IN THE U.S. (1979)
-------
Atmospheric emissions of copper will consist mostly of copper sorbed
to submicron particulate matter and the oxide of copper. A large per-
centage of the copper is expected to be short-lived in the atmosphere;
dry fallout and washout of copper particulates will contribute to depo-
sition upon local soils, urban pavements, and surface waters.
Copper is present in soils as a result of atmospheric deposition,
solid wasce and sludge disposal, and agricultural uses. Most of this
copper will remain in the top few centimeters of soil, sorbed to organic
matter, clays, and iron and manganese oxides, above a pH of about 5. The
potential for translocation of copper to the groundwaters is small but
can be an area of concern in sandy, porous sites, or in low pH environ-
ments, with a correspondingly high water table.
2.. Physicochemical Pathways
a. General Fate Discussion
Aqueous Complexation; The concentration of soluble copper in water
is directly related to parameters such as pH, the oxidizing potential of
the water, the presence of other competing ions (e.g-, calcium, magne-
sium, and iron), the concentration of precipitating agents (e.g., OH",
S=, P0^=, CO-j3 ), and the concentration of complexing agents. Generally,
at low pH values and in waters of low alkalinity copper will be more
soluble; at high pH levels, and in highly alkaline waters, copper is
usually found in a complexed form with organic ligands, carbonates and
hydroxides. In natural, aerated waters cuprous copper (Cu(I)) is un-
stable, and will immediately oxidize to cupric copper (Cu(II)). Chloride,
nitrate and sulfate complexes are highly soluble in water: 70.6 g, 138-
244 g, and 14.3 g/100 H20, respectively (Weast, 1972). Insoluble forms
of copper typically found in aerated natural waters are the oxide and
hydroxide; ;a anaerobic waters, the insoluble sulfide, cuprous oxide,
and metallic copper will predominate. Stumm and Morgan (1974) determined
the copper complexes that predominate'over a pH range of 0 to 14 in equil-
ibrium with copper crystalline solids: malachite (Cu2(OH)2C03), azurite
(Cu3 (OH) 2^03)2) and tenorite (CuO)_ The predominating soluble species
above pH 7 are CuC03(aq), Cu(C03)2 = and hydroxy copper complexes; below
this pH, the free ion exists. Figure 8 indicates how complex copper
chemistry may become.
Adsorption to Sediments and Suspended Solids; The computer program
used by Vuceta and Morgan (1978) to calculate equilibrium species of
heavy metals between pH 6.2-8.0.in the presence of naturally occurring
inorganic and organic liquids indicates that copper solubility is dic-
tated by the available colloidal surface area, represented in their cal-
culations as Si02- When complexing agents (i.e., inorganic and organic
ligands) are present in low concentration, sorption of Fe, Mn and Si oxides
controls copper solubility. Figure 9 illustrates che ease with which
cooper is adsorbed compared vith ocher divalent metals. The major
aqueous species in solution would be Cu-OH and Cu-CO^ complexes. Another
44
-------
J
o>
3 6
10 -
CujlOl J*-'\ N \
NT3£i£Y>K-
/ \ >v .A \/CU«OH«?
c^viy x x< V\o^
L - I / I VI X I •<' \|\
10
12 14
pM
Reference: Stumm and Morgan (1970).
FIGURE 8. SOLUBILITY DIAGRAM OF Cu(ll) IN EQUILIBRIUM
WITH MALACHITE, AZURITE, AND TENORITE
FROM pH 0-14
Reference: Vucsta and Morgan (1978).
FIGURE 9. ADSORPTION OF HEAVY METALS IN OXIDIZING FRESH
WATERS (pH=7, ?£=12, pCO^IO'3'5 arm., pCt-4.16) AS A
FUNCTION OF SURFACE AREA OF Si02 IN ha/L. pS=»-log
(Si02) ha/L
-------
study determined that humic acids are significant complexing agents for
copper, and enhance metal adsorption to iron and manganese oxides by
laying a thin film over suspended particulate matter (Davis and Leckie,
1978). As the concentration of complexing species increases (i.e.,
003=, OH~, humic acid) partial or total desorption of copper may occur,
with the dissolved copper complexing primarily with organic liquids
(Vuceta and Morgan, 1978).
Distribution of Copper in Surface Waters; Perhac (1974) investigated
the distribution of copper within stream bed sediments and the water
column of three rivers in Tennessee. The results obtained are summarized
in Table 10. These rivers drain (1) a rural area containing visible zinc
mineralization, (2) a control stream and (3) an industrial river. The
results indicate that the bulk of copper in the water column is trans-
ported through surface waters in the dissolved phase in these examoles, although
the highest concentrations exist in the particulate fractions. These data show
a higher copper concentration in the colloidal particulates than in the
coarse particulates, which agrees with other data showing an inverse
correlation between copper concentration and sediment grain size.
TABLE 10. AVERAGE DISTRIBUTION OF COPPER IN THREE RIVER WATERS
Particle Size
(um)
Average Copper
7, Total Concentration % Total
Solids (mg/kg) Copper
94.5
5.3
0.11
0.02
129
2454
1729
92.3
1.3
6.3
Water
Dissolved Solids1
Colloids <0.15
Coarse Particulate >0.15
^Brought to dryness.
Source: Perhac (1974)
In contrast, Stiff (1971) reported that 12-57% of the total copper
was present in the dissolved form in British rivers. Unfortunately,
insufficient' information is available to generalize from these conflict-
ing results.
Another work determined the correlation between sediment and heavy
metals by studying a river during periods of high discharge, at which
time, deposiced sediments are resuspended and transported downstream
(Delfino, 1977). Although the correlation coefficient (r) between
copper concsntration and flow of total suspended solids vas not very
significant (about 0.5), the correlation of Cu vith Fa vas 0.94, and
with Mr., 0.92. Sines both ?e and Mn were primarily asscciatad with
suspended sediment (90%), the author concluded "hat copper must also
be distributed in a similar manner, although measurements vera not
made to confirm this.
-------
TABLE 11 COPPER CONCENTRATIONS AS A FUNCTION OF WATER HARDNESS
AND URBANIZATION—TRIBUTARIES OF LAKE CAYUGA. N.Y.
Water Hardness/ Particulate Cu
Urbanization (mg/L)
Ihird Waters (n = 6)1
Soft Waters (n * 6)
Ililuut Streams (n = 4)
Km til Streams (n = 8)
Haul, Rural Streams (n - 6)
Soft, Rural Streams (n = 2)
1.8
2.6
3.1
1.7
1.7
1.55
Soluble Cu
(niR/L)
0.49
0.86
1.02
0.50
0.49
0.53
Ratio of
Particulate to
Soluble Cu
3.7
3.0
3.0
3.4
3.5
2.9
Average
Alkalinity
(mg/L)
154
90
88
139
154
94
n = number of sites for which data were available.
Source: Kubota et al, (1974)
-------
Kubota et al. (1974) reviewed the concentrations of trace metals
associated with geocheniical and soil weathering on twelve tributaries
draining into Lake Cayuga, New York. Four of the streams also receive
some anthropogenic contributions from urbanized areas. Table 11 sum-
marizes the concentration of soluble and particulate copper as a func-
tion of alkalinity and urbanization. The pH was consistently between
8.1 and 8.3 and temperature between 10"C and 13°C.
The data in this table indicate that the concentrations of both
soluble and particulate forms in hard water and in soft water rural
streams do not differ significantly. The authors did not draw any
parallels between copper concentration and alkalinity other than noting
that high levels of hardness corresponded to high alkalinity values.
Copper concentrations in the tributaries draining Ithaca, New York, were
about two times those of rural streams, regardless of water hardness,
or alkalinity.
Copper in the bottom sediments of the streams studied by Perhac (1974)
associated with carbonates and iron oxides with minor amounts sorbed to
organic matter, clays and perhaps sulfides. The form of copper in the
sediments is not readily exchangeable or soluble in natural, alkaline
waters, and would not be likely to contribute to biotic uptake. Table
12 summarizes the data pertaining to the stream water just after it passes
over the mineralized area. It appears that the concentration of copper
in the water column is not significantly affected by local fluxes in the
sediment composition.
TABLE 12.. COPPER CONCENTRATION IN WATER AND
SEDIMENTS AFTER EXPOSURE TO ZINC OUTCROP
Copper Concentration
Bottom Sediment Water
Sample Site me/kg ug/L
Mineralized Outcrop (carbonate rocks) 10 22
1 km downstream (carbonate rocks) 26 is
1.5 km downstream (clay strata) 25 21
Source: Perhac (1974)
The suspended particulates in the water column were found to con-
centrate copper more than the bottom sediments. This is due to the
reduced surface araa (and subsequent loss of sorption sites) of the
sediments resulting from particulate flocculation prior to settling
-------
Soils;. The behavior of copper-in-soils—is dependent upon che ad-
sorptive properties of che soil, as well as che pH and redox potential
of che soil solution. In aerobic soils, the solubility of copper is
controlled by CuO at a soil pH of 5 and carbonate and sulfur concentra-
tions at 10"% (Huang et_ al., 1977); under the same conditions, CuS will
control the availability of soluble copper in anaerobic soils. Copper
is easily sorbed; it exceeds zinc, lead and cadmium in adsorbing poten-
tial. Adsorption of copper as well as other heavy metals onto hydrous
oxides and soil particulates is strongly dependent on pH, as illustrated
in Figure 10. At a pH range of 5-6, adsorption is the principal means
of removing copper from solution; above this pH, chemical precipitation
becomes more dominant. Below a pH of 5, sorption of copper becomes
insignificant. Figure 10 illustrates this trend. The presence of
organic ligands, such as humic acids, enhances metal adsorption at low
pH values. Humic acid was the most effective ligand in this respect,
out of five tested.
Summary; The concentration and speciation of soluble copper in the
water column is dependent upon the pH and redox potential of the water
and nature of complexing ligands. In natural aerated waters, Cu(II)
complexes with organic ligands, carbonates, and hydroxides. In reduced
environments, copper will be present as cuprous oxide, metallic copper
and CuS.
Copper adsorbs to iron and manganese oxides, clays, and organic
matter in the sediments. Its tendency to adsorb exceeds that of other
divalent metals. Suspended solids concentrate copper; at times this
concentration exceeds that of the sediments due to a greater number of
adsorption sites on suspended sediment. However, the amount of copper
in suspended sediments is usually small compared with Che amount of
copper found in the sediment.
In conclusion, most of the copper found in natural waters, is par-
titioned with the sediment component. In the water column, concentra-
tions of copper are greatest in the suspended sediment, but the greatest
mass of copper may be found with che dissolved solids.
In soils, copper adsorbs above a pH of 5; organic liquids, especially
humic acid, enhance this trend. Compared with other metals, copper
demonstrates the greatest tendency toward adsorption. In acid environ-
ments, copper will be available in the soil solution, although to less
of an extent than other metals.
49
-------
Reference: Huang at al.(1977)
FIGURE 10. ADSORPTION OF HEAVY
METALS ON SOIL MINERALS
AND OXIDES
Incinerator _
Open hearth furnaces uncontrolled COPPER
"Zinc smelter coker
Open hearth furnaces. E.S.P. controlled
Zinc sinter plant
Zinc vertical retort
4 6 3 10 12
Aerodynamic diameter, microns
Reference: Jacko and Neuendorf (1977)
FIGURE 11. AERODYNAMIC PARTICLE SIZE
DISTRIBUTION OF COPPER IN
INDUSTRIAL STACK EFFLUENT
30
-------
b. Atmospheric Transport
Pathway #1
Atmospheric
Emissions
Groundwaer
Ocean
Smelting
Iron and Steel
Coal Combustion
Incineration
Chrome and Brass Corrosion
POTW
Air
Sources; Pathway #1 describes the fate of copper as a result of
stationary source air emission from smelting, iron and steel coal combus-
tion and incineration. In addition, area sources such as chrome and
brass corrosion have been included in this pathway. Although these
releases may not be strictly atmospheric, their pathway to pavement and
local soils is similar. The forms of copper released due to thermal
processes are the oxide, (CuO), elemental copper, as the vapor, and
absorbed on.particulates; copper sulfide, as the dust, is the result of
entrainment from coal pits.
Once copper has been released into the atmosphere, its residence
time and distance travelled are dependent upon its particle size, as
well as meteorological factors. Copper from combustion sources tends
to associate with sub-micron particulate matter due to selective adsorp-
tion of the copper vapor upon particulates with a large surface area to
volume ratio (Jacko and Nueundorf, 1977). Jacko _et_ al^ (1975) investi-
gated the metal distribution upon particulates emanating from municipal
and industrial incinerators. They found that .the concentration of copper
adsorbed to particulates increased twenty times as the diameter of the
particle decreased from 4.6 urn to 0.6 urn. The work of Coles et al.
(1979) supports this trend. Copper was partitioned amongst fly ash
particulatas in the following manner: 56 mg/kg on 18.5 ym fraction, 89
mg/kg on 6.0 urn, 107 mg/kg on 3.7 urn and 137 mg/kg on 2.4u m fraction.
Figure 11 illustrates the distribution of copper adsorbed co oarticulatas
resulting from a variety of industrial stacks (Jacko and Neuendorf, 19/7).
The zinc vertical recor-, zinc saeltsr, and open.hearth furnaces had no
31
-------
air pollucion control devices, Che zinc sinter plant, and indicated open
hearth furnaces were controlled by electrostatic precipitators; the
incinerator was equipped with a scrubber. Although no trend is observable
concerning the types of controls, the diagram does indicate that the
largest percentage of copper is associated with a particle diameter of
somewhat less than 2 urn.
Jacko _e_t _al. (1975) investigated the cleaning efficiencies of
incinerators equipped with horizontal plate scrubbers, and venturi
scrubbers. The average atmospheric emission from the former incinerator
(for refuse) was 38% of the initial copper input, while from the latter
(for sewage sludge) about 0.10% was released. The authors concluded
that the large discrepancy was caused by scrubber efficiencies, not by
differences in the incinerated contents.
Deposition on Soils: Once in the atmosphere, particulates are
deposited quickly via rainout or dry fallout, and this results in a
mean residence time of 7-30 days (Versar, 1979b). Though most of this
deposition will occur over land surfaces in the Immediate vicinity of
the emission source, some of the copper will clearly be transported
over much greater distances due to the small particle size; the fallout
will vary from location to location depending on climatic and other factors,
The trace metal enrichment in the soils and grasses near a lead smelting
complex gives an indication of the extent of metal deposition from aerial
sources (Ragaini _£££!., 1977). The average concentration of copper in
the top 2 cm of soil was 278 (+ 108) mg/kg within 2 miles of the smelter.
The background concentration, measured between 3.3 and 7.8 miles from the
smelter, did not exceed 185 mg/kg. For grasses, the copper concentration
ranged from 38 mg/kg to 110 mg/kg in the contaminated sites, and from
21 mg/kg to 26 mg/kg in the background area.
Versar (1979a) states that copper is tightly bound to hydrous iron
and manganese oxides, and clays, making these components of the soil the
major control mechanisms for copper mobilization. The work of Huang
.et al. (1977) supports this statement, which concludes that even at
pH values as low as 5, copper does not readily desorb off soil particles.
(See previous discussion of general fate in soils—IV-B-1. O
According to Versar (1979b), the deposition of copper upon the soil
surface allows for the entrainment of soil particles containing copper
back into the atmosphere. This cycle is dependent on, among other
parameters, groundcover and soil moisture, and will continue indefinitely.
Once the copper is airborne, the same type of physical phenomena discussed
previously will apply. Surface runoff of soil particulaces will also
result in the introduction of copper into surface waters and sediments.
Bioaccumulation of deposited copper will be another pathway, among boch
terrestrial and aquatic organisms. However, the bulk of the copper chat
is deposited upon soil surfaces will remain bound up in the soil compart-
ment.
32
-------
Fallout in Urban Areas; Deposicion of particulates in urban areas
is due co combustion plants within the city, 'such as incinerators and •
coal-fired power plants, and corrosion of products containing copper,
such as chrome and brass. Kleinman e_t al. (1977) determined the flux
of atmospheric fallout over New York City by placing dust collectors on
three rooftops in Manhattan. The data for copper indicated that the
element remains at a relatively low constant baseline, with sporadic
large spikes of concentration, as indicated in Figure 12. The range in
the average deposition rates for copper was 800-1,700 ng/cmVmonth.
The authors then determined the concentration of copper in street runoff
entering the New York Harbor resulting from atmospheric deposition:
Atmospheric copper dustfall (ng/cm /month) 750
Estimated [Cu] in runoff (mg/L) 0.06
Discharge of Cu in runoff (kg/day) 210
Discharge of Cu - other sources (kg/day) 1,100
% Contributed by runoff to surface waters 16%
According to this study, fallout of copper over urban areas contributes
appreciably to the flux of copper entering surface waters via runoff.
Deposition on Surface Waters: Fallout of heavy metals in the
southern California coastal zone has been studied by Bruland ££ al.
(1974). They estimated that anthropogenic sources of copper contribute
1.3 ug/cm2/yr (= 108 ng/cm2/month) to the sediments, while natural pro-
cesses account for 1.6 ug/cm2/yr (133 ng/cm2/month). The flux of copper
due to rainfall had been reported in a previous study as 0.5 ug/cm2/yr
(42 ng/cm2/month). In order to determine the relative contribution of
washout to the anthropogenic fluxes observed in the bay, they estimated
that over a 12,000 km2 area, 567 tons Cu/yr was due to contributions
from wastewaters, 18 tons/yr from stormwater runoff, and 60 tons/yr from
washout. The flux of copper from anthropogenic sources to the sediments
amounts to 160 tons/yr. Therefore, both the stormwater runoff and wash-
out contribute significantly to the anthropogenic fluxes observed in
the bay (12%).
The airrwater interface, or surface microlayer, is frequently studied
due to its ability to concentrate pollutants. In southern Lake Michigan,
the surface particulate microlayer contained 190 Ug Cu/g, while the bulk
water particulates. contained 30 ug/g (Elzerman ££.aJL. 1972). Entrain-
ment.of aerosols containing copper from the air-water interface is a
probable means of copper transport.
Peyton and Mclntosh (1974) compared the sediments of a borrow pit near
industrialized Gary, Indiana, with chose in a rural control pond. In
the cop 5 cm of sediments, che borrow pic contained 52.1 ag/kg Cu, while
the rural pond contained 10.0 mg/kg.- the metals entering che system
-------
I I I '_ I i i I i i i I i : i i i i
.'J«*» YnrK U'»vr>v(\ .'.Viln .11 l.V-Ir
/ I
I
and Sa'etv
MJJASONOJFMAMJ JASOI'iOJ
1974
Raferenea: Kleinman et at. (1977).
FIGURE 12. MONTHLY DEPOSITION OF ATMOSPHERIC COPPER IN NEW YORK CITY
-------
through che air were associated with a maximum particle size of 10 urn.
The concentration of copper in one core typified the distribution:
Sediment Size Range (urn) [Cu] mg/kg
750 13
50-20 60
20-10 80
10-2 66
< 2 89
About 50% of copper resides with particulates of less than 10-um diam-
eter that apparently originated from the air.
Groundwater; Groundwater contamination by the copper ion will be
a function of a number of parameters, the two most obvious being the
depth to the groundwater table and the composition of the soil. How-
ever, as demonstrated by copper's affinity toward soil particulates,
groundwater contamination is not probable except in sandy, porous
soils. Most of the particulate copper that is deposited exists as the
oxide. Initial copper mobility will depend upon the solubility of the
copper compounds deposited. Copper oxide is highly insoluble in water,
as is copper sulfide. Copper sorbed to particulates will not readily
desorb.
SitTTtma-ry; Copper enters the atmosphere primarily from point-source
combustion processes and to a lesser extent from dust from coal piles
and tailings and aerosol entrainment and corrosion. Copper is sorbed
preferentially to submicron particulates, whose residence time in the
atmosphere is subject to meteorological conditions such as washout and
fallout. Localized pollution of soils, pavements and surface waters
results from point.source emissions. The percentage of copper from
aerial deposition contributing to the concentrations found in urban
runoff and washout has been found to be significant.
-------
c. Solid Wastes
Pathway #2
Air
Solid Wastes,
Coal Piles &
Open. Mines
Surface
Water <
Sediment
ff
I
Ocean
Groundwater
Sources of Solid Wastes, Tailings and Coal Piles, etc.: Most of
these materials arise from mineral ore processing, and coal mining. The
solid vastes result from the overburden of surface mining and the
low-grade portions of mineral ore deposits. The tailings, which contain
highly concentrated minerals, are produced as a final waste product of
mineral concentrating operations (Martin and Mills, 1976). Other
wastes may be derived from a variety of other industrial processes or
from municipal refuse.
Since 1845, the production of copper has contributed 5780 million
MT of tailings, and 14450 million MT of combined tailings and waste
(Martin and Mills, 1976). Disposal of these wastes in the 19th and 20th
centuries was without regard to environmental considerations, and thus,
erosion and weathering contributed to adverse ecological impacts.
Currently, tailings are left to settle in lagoons, after treatment with
lime to raise the pH and precipitate heavy metals.
The nature of the solid wastes and tailings depends upon the nature
of the ora. • Copper ores are numerous. A few representative ores are
azurite (2 CuC03.CU(OH)2), cuprite (Cu20), bornite (CusFeS^),
chalcocite (Cu2S), and chalcopyrite (CuFeS2); this last one being the
most abundant (Versar, 1979a). The host rocks for these minerals are
granite (10 mg/kg Cu), sandstone (30 mg/kg Cu), limestone (4 mg/kg Cu),
and basalt (100 mg/kg Cu). Coal piles and solid wastes from coal
cleaning processes may also be sources of copper for the pathway being
considered. One survey of L01 samples of U.S. coal showed a aea.n
copper concentration of 15 mg/kg, with a range of 5 nig/kg co 51 ag/kg
and 3. standard deviation of 3 ag/kg (Mesey _££ zL_. , 1976). Levels of
copper have been shown co have a positive correlation with ?yrice (7eS?)
-------
in coal, and copper often occurs in conjunction with nickel. Copper is
mostly concentrated in the mineral matter of coal, but can be associated
vith organic matter. The association of copper with pyrite implies that
copper may'be concentrated in the solid wastes from any coal cleaning
operation designed to remove pyritic sulfur and/or other inorganic
mineral matter from coal.
Acid Mine Drainage; Tailings and solid waste from mineral mining
aid. in the.formation of mineralized acid discharge. This is caused by
the exposure of fine particulates to air, upon which the oxidation of
metal sulfides results in the formation of sulfuric acid. The impact
of acid mine drainage to local surface waters is largely dependent upon
the alkalinity, or buffering capacity, of the waters upstream and down-
stream of the point of discharge. Pyrite, with which copper associates,
is easily oxided to Fe(OH)3, producing acidic waters as a consequence
of the reaction. Igneous rocks, which host pyrite, are low in calciferous
material and, therefore, the water that passes over the gangue has little
opportunity to dissolve carbonates and become a buffered solution. For
these reasons, a large potential exists for adverse impacts to the local
waters of a mined region.
Fate Processes in Streams; Figures 13 - 15 summarize observa-
tions for a stream that receives acid mine drainage (AMD) (Martin and
Mills, 1976). The mine occurs at kilometer 35 and the confluence of
two streams occurs at 0 kilometers.. The pH and bicarbonate concen-
tration in stream waters drop immediately. At the same time, the con-
centration of dissolved copper increases dramatically. These figures
also give an indication of how the stream's recovery is a function
of distance from the source.
Precipitation, adsorption and dilution reduce the concentration of
copper in the water column (Martin and Mills, 1976). A literature review
performed by Versar (1979a) concludes that sorption is the dominant
process affecting the reduction of copper in surface waters. Sorption
upon hydrous iron and manganese oxides, clays and organic matter results
in enriched sediments and suspended solids so that Cu concentrations in
these fractions are in the mg/kg range, while the water column exhibits
concentrations of copper in the ug/L range. Holcombe (1977) found that
copper draining a mined area sorfaed preferentially to manganese oxides
rather than to iron oxides. Iron oxides exhibit a positive surface
charge at low pH values, repelling the copper ions, while the opposite
is true of manganese oxides.
Groundwater Contamination; Contamination of groundwaters by metals
leaching through tailing piles has been cited by Martin and Mills (1976) .
Leaching of acid mine drainage is a function of the tailing pile porosity.
Tailings from years ago vers higher in porosity, and chis allows more
"active leaching co occur. One may surmise chat the acid nacure of the
leachata and porosity of she piles allow greater translocacion of copper
chan vould be found under controlled landfill conditions.
-------
to
9
3
7
9
'
4
3
2
1
39 30 23 20 19 10 9
KilOfTMTVTl
FIGURE 13. THE pH IN KERBER CREEK
.5
.§
1
5
200
180
160
140
130
80
60
40
20
•0
100
90
30
. 70
' 60
SO
40
30
20
10
Oct. 77 '-U
Otc. 72 — — —•
F«d. 73
M>v 73 ---O
Jun» 73 —..— ..—..
QQ- Indieatn Oira at Station-
not abit to imvpoUit 3ttw««n
Stniom Out to UMK a< 0»t»
:«*•-•
19
10
39 30 29 20
Kiianwnn
FIGURE 14. BICARBONATE CONCENTRATIONS IN KERBER CREEK
\
40
S M 29 20
Kilomttm
Mtrtinjna Milli (1978).
10
FIGURE 13. DISSOLVED COPPER CONCENTRATION IN KSaSES Cfl6=X
53
-------
Disposal of municipal solid wastes and subsequent leaching of metal
were studied at two sites (Roulier,.1975). At the first site, leachate
was collected from 1390 kg of municipal refuse under anaerobic conditions.
The concentration of .copper was below the detection limit of 0.05 mg/L.
In order to simulate contaminant migration, metal salts were brought into
solution (100 mg/L) and slowly passed through soil columns packed with
sand and clay minerals. The soil columns were then leached with water
in order to distinguish the more mobile metals, and subsequently, with
0.1 N HC1 to identify the tightly-bound metals. Copper fell into the
category of "least generally mobile." At the second site, soil columns
were packed with whole soils (organic and inorganic components) and the
initial metal concentrations and flow rates were higher. Even under
these conditions, copper was almost completely attenuated. Data from
other landfills show copper concentrations in leachate ranging from
0.01 mg/L to 2.0 mg/L, with 0.04 mg/L being a typical value; copper was
considered to be a significant pollutant in leachate since the concen-
trations found were significantly higher than those found in nearby
(unaffected) groundwaters (U.S. EPA, 1977b). Another study of 12 land-
fills ranging in age from 0.25 years to 16 years showed a mean copper
concentration in the leachate of 0.41 mg/L (range 0.1 - 1.0 mg/L range)
(Chian and DeWalle, 1977); this is an order of magnitude greater than
the results of the above study.
Analysis of leachate from a power plant ash pond revealed 12.2
mg/L particulate copper and 275 mg/L soluble copper (Theis and Richter,
1979). Within 100 m of the pond, copper was available as the ion and
as copper sulfate. At a distance of 400 m from the pond, some of the
copper was associated with hydrous iron and manganese oxides, while
most precipitated as Cu2(OH)2C03(s). However, fly ash also serves to
attenuate the migration of heavy metals. One study found that about
4.7 ng of copper will sorb to 1 g of fly ash; the alkalinity and pH
of the fly ash ponds promote the precipitation and deposition of copper
in an insoluble form (Chu e£ a_l., 1978).
Ultimate Sinks; Lakes or oceans that are fed by streams or ground-
water from mined areas and solid and hazardous waste sites may serve as
the ultimate sink for copper. The effect of a polluted stream on a lake
is a function of the volume of pollutants introduced to the lake and the
natural buffering capacity of the lake. Martin and Mills (1976) suggest
that the most notable effects of acid mine drainage will result at the
mouth of the stream. It is likely that the stream drops its suspended
load when its velocity is slowed upon entry into the lake.
Summary; Solid wastes, coal piles, and tailings are sources of
copper disposed of on land. Copper disposed as a result of mining
practices is subject to greater trans location in the environment due to
the acid nature of the leachate. Surface streams draining mined areas
experience localized spikes in copper concentration. The level quickly
decreases as che scream recovers in pH and alkalinity values as a function
of distance from the release. The major processes affacting the reduction
in copper concentration are dilution, sorption and precipitation.
-------
Studies of municipal waste landfills found that the copper concen-
tration in leachate typically falls between 0.04 mg/L and 0.4 mg/L.
Copper is quickly attenuated by the soil. No data was found regarding
groundwater contamination. Such contamination is not likely to occur.
in a properly operated landfill. In old sained areas, acid mine
drainage and porous tailings enhance the possibility of groundwater
contamination.
d. Aqueous Industrial Discharge
Pathway if3
Effluent
Aqueous
Discharge
Treatment
sludge
Surface Waters
Sediments
Oceans
Hazardous
•Waste /Dump
Sites
Pathway #4
Sources and Treatment; Pathway #3 considers the fate of copper
discharged with industrial wastewater effluents. The industries that
discharge copper are numerous; the major ones are involved in copper wire
production,-electroplating, brass manufacture and scrap refining. In-
dustrial effluents are discharged with or without treatment into natu-
ral waters or municipal wastewater treatment systems. Yost and Masarik
(1977) have investigated the efficiency of "chemical-destruct" systems,
of the sort employed by the metal finishing industries. Neutralization
and precipitation of copper in a waste effluent originating from 90%
steel, and 10% brass were found to result in copper removal as sum-
marized below:
60
-------
Treatment [Cu] mg/L % Removed
CN system output 0.65 70%
Settling Tank Output 0.15 64%
The distribution of copper in the treated wastewater averaged 0.07
mg/L (28.5%) in the dissolved phase, and 0.41 oig/L (71.5%) in the sus-
pended solid phase. These results suggest that copper discharged with
treated wastewater effluents is most concentrated in the particulate
phase.
Yost and Scarfi (1979) determined the factors affecting copper
solubility in electroplating wastes. Their results indicated that at
the pH normally used for alkaline precipitation (8.5-9.5), CuCn was more
soluble than CuSO^, and that as the initial Cu concentration increased,
the solubility of CuCn increased; the solubility of CuSOi» was not affected.
This indicates that concentrating a CuCN waste prior to treatment will
increase the amount of copper discharged. Their data also revealed that
the concentration of soluble copper increased when CuCN was mixed with
zinc and cadmium plating solutions and decreased with nickel plating
solutions. These observations led the authors to suggest that effective
copper treatment is realized by treating copper cyanide solutions
separately from zinc and cadmium plating wastes, or in conjunction with
a nickel plating solution.
The effluent of industrial waste treatment is discharged to
municipal sewers or surface waters. The fate of copper, once it reaches
a POTW, will be discussed separately in Pathway #4.
Distribution in Surface Waters; The distribution of copper
discharged into surface waters from industrial plants has been studied
by Mathis and Cummings (1973), who used the Illinois River as their
environmental system. The river is known to receive both municipal
and industrial waste discharges. When compared with non-industrial-use
(rural) rivers, the average copper concentration in the sediments
of the Illinois River (19 tng/kg) was found to be 2.5 times that of
the rural rivers (7.7 mg/L). A study of trophic level concentrations
revealed that the sediments and benthic feeders were the greatest
accumulators of copper as revealed below:
Ecosystem Component Average Copper Concentration (mg/kg)
Water Body 0.005
Carnivorous Fish 0.13
Omnivorous Fish 0.21
Clams 1.5 .
Tubificid Annelids 23
Sediments 19
-------
A study of methods for treatment of copper wastes resulting from
scale and corrosion products from boiler tubes showed that discharge
of the effluent into a fly ash pond results in removal of copper both
by precipitation (at pH greater than 10) and adsorption (Chu et_ al.,
1978). Generally, about 4.7 ug of copper will be adsorbed onto each
gram of fly ash, regardless of the pH level.
The behavior and distribution of copper discharged as an industrial
waste into a marine environment has been investigated by Stoffers e_t al.
(1977). The waste effluent studied was reponsible for adding approxi-
mately 200 Ib Cu per day into Buzzards Bay. Analysis of the clay
fraction (<2 u) of sediment cores sampled in the Bay revealed the
following:
Core Sample & Depth [Cu](mg/kg) in Clay
A. Near discharge, 0-20 cm 3136
B. Midway, 0-10 on 580
C. Edge of Bay, 0-5 cm 117
0. Background 20
Unfortunately, it is difficult to discern a definite trend in these
data, since the core sampling depth was not held constant. It is inter-
esting to note, however, that the copper concentration at the end of the
Bay is three times the background level, suggesting that the estuary may
act as a pollutant sink.- The authors found that 39% of the copper
resided with the insoluble mineral detritus (clays), 18% with the
authigenic phase (minerals residing in sedimentary rock), and 42% with
the organic fraction of the sediment. The work of Seme (1977) supports
this distribution. He found that copper in the San Francisco Bay
sediments is partitioned as follows:
Copper
Average
Sediment Component Concentration (mg/kg)
Interstitial water
Exchangeable phase
Carbonates, Mn Oxides
Organics, Sulfides
Iron Oxides
Clays
TOTAL 98.7
-------
Sludge Disposal; the sludge generated by industrial effluent treat-
ment is normally disposed of in a solid or hazardous waste dump or a
settling pond. A properly designed hazardous waste dump should prevent
further translocation of copper due to leaching. At some sites the
leachate is collected and sent to a POTW (with or without further treat-
ment). Groundwater contamination is possible in a poorly operated land-
fill or settling pond. The speed at which copper is translocated in
this pathway is very slow, due to copper's affinity to soils. The
fate of copper in solid waste disposal sites was reviewed in Pathway
#2.
Ultimate Sinks: The major sinks for copper associated with treated
industrial effluents are, in the short term, local waterways and hazardous
waste dumps, settling ponds, or sites used for the disposal of sludge
generated by POTW's. The long-term sinks, as discussed earlier, are the
oceans and lake sediments.
Summary; The concentration of copper in aqueous industrial dis-
charges may be lowered by treatment of the waste effluent prior to
discharge, as demonstrated by the metal-finishing industry. Surface
water sediments are the best indicators of anthropogenic inputs, as are
the benthic organisms. Marine sediments also reflect these inputs,
with copper distributed principally with the organic, sulfide and clay
components of the sediments. Disposal of sludge generated by waste
treatment in a properly-operated landfill should prevent further
translocation of copper.
63
-------
e. POTW
Pathway
Effluent
POTW
Influent
-
Primary
Treatment
-*
Biological
.Treatment .
-
Surface
Waters
-
Ocean
X
Sludge
Incineration
Land disposal
Ocean disposal
Treatment Schemes; Pathway #4 describes the fate of copper in
vastewaters that are introduced into a POTW. The inflow to the POTW
may consist of combinations of industrial and commercial effluents-,
domestic wastes, and surface runoff. Though the nature of the
influent in,to each POTW is quite varied, typical copper concentrations
are about 0.01-1.97 mg/L* (Sverdrup and Parcel, 1977). Domestic
wastes have been estimated to contribute about 50% of'the copper as
determined by averaging the data of the three cities used for the
study of Davis and Jacknow (1975).
The degree to which copper is removed from the raw wastewaters,
and thus the concentration of copper in the discharged wastewaters,
depends on the type of treatment involved. One report provides a
summary of data from 269 municipal treatment plants in the U.S.
using various treatment methods (U.S. EPA, 1977a). The data for
copper are summarized below.
Activated sludge craacaenc processes ara likely Co be ir.hibi.cad
by influent copper concentrations above I 2g/L (U.S. E?A,
1979a).
-------
Effluent Data (Means)
Removal Cu Concentration
Type of Treatment of Cu (%) (mg/L)
Primary 26 .19
Biological (all types) 26 .13
Activated sludge 37 .19
Trickling filter 54 .13
Biological with chemical addition 75 not available
Tertiary 73 not available.
These data, as well as other sources, are described in Section III.
The notion of concentration-dependent removal efficiency for copper
from POTW influents can be demonstrated from the data generated from
an activated sludge treatment plant in Grand Rapids, Michigan (Biener
and Bourma, 1978). In 1968, the metal platers and other industries
were forced to pretreat their waste prior to discharge into the sewer.
Before this requirement, 25% of 2.8 mg/L copper in the influent was
removed in the municipal treatment plants; after pretreatment enforce-
ment, 63% of 0.30 mg/L copper was removed. Figure 16 illustrates the
reduction of copper concentrations in sewage at the Grand Rapids plant.
•Support for enforcement of pretreatment regulations is indicated
in the work of Mytelka e_t al. (1973). They found that high copper con-
centrations in the effluent following secondary treatment were due to
influent concentrations too large for the capacity of the treatment
system. When the waste was treated at the industrial site where itr is
generated, the municipal systems were not overstrained and were able to
ensure proper treatment of the heavy metals in the waste.
Copper is partitioned into the sludge portion of the waste during
treatment. A study of 205 sewage sludges showed copper levels of 84
mg/kg to 10,400 mg/kg, with 1210 mg/kg as the mean value and 850 mg/kg
as the median (U.S. EPA, 1979). Industrial pretreatment of wastes
destined for POTW's can significantly reduce the copper content of POTW
sludges. The percentage of industrial contributions to these POTW's was
not stated. However, it is known that all three cities sampled are highly
industrialized. Three examples are given below (U.S. EPA, 1979a):
Copoer Concentration (dry basis) in POTW Sludges
Before Pretreatment After Pretreatment
City • (me/kg) (mg/kg)
Buffalo, NY 1,570 33Q1
Grand Rapids, MI 3,000 2,500
Muncia, IN 1,750 700
•Projected
65
-------
3.0
2.0
o
5
O
O
1.0
Influent 39% Reduction
Effluent 93% Reduction
68 69 70 71 72 73 74 75 76 77 78
Year
Reference: Biener and Bourma (1978)
FIGURE 16. TOTAL COPPER IN SEWAGE AT GRAND RAPIDS, MICHIGAN
BEFORE AND AFTER PRETREATMENT OF INDUSTRIAL
DISCHARGES TO A POTW
-------
Sonmers at-al-.-~(19-76-)-found-that after 9 weeks of anaerobic diges-
tion, a 2-L quantity of synthetic sludge containing ash and organic
matter typical of municipal sludge, plus 96.1 mg Cu(N03)2«3H20, retained
less than 0.2 mg/L (the detection limit) of water-soluble Cu. The air-
dried sludge retained approximately 700 mg/kg Cu. The authors also
found that organic matter is responsible for tight binding of copper as
determined by an extraction method for inorganically and organically
bound copper. In comparison with other metals, the adsorption potential
for copper is superseded only by iron; it is greater than that found for
Cr, Zn, ?b, Cd, Hg and Ni (Patterson, 1978).
Sludge Disposal; Sludge that is disposed of on land may go to a
sanitary landfill, or be spread for the purpose of amending the soil.
The form of copper in sludge is not exactly known. Sommers at al. (1976)
detected no copper sulfides, phosphates, or hydroxides in sludges con-
taining relatively high concentrations of copper. They did find a copper-
hydroxy-carbonate complex, and suggested that the chemistry of copper in
sludge is relatively complicated. The same study found that the move-
ment of copper in sludge-amended soils was unaffected by the soil type,
pH or clay content. Minimal movement of heavy metals was observed in
the top 7.5 cm of soil, and no translocation was detected between 7.5 cm
and 15 cm. The authors concluded that the application of sludge to
soils does not enhance the solubility or movement of copper.
The concentration of copper found in leachate from cropland amended
with sewage sludge was found to be a function of the magnitude of the
initial copper loading (CAST, 1976). For instance, leachate from a
sludge loading of 11.3 kg Cu/ha at a 15-cm and 120-cm soil depth con-
tained higher concentraions of Cu than the control at a depth of 15 cm.
Even so, the amount of copper moving past the 120-cm depth is not expected
to exceed 0.3% and 0.5% of the initial copper loading for the high and
low treatments, respectively; the concentration of dissolved copper in
the leachate was in all cases less than 12 ug/L.
The copper in sewage sludges and other wastes disposed of in sanitary
landfills may be more mobile than the case described above for soil appli-
cation. Data on the mobility and concentrations of copper in leachate
from landfills accepting sewage sludges were not available for this study.
The studies discussed in Pathway #2 indicate a typical copper concentra-
tion of 0.04-0.4 mg/L in leachate from municipal refuse landfills. Under
proper operating conditions, copper will quickly be attenuated by the
soil. Sludge that is incinerated will contribute to the concentrations
of copper in the atmosphere. The fate processes will be similar to the
chain of events described in Pathway #1.
Surface Water Discharge; A survey of 192 POTW's showed effluent
copper concentrations ranging from 0.003 mg/L to 1.8 mg/L, with a mean
of 6.126 mg/L and associated standard deviation of 0.242 tng/L (U.S. SPA,
1979a). The behavior of copper discharged with ?OTW affluents into
local surface waters viil be similar to nhac already described for
aqueous pathways (Pachway r>'3) ; concentrations will be rapidly rsduced
57
-------
through adsorption and dilution. The fate of copper discharged by the
Joint Water Pollution Control Project (JWPCP) of the Los Angeles County
Sanitation District has been studied in some detail (Morel _ejt al., 1975),
and may be generally representative of POTW discharges to the ocean.*
While copper was found in the fairly insoluble sulfide form in the
effluent (^370 million gallons per day effluent, discharged through sub-
marine outfalls at a depth of 60 m), the studies indicated that the com-
bined processes of dilution and oxidation resulted in substantial solu-
bilization of copper (as well as other metals); this increases the
residence time of metals in the water and allows them to be transported
greater distances where the effects on background copper concentrations
would be negligible. It was estimated that only about 17, of the metals
were deposited in the general area of the outfall. The sediments that
do settle near the outfall are likely to be anoxic (Bertine and Goldberg,
1977) and copper would thus be in the sulfide form. The point source dis-
charges of wastewater were initially diluted by a factor of 100, followed
by a five-fold dilution in one tidal cycle. Similarly, outfall was at
or below the concentrations found in the open ocean (Schell and Nevissi,
1977).
Smmnfiry; The concentration of copper in POTW effluent, and the
effectiveness of its removal is dependent upon the initial influent
concentration and type of treatment inacted. There is evidence that
industrial waste pretreatment reduces the concentration of copper in
POTW effluents (both wastewaters and sludges). Most of the copper is
partitioned into the sludge portion of sewage during treatment. Sludge
spread for the purposes of soil amendment does not enhance the solubility
or mobility of copper. . Copper is expected to be attenuated quickly in
the soil. Coppe'r in aqueous effluents will be adsorbed to sediment and
particulate, and be diluted. Discharge to marine system causes solu-'
•bilization of copper, prohibiting localized "hot-spots" in the sediments.
f. Copper Sulfate Use
Pathway //5
Applicatio:
Surface
Water_
Soils
Ocean
Groundwatet
*The wastes, containing both domestic and industrial wastes, contain
high levels of copper (560 mg/L) after primary treatment.
53
-------
Copper sulfate is used for agricultural purposes as a fungicide, feed,
and fertilizer for citrus fruits, deciduous fruits, and vegetables.
In water bodies, it is used as an algicide.
Fate of Dissolved Coooer: Copper dispersal in a water body has
been studied with regard to its use as an algicide +(Button _et al.,
1977). The experiment consisted of putting 0.2g Cu2 /m2and O.AgCu^/m2
into a reservoir with-a pH of 7.3-7.8 and fairly hard water. All but .
5% of the CuSO^ was dissolved within the top 1.75 m of water Within
2.5 hrs the concentration of soluble copper returned to baseline values;
for 0.4g Cu2"1"/!!2, baseline levels were evident after 24 hrs. The decrease
in soluble copper was accompanied by an increase in particulate copper.
This is caused, in part, by the sorption of copper to plankton, which
settled to the bottom. The effectiveness of CuSOi* as an algicide was
demonstrated by applying 0.4g Cu247m2 to an algal bloom consisting
mostly of diatoms. Although toxic levels were present for only a few
hours, the bloom was controlled and did not reappear over the course of
the summer.
Fate in Sediments; The binding capacity of the sediments for copper
was studied in Lake Monona, which had received 1.5 x 10s Ib. of CuSOu.
within a span of 50 years (Sanchez and Lee, 1973). These authors
found that carbonate alkalinity was proportional to the binding capacity
of the sediments. The authors suggested that copper replaced calcium
and magnesium ions within the carbonate crystal lattice. The authors
did not investigate binding to organics, iron and manganese oxides or
clays. Other studies cited found that copper could not be leached from
Lake Monona sediments with 0.1 IT HC1. This implies that copper is not
easily desorbed from whatever it is bound to in the sediments. Two
successive extractions with 1.0 N HC1 released only 71% of the added
copper; at least 29% of the copper is not, therefore, in a form accessible
for biotic uptake* or dissolution.
Another study of two. reservoirs outside New Haven, Connecticut, found
that the pattern of concentration of copper in the sediments closely
parallels that of CuSOi^ use (Bertine and Mendeck, 1978). The range of
copper sulfate additions to the reservoirs since 1935 spans 1000 kg to
10,000 kg per year. For both lakes, the sediment depth of the highest
copper concentration corresponds to the year of greatest use; for Lake
Whitney, the year was 1961, corresponding to a 15-cm depth, for Lake
Saltonstall, the year was 1971, near the top 5 cm. Figure 17 illustrates
the copper concentration in the sediments vs. depth.
Summary; Copper sulfate appears to be an effective algicidal agent
within a very short time frame. The concentrations of copper ion in the
water column are returned to background levels within a day of appli-
cation. The copper sorbs to particulates (in this case, algae) and
sediments. Concentrations in core samples of sediment reflect the use
of CuSOu over che
-------
10
f 20
z
2
e 30
1
40
50
— — -" 71971; 234 jig Cu/cm2/yr
<1961;480ng
/yr)
(Lake Whitney)
Referanca: Bertine and Mendeck (1978)
5000 10,000 1S.OOO 20,000 25,000 30,000
Concentration (mg/kg)
FIGURE 17, COPPER CONCENTRATION IN RESERVOIR SEDIMENT
VS. SEDIMENT DEPTH
70
-------
3. Biological Pathways
This section considers the fate of copper in biological systems.
Uptake and bioaccumulation have been considered.
Copper is accumulated in the tissues of fresh and salt water fish
and invertebrate species to concentrations greater than those measured
in the surrounding water. Tables 13 and 14 present reported copper
bioconcentration ratios (concentration of Cu in the organism divided
by concentration of Cu in water) in various aquatic species and, when
available, Cu concentrations, in the surrounding water. The levels
accumulated are dependent primarily upon those environmental factors
affecting the availability of the cupric ion. Particularly important
are pH (which affects the degree of completing by organic and inorganic
ligands) and water hardness. It has been hypothesized that there is
less uptake at low pH because of reduction in electrostatic forces of
negatively charged groups in cell membranes (Wright and Diamond, 1963;
Mierle and Stokes, 1976), and because less ionic copper is available
for uptake. Water hardness affects uptake by reducing adsorption at
relatively high concentrations of Ca-f+ (Mierle and Stokes, 1976).
In two algal species, Scendesmus acuminatus and Scendesmus acutiformis,
copper uptake occurs through (1) adsorption to the cell wall and (2) trans-
port via diffusion across the cell wall, followed by binding, probably to
sulfhydryl ligands (Mierle and Stokes, 1976). Different species appear
to have different propensities for uptake. Bioconcentration ratios
can range from 12 to 3040 for various algal species (Table 13).
Aquatic invertebrate species, both fresh and salt water, accumulate
copper in their body tissues and shells. Copper is an important trace
element in the heme pigment of molluscs (Greig, 1979). Accumulation
occurs through uptake of copper adsorbed to particulates or sediment
containing copper residues, as well as directly from soluble forms in
the water column (Greig and Wenzloff, 1978). The Atlantic Oyster has
accumulated copper levels one order of magnitude higher than concentra-
tions dissolved in water (Shuster and Pringle, 1969 as cited in Phillips
and Russo, 1979). Uptake in this species continued until a plateau con-
centration of 200 mg/kg was reached after approximately 30 weeks. Copper
is concentrated by the mucous sheets of the oyster, leading one author
to suggest that intake of particulates may be the primary mode of uptake
(Pringle, ec al., 1968 as cited in Grieg, 1979). In the mussel, Mytilus
edulus, tissue concentrations of copper decreased with increased mucous
excretion (Scott and Major, 1972, as cited in Phillips and Russo, 1978).
The excreted copper was unavailable for reaccumulation under the static
conditions in which the experiment was conducted; however, in an exper-
iment providing a continual inflow of copper, the lost metal may be
replaced through further uptake. In fresh water clams, copper concen-
trations reached levels several orders of magnitude higher than copper con-
centrations in water, but slightly lower Chan chose aeasured in sediments
(Anderson. L973; Mat his and Cummir.gs, 1973). Levels vere highest in gill
-------
TABLE 13. BIOCONCENTRATION FACTORS FOR ALGAE AND AQUATIC INVERTEBRATES
AJ j;ae
St:euedesi»>is sp.
Suenedesmus sp.
Rtiadrlcavda
varlabllls
Chore I la sp.
I' hints, marine and fresh
I live neb rates
F or L
Bioconcentratlon Aqueous Cone.
Factor/Ratio (ing/L)
2,400
<1,000-2.000 (day)
12
300
2,400
1,000
Tubl fields
Chiruiiomld larvae
I'ol ychaete (Nereis sp.)
hiiinacle (llalanus ahurneus)
Crab (Call inectes sapldus)
Oyster (Crassostrea
v 1 rgl nl ca)
Oyster (Crassostrea
v i i'g in 1 ca)
Clam (Kangea cuneata)
Hardshell clam
(Nureeiuir la mercenarJa)
(.'lams (3 specl.es)
F
F
F
F
F
F
L
F
F
8,077
546
32.27
11.66
2.28
31.04
28,000
17.37
30,000
692
0.0052
1.91
1.31
1.31
1.31
1.31
0.025
1.31
0.0052
Duration Reference
Stokes ejt al^. (1973)2
1-60 min Mlerle and Stokes (1976)
.2
Khobot£v ejt
Khobotev et
(1976)
_ a±. (1976)
Stokea ^t a_l. (1973)2
lil'A (1977a)2
Mathla and Cummings (1973)
Naininlnga and Willim (1977)
Cuthrie et^ al^. (1979)
Guthrie e£ al^. (1979)
Cuthrie et^ _a_l. (1979)
Cuthrie e± al. (1979)
20 wks Shuster and Prlngle (1969)
Cuthrie e£ al,. (1979)
Kaymont (1972)2
Mathis and Cummings (1973)
-------
TABLE 13 (CONTINUED)
Mussel (Mytilus
£u 1 'loprovincialls)
freshwater invertebrates
St|iiid (3 species)
Marine invertebrates
. Bioconcentratlon
P or L Factor/Ratio
184
1,000
21 x 106
1,670
5,000
Aqueous Cone,
(mg/L)
0.007
Duration Reference
Major L and Pelronlo (I'J/i)
U.S. liPA (1977a); Ross
(1977)2
Martin and Flegal (J.97!))
as cited in Phillipa ami
Russo (1978)
U.S. EPA (1977a);
(1977)2
U.S. EPA (1977a)2
1
K = l-'ield study; L = Laboratory study
As.cited in Versar (1979b)
-------
TABLE 14. BIOCENCENTRATION IN FISH
Specl.es_
lit own bullhead
(IcfcaLurua nebulosus)
It rook trout
(Salvelinus fontinalia)
Uainliow trout
(Salmo galrdneri)
, Dloconcentration
F or L Factor/Ratio
L -500-3,000
i
slgnlf. accum.
Aqueous Cone.
(nig/L)
0.027
0.0094
0.003
Duration
Reference
30 days Urungs et_ aJ.. (1
-------
tissue, followed by the viscera (implicacing upcake through ingestion)
'and the muscle, wich che lowest concentration measured in the shell
(Anderson, 1973). In a microcosm study, copper concentrations were
approximately one order of magnitude greater in five estuarine inver-
tebrate species [oyster (Crassostrea virginica), barnacle (Balanus
aburneus), clam (Rangia cuneata), blue crab (Callinecces sapidus), and
polychaete (Nereis so.)] than concentrations in water (Greig, 1979).
Concentrations in the sediment, however, were higher than concentrations
measured in the organisms by one order of magnitude. Three species of
squid (Loligo opalescens. Ommastrephes bartrami, and Synrolectoteuchis
oualaniensis) were found to concentrate copper in their livers up to
six orders of magnitude over concentrations in water (Martin and Flegal,
1975, as cited in Phillips and Russo, 1978). The authors suggested that
the high levels were due to copper requirements for metabolic processes
in squid.
Lower invertebrates, chironomids and tubificids also showed tissue
copper concentrations higher than water concentrations (by two to four
orders of magnitude) but equal to or lower than sediment concentrations
in field studies (Namminga and Wilhm, 1977; Mathis and Cummings, 1973).
Fish species have been shown to accumulate copper in their tissues
(Table 14); however, bioaccumulation may depend on the.concentration to
which they are exposed. For example, McKim and Benoit (1974) found no
copper uptake by brook trout at a concentration of 9.4 ug/L in water. On
the other hand, Goettel ££ a^. (1974, as cited in Phillips and Russo,
1978) reported that rainbow trout accumulate copper in the liver when
exposed to concentrations in water of 3 ug/L. Other species reported to'
accumulate copper in various tissues are bluegill (Benoit, 1975), brown
bullhead (Brungs e^ al., 1973), stone loach (Solbe and Cooper, 1976),
and mummichog (Eisler and Gardner, 1973 as cited in Phillips and Russo,
1978). The liver apparently is a common site for copper concentration
in fish, often containing the highest copper levels of all tissues in
the body, and is more apt to retain copper when the organism is removed
from contaminated water and placed in clean water (Solbe and Cooper,
1976). In a field study, ten species of fish were found to accumulate
copper at a concentration one to two orders of magnitude greater than
the water concentrations, but one to two 'orders lower than sediment
concentrations (Mathis and Cummings, 1973).
Plants in general require some copper for metabolic processes.
The amount required varies among species. Concentrations of copper in
plant tissue at less than 5 yg/g (dry weight) probably indicate a
deficiency (NRC, 1977). Copper is one of the least available of che
essential nutrients (NRC, 1977), and deficiency problems are common in
some parts of the U.S. Background concentrations of copper in crops
grown in mineral soil (presumably where copper is abundant) range from
1 ins/kg to over 50 tag/kg (dry weight). 3eeson (19^1) and MRC (19/7)
provide a aora detailed discussion of background levels' in crops.
-------
The amount available for uptake by planes often differs considerably
from the total copper content in soil. Factors that influence avail-
ability include pH, clay content, microbial activity, moisture, and
organic content, and the concentrations of phosphate, manganese, and
zinc, which apparently compete wish copper for transport sites on plant
roots (NRC, 1977). As a result, concentrations of copper in plants are
considered by some to be independent of copper concentrations in soil
(Timperley £t al., 1977, as cited in EPA, 1979b). Various crops grow-
ing in sewage-sludge treated fields with soil copper concentrations
of up to 280 mg/kg, had copper concentrations (in the utilizable part
of the plant) similar to concentrations in plants grown in non-created
soil (Dietz and Rosopulo, 1976, as cited in EPA, 1979b). Leaves and
stalks, however, had concentrations approaching toxic levels for live-
stock. An application to soil of 164 kg of copper per hectare in domestic
waste water sludge had different effects on different crop species
(CAST, 1976). Tissue concentrations increased from 7.7 mg/kg to 14.4
mg/kg in cucumbers and from 7.5 mg/kg to 12.2 mg/kg in broccoli. On
the other hand, concentrations in potatoes did not change. There was
no consistent trend in the location of copper.
Some typical copper residues measured in plants, both crop and wild
species, growing in the vicinity of anthropogenic sources of copper
were presented previously in Section IV-A.
In conclusion, copper is accumulated by biota to various degrees.
Where unusually high concentrations of copper are available in soil or
water, tissue concentrations of Cu may increase over background levels,
depending on the species exposed. Bioconcentration factors in aquatic
organisms range from less than one to six orders of magnitude higher
than water concentrations. High bioaccumulation potential may be due
to greater metabolic requirements for copper. The limited information
on bioconcentration factors in plants indicatesranges of from one to
three orders of magnitude over water levels for algae and for terrestrial
plants ranges of from one to three orders of magnitude higher than soil
concentrations. Little information was available on the contribution
of background levels of copper to these bioconcentration factors. Limited
information available suggests that copper is not biomagnified in food
chains.
C. SUMMARY
1. Distribution
Ambient copper levels in seawater generally range between 1 ug/L and
5 ug/L. STORET data for U.S. major river basins indicate that most
observations of total copper were between 1 ug/L and 100 ug/L. The
major basins with the highest percentage of samples with concentrations
exceeding 100 ug/L are the New England, Western Gulf and Lower Colorado
regions.
76
-------
STORE! data on sediment concentrations in the major river basins
are in the range of 1 mg/kg to 1,000 mg/kg which are two to four
orders of magnitude greater than concentrations found in river water.
The highest mean copper levels in sediments are found in Hawaii, the
Lower Colorado River, the Upper Mississippi Valley and the Great Lakes.
STORET also provided the most comprehensive compilation of copper
residues in freshwater fish tissues. The majority of the samples had
concentrations between 1 mg/kg and 10 mg/kg. Hawaii, Puerto Rico and
the-Colorado River Basin had the highest mean residues among the STORET
regions. Marine species had residues similar to those of freshwater
species, except for oysters, which sometimes had copper levels exceeding
1,000 mg/kg.
Copper is an essential micronutrient for plants, and appears in
concentrations of 4-15 mg/kg in edible species. Copper occurs naturally
at concentrations of 50 mg/kg in the earth's crust, although parent
materials such as biotite and pyroxene basalts average 140 mg/kg copper.
Airborne concentrations of copper in rural and urban areas normally
range from 0.01 ug/m-* to 0.3 ug/m3. Levels as high as 2 ug/m3 have
been measured near a copper smelter.
2. General Fate
The speciation and concentration of copper in the water column is
a function of numerous parameters. Generally, however, an aerated water.
system will contain the aqueous carbonate and hydroxide species above
pH 7, and the divalent ion below this pH. Copper exhibits a great
tendency toward adsorption to the extent that it exceeds other divalent
metal ions in this capacity. Therefore, one finds it sorbed to sub-
micron particulate matter in the sediments,-and suspended solids qf
aqueous systems, as well as to the particulate matter in air and soils.
Hydrous iron and manganese oxides, clays and organic matter serve as
sorption sites.
In soils, sorption of copper occurs above pH 5. Below this level,
translocation of copper as the divalent ion becomes possible.
3. Specific Pathways
a. Air
Point source combustion sources are the primary contributors of
copper to' the atmosphere. Copper is emitted as a vapor, oxide and
sorbed to sub-micron particulates No clear evidence exists for the
role air-pollution control devices play in the regulation of copper
emissions to che atmosphere. Wee and dry fallout results in localized
increases to che copper concentrations found in nearby soils, surface
waters and urban pavement:. The concentration of copper in urban runoff
has been noted co concributa significantly co ultimata discharge inco
3ur-faca waters.
-------
b. Solid Waste
The land receives the bulk of copper resulting from anthropogenic
sources. Hazardous and municipal waste sites that receive copper-con-
taining sludges have been found to average about 0.04-0.4 mg/L of copper
in the leachate. Acid mine drainage from abandoned mines causes initial
spikes in the surface water copper concentrations. The stream's recovery
is a function of distance downstream.
c. Industrial Wastevater
Pretreatment of industrial wastewaters of the metal finishing
industry resulted in lower concentrations discharged to surface waters
and concentrated copper-containing sludges destined for landfill disposal.
Surface water sediments are the best indicators of industrial discharge;
remaining copper in the water column is ultimately destined for lake or
ocean sediments.
d. POTW's
Copper removal from POTW influents is affected by the treatment
scheme, and incoming copper concentration. Industrial wastewater pre-
treatment was necessary to ensure effective removal of copper during
treatment at the POTW in several cases. The copper partitions into
the sludge portions of the waste during treatment. Land disposal
(agricultural or municipal landfill) does not appear to render copper
mobile from the sludge. Incineration of the sludge contributes to the
concentrations of copper in the air.
e. Copper Sulfate Use
Use of copper sulfate as an algicide in reservoirs and other surface
waters increases the concentration of copper in sediments. The concen-
tration of the divalent ion resumes background levels with 1 day of
application.
4. Biological Pathways
Copper is accumulated by biota to various degrees, depending on the
concentration in the medium and environmental conditions. For aquatic
organisms, high hardness and pH tend to promote accumulation. Biocon-
centration factors can be up to six orders of magnitude greater chan
water concentrations. Plants may also take up copper to levels up to
three orders of magnitude over soil concentrations.
73
-------
REFERENCES
Allavay, W.H. 1974. Agronomic controls over Che environmental cycling
of trace elements. Adv. Agronomy 20;235-275.
Anderson, 3..V. 1973. Concentration of cadmium, copper, lead and zinc
in six species of freshwater clams. Bull, of Env. Contam. Toxicol. 18(4);
492-496.
Anon. 1977. U.S. Environmental Protection Agency. Copper-computer
printout. Office of Oil and Hazardous Materials - Technical Assistance
Data System, Washington, D.C. 3p.
Beeson, K.C. 1941. The mineral composition of crops with particular
reference to the soils in which they were grown. A review and compila-
tion. U.S. Department of Agriculture Miscellaneous Publication 369.
U.S. Government Printing Office, Washington, D.C.
Benoit, D.A. 1975. Chronic effects of copper on survival, growth, and
reproduction of the Bluegill (Lepomis macrochirus). Trans, of the Amer.
Fish. Soc. 104(2):353-358.
Berger, K.C. 1976. Sun, Soil and Survival. University o£ Oklahoma
Press. .
Bertine, K.K. and E.D. Goldberg. 1977. History of heavy metal pollution -
Southern California coastal zone - reprise. Environ. Sci. Technol. LI(3):
297-299.
Bertine, K.K. and M.F. Mendeck. 1978. Industrialization of New Haven,
Conn., as recorded in reservoir sediments. Environ. Sci. Technol.
12(2) .-201-207.
Biener, J.A. and W.H. Bourma. 1978. Case history of city of Grand Rapids,
Michigan program of industrial waste control. Pretreatment of industrial
wastes - Joint Municipal and Industrial Seminar, A.S. Vernick, H.D. Feiler,
P.D. Lanik, (Eds.) EPA Seminar Handout.
Bruland, K.W., K. Bertine, M. Koide, and E.D. Goldberg. 1974. History
of metal pollution - Southern California coastal zone. Environ. Sci.
Technol. 8_(5) :425-432.
Brungs, W.A., E.N. Leonard, and J.M. McKim. 1973. Acute and long-term
accumulation of copper by the brown bullhead, Icttalurus nebulosus.
Journ. Fish. Res. Bd. Can. 30;583-586.
Button, S.S., H.?. Hostettar and D.M. Mair. 1977. Copper dispersal in
a vatar-smjpiy reservoir. Water Research. 11(7) :539-5
-------
Cataldo, D.A. and R.E. Wilding. 1978. Soil and plant factors influenc-
ing the accumulation of heavy metals by plants. Environ. Health
Perspectives 27:149-159.
Chian, E.S.K. and F.B. DeWalle. 1977. Evaluation of leachate treatment.
Vol. 1, Characterization of leachate. U.S. EPA, Office of Research and
Development. EPA-6001/2-77-186a.
Chu, T-Y., G.R. Steiner, C.C. McEntyre. 1978. Removal of complex copper-
ammonia ions from aqueous wastes with fly ash. J. Watar Poll. Control
Fed. 5_2(9):2157-2174.
Coles, D.G., R.C. Ragaini, J.H. Ondor, G.L. Fisher, D. Silberman, and
B.A. Prentice. 1979. Chemical studies of fly ash from a coal-fired
power plant. Environ. Sci. Techn. 13(4):455-459.
Council for Agricultural Science and Technology (CAST). 1976. Application of sew-
age sludge to cropland: Appraisal of potential hazards of the heavy metals to
plants and animals. Prepared for U.S. EPA, Office of Water Program Operations
EPA-430/9-76-013.
Davis, J. and J. Jacknow. 1975. Heavy metals in wastewater in three urban
areas. J. Water Pollut. Control Fed. 47^(9):2292-2297.
Davis, J.A. and J.O. Leckie. 1978. Effects of absorbed complexing ligands
on trace metal uptake by hydrous oxides. Environ. Sci. Technol. 12(12):
1309-1315.
Delfino, J.S. 1977. Effects of river discharge and suspended sediment on
water quality in the Mississippi River. J. Environ. Sci. Health. A12(3);
79-94.
Dietz, 7.T. and A. Rosopulo. 1976. Schwermetallgehalte in Boden und Pflanzen
nach extrem hohen Klairschlammgabe. Landwirtsch. Forsch. 33_:236-248 (In
German with English summary), as cited in Versar (1979).
Duce, R.A., J.G. Quinn, C.E. Olney and S.R. Piotrowicz. 1972, Enrichment
of heavy metals and organic compounds in the surface microlayer of
Narragansett Bay, Rhode Island. Science. 176(14);161-163.
Eaton, A. 1979. Observations of the geochemistry of soluble copper, iron,
nickel and zinc in the San Francisco Bay)estuary. Environ. Sci. Technol.
13 (4): 425-432.
Elzerman, A.W., D.E. Armstrong and A.W. Andren. 1979. Particulate
rinc, cadmium, lead, and copper in the surface microlayer of Southern
Lake Michigan. Environ. Sci. Technol. JL3(6) : 720-725 .
Fink, Jr., L.X., D.M. Pope, A.3. Harris, andL.L. Schick. 1975. Land
and Water Resources Inscitute. university of Maine at Orono. (PB-253 ^97)
30
-------
Frlberg, L., It al. 1977. Toxicology of Metals - Volume II. EPA-600/1-
77-022.
Greig, R.A. and D.R. Wenzloff. 1973. Metal accumulation and depuration
by the American Oyster, Crassostrea virginica. Bull. Environ. Contam.
Toxicol. 20:499-504.
Greig, R.A. 1979. Trace metal uptake by three species of mollusks.
Bull. Environ. Contain. Toxicol. 22:643-647.
Grimwood, C. and T.J. McGhee. 1979. Prediction of pollutant release
resulting from dredging. J. Water Pollution Control. Fed. 51(7);1811-1815,
Guthrie, R.E., E.M. Davis, D.S. Cherry, and H.E. Murray. -1979. Biomagni-
fication of heavy metals by organisms in .a marine microcosm. Bull. Environ.
Concam. Toxicol. 21:53-61.
Holcombe, L.A. 1977. Adsorption and desorption in mine drainages.
NTIS PB-290 614/7WP.
Huang, C.P., H.A. Elliott, and R.M. Ashead. 1977. Interfacial reactions
and the fate of heavy metals in soil-water systems. J. Water Poll. Control
Fed. 49(5):745-756.
Jacko, R.B. and D.W. Neuendorf. 1977. Trace metal particulate emission
test results from a number of industrial and municipal plant sources.
J. Air Pollution Assoc. 2_7(10):989-994.
Jacko, R.B., D.W. Neuendorf, and F. Faure. 1976. Fractional collection
efficiency of electrostatic precipitator for open hearth furnace trace
metal emissions. Environ. Sci. Technol. 10(10);1002-1005.
Jacko, R.B., D.W. Neuendorf., and K.J. Yost. 1975. Trace metal emissions
from a scrubber controlled municipal incinerator. ASME Paper #N75-WA/APC-2.
Khobot' ev, V.G., V.I. Kapkov, E.G. Rukhodze, N.V. Turunina, and N.A.
Shidlovskaya. 1976. Copper uptake by algae from copper-containing com-
pounds and the effect of this process on their salt metabolism. Gidrobiol.
Zh. 12(l):40-46 (Russian).
Kleinman, M.T., T.J. Knelp, D.M. Bernstein, and M. Eisenbud. 1977.
Fallout of toxic metals in New York City. Biological Implications of
Metals in the Environment. H. Drucker and R.E. Wildung (Eds.). Technical
Information Center, Energy Research and Development Administration.
Kubota, J., E.L. Mills, and R.T. Oglesby. 1974. Lead, cadmium, zinc,
copper and cobalt in streams and lake waters of Cayuga Lake Basin, New
York.. Environ. Sci. Technol. 8(3):243-243.
31
-------
Major!, L. and F. Patronio. 1973. Accumulation phenomenon which takes
place in a mussel (Mytilus galloorovincialis LMK) grown in an artificially
polluted environment. II. Pollution from copper. Ig. Mod. 66(1);64-78
(Italian)
Martin, H.W. and W.R. Mills, Jr. 1976. Water pollution caused by inactive
ore and mineral mines - a national assessment. tfTIS #P3-264 956. Prepared
for the Office of Research & Development, U.S. EPA, Cincinnati, OH
Mathis, B.J. and T.F. Cummings. 1973. Selected metals in sediments,
water, and biota in the Illinois River. Water Pollution Control Fed.
45_(7):1573-1583.
McKim, J.M. and D.A. Benoit. 1974. Duration of toxicity tests for
establishing "No Effect" concentrations for copper with brook trout
(Salvelinus fontinalis). Fish. Res. Bd. Can. _3_1(4) :449-451.
Mezey, E.J., S. Singh, and D.W. Hissong. 1976. Fuel Contaminants: Vol. 1
Chemistry. Report by Battelle-Columbus Laboratories to the EPA, Office of
Research & Development (EPA-600/2-76-177a; PB-256 020)
Mierle, G. and P.M. Stokes. 1976. Heavy metal tolerance and metal accumu-
lation by planktonic algae. Trace Substances in Environmental Health.
D.D. Hemphill (Ed.), Proc. Symp., Columbia, Mo; Univ. of Mo.
Milanovich, F.P., R. Spies, M.S. Guram, and E.E. Sykes. 1976. Uptake of
copper by the polychaete Cirriformia spirabrancha in the presence of
dissolved yellow organic matter of natural origin. Est. Coast. Mar. Sci.
4_(5):585-588.
Morel, F., R.E. McDuff, and J.J. Morgan. 1973. Interactions and Chemo-
stasis in aquatic chemical systems: Role of pH, pE, Solubility and
complexation. Trace Metals and Metal Organic Interaction in Natural Waters.
Phillip C. Singer (Ed.), Ann Arbor Science, Ann Arbor, MI
Morel, F.M.M., J.C. Westall, C.R. O'Melia, and J.J. Morgan. 1975. Fate of
trace metals in Los Angeles County wastewater discharge. Environ. Sci.
Technol. 9.(8): 756-761
Mytelka, A.I., J.S. Czachov, W.B. Guggino, and H. Golub. 1973. Heavy
metals in wastewater and treatment plant effluent. J. Water Pollution
Control Fed. 45_(9) : 1859-1864.
Namminga, H. and J. Wilhm. 1977. Heavy metals in water, sediments and
chironomids. J. Water Pollution Control Fed. ^9(7)1725-1731.
-------
National Academy of Sciences. 1977. Copper, subcommittee on copper
committee on medical and biologic effects of environmental pollutants."
national .research council, EPA-600/1-77-003, Washington, D.C.
National Research Council (NRC). 1977. Copper. (PS-262 425)
Patterson, J.W. 1978. Heavy metals removal in combined wastewater
treatment. Presented at International Environment Colloquium, University of
Liege, Belgium, May 16-19
Perhac, R.M.. 1974. Water transport of heavy metals in solution and by
different sizes of particulate solids. (NTIS #PB-232 427)
Peyton, T. and A. Mclntosh. 1974. A field study on the distribution of
aerially deposited trace elements in an aquatic ecosystem I Sediment
component. Trace Subst. Environ. Health. 8^:193-201
Phillips, G.R. and R.C. Russo. 1978. Metal bioaccumulation in fishes and
aquatic invertebrates: A literature review. US EPA-600/3-78-103
Pringle, B.H., D.E. Hissong, E.L. Katz, and S.T. Mulawka. 1968. A.S.C.E.
.Proc. J. Sanit. Engineer. Div. 94 (Sa3) pp. 455
Ragaini, R.C., H.R. Ralston, and N. Roberts. 1977. Environmental trace
metal contamination in Kellogg, Idaho near a lead smelting complex.
Environ. Sci. Technol. 11(8):773-784
Raymont, J.E.G. 1972. Pollution in Southhampton water. Proc. Roy. Soc.
Ser. B. 180(1061);451-468
Ross, R.H. 1977. Environmental interactions. Environmental, health, and
control aspects of coal conversion; An information overview, pp. 6-98.
Braunstein, H.M., E.D. Copenhaver, and H.A. Pfuderer (Eds.). Oak Ridge
National Lab, Oak Ridge, TN.
Roulier, M.H. 1975. Research on contaminant movement in soils. Paper
presented at NATO/CCMS meeting on landfill research, London, England,
Oct. 20-22.
Sagik, 3.P. and C.A. Sorber. 1977. Risk Assessment and Health Effects of
Land Application of Municipal Wastewater and Sludges. Proceedings of
Conference, Dec. 12-14, 1977, Center for Applied Research Technology,
University of Texas, San Antonio.
Sanchez, I., and G.F. Lee. 1973. Sorption of copper on Lake Monona
sediments - effect of NTA on copper release from sediments. Water
Research. 75:87-593.
Schell, W.S.. and A. Mevissi. 1977. Heavy metals from waste disposal in
car.trai Puget Sound. Invir. Sci. Tech. 11(9) :387-393.
-------
Seme, R.J. 1977. Geochemical distribution of selected trace metals in
San Francisco Bay sediments. In: Biological Implications of Metals in
the Environment. H. Drucker and R.E. Wildung (Eds.). Technical Informa-
tion Center,Energy Research and Development Administration.
Solbe, J.F. de L.G. and V.A. Cooper. 1976. Studies on the toxicity of
copper sulphate to stone loach Noemacheilus barbatulus (L.). Water Res.
10:523-527".
Sommers, L.E., D.W. Nelson, R.E. Terry, and D. J. Siiviera. 1976.
Nitrogen and metal contamination of natural waters from sewage sludge
disposal on land. Purdue University Water Resources Research Center, //89.
Stiff, M.J. 1971. The chemical states of copper in polluted fresh water
and a scheme of analysis to differentiate them. Water Res. 5_: 585-599.
Stoffers, P., C. Summerhayes, V. Forstner, and S.R. Patchineelam. 1977.
Copper and other heavy metal contamination in sediments from New Bedford
Harbor, Massachusetts: A preliminary note. Environ. Sci. Technol.
11(8):819-821.
Stokes, P.M., T.C. Hutchinson, and K. Krauter. 1973. Heavy metal toler-
ance in algae isolated from polluted lakes near the Sudbury, Ontario
smelters. Water Poll. Res. Can. J3:178-201.
Stumm, W. and J. J. Morgan. 1970. Aquatic chemistry. Wiley-Interscience,
New York.
Sverdrup & Parcel and Associates, Inc. 1977. Study of selected pollutant
parameters in publicly owned treatment works (Draft) - Task Order No. 7
under EPA Contract 68-01-3289.
Theis, T.L. and R.O. Richter. 1979. Chemical speciations of heavy metals
in power plants ash pond leachate. Environ. Sci. Technol. 12:1302-1308.
Timperley, M.H., R.R. Brooks, and P.J. Peterson. 1977. The significance
of essential and tion-essential trace elements in plants in relation to
biogeochemical prospecting. Jour. Applied Ecology. _7_:429. As cited in
Versar (1979).
U.S. Dept. of Health, Education and Welfare (HEW). 1970. Community Water
Supply Study. Public Health Service, Environmental Health Service, Bureau
of Water Hygiene.
U.S. Environmental Protection Agency. 1977a. Information for proposed
general pretreatment regulations (40 CFR 405), Washington, D.C.
U.S. Environmental Protection Agency. 1977b. The pravalenca of subsurface
migrations of hazardous chemical substances at selected industrial vasts
disposal sites.
-------
U.S. Environmental Protection Agency. 1979a. Effluent guidelines and
standards; electroplating point source category; pretreatment standards
for existing sources. Federal Register 44/175):52590-52628.
U.S. Environmental Protection Agency. 1979b. Copper - ambient water
quality criteria. Criteria and Standards Division, Office of Water
Planning and Standards.
U.S. Environmental Protection Agency. 1979c. STORE!.
Versar, Inc. 1979a. Copper statement of probable fate. Draft report
to Monitoring and Data Support Division, U.S. Environmental Protection
Agency.
Versar, Inc. 1979b. Non-aquatic fate of copper. Draft report to
Monitoring and Data Support Division, U.S. Environmental Protection Agency.
Vuceta, J. and J.J. Morgan. 1978. Chemical modeling of trace metals in
fresh waters: Role of complexation and adsorption. Environ. Sci. Technol.
12(12):1302-1308.
Weast, R.C. (Ed.). 1972. Handbook of Chemistry and Physics, 53rd Edition.
The Chemical Rubber Co., Cleveland, OH.
Whaling, P.J., R.T. Barber, and J.C. Paul. 1977. The distribution of
toxic metals in marine ecosystems as a result of sewage disposal and
natural processes. Water Resources Research Institute of the University
of North Carolina (NTIS PB-277 644).
Wright, E.M. and J.M. Diamond. 1968. Effects of pH and polyvalent cations
on the selective permeability of gall-bladder epithelium to monovalent
ions. Biochem. Biophys. Act 168:57-74. As cited in Mierle & Stokes
(1976).
Yopp, J.H., W.E. Schmid, and R.W. Hoist. 1974. Determination of maximum
permissible levels of selected chemicals that exert toxic effects on
plants of economic importance in Illinois. Report to Illinois Institute
for Environmental Quality.
Yost, K.J. and A. Scarfi. 1979. Factors affecting copper solubility in
electroplating waste. J. Water Pollution Control Fed. 51(7):1887-1896.
Yost, K.J. and D.R. Masarik. 1977. A study of chemical destruct waste
treatment systems in the electroplating industry. Plating and Surface
Finishing, January:35-40.
85
-------
SECTION V.
EFFECTS OF AND EXPOSURE TO COPPER - AQUATIC ORGANISMS
A. EFFECTS OF COPPER
1. Introduction
This section provides information about the levels of copper exposure
at which the normal behavior and metabolic processes of aquatic organisms
are disrupted, as indicated by laboratory and field studies. Copper is a
contaminant for which a considerable amount of data on effects are available,
and'the opportunity exists to investigate the biological and chemical aspects
of toxicity more thoroughly than with most other priority pollutants.
While such data have provided a better understanding of copper
toxicity, they have also illustrated the complexity of the interactions
between copper and the aquatic environment. Laboratory experiments that
attempt to isolate the effects of a single variable on copper toxicity
may fail to account for other parameters that are known to modify substan-
tially the availability of copper to an organism. For example, copper
complexes with a wide variety of organic compounds, which effectively re-
duce its toxicity. Yet levels of organic completing agents are
seldom measured or reported in field studies. Other metals in the water,
such as zinc or lead, may act synergistically or antagonistically with
copper to increase or decrease its toxicity. Since the toxicant solutions
used in laboratory studies usually have negligible concentrations of
either organic complexing agents or other heavy metals, the resulting data
are inaccurate to the extent that they cannot be extrapolated to field
situations where these other factors are significant. On the other hand,
so many variables exist in field experiments that the results
are difficult to generalize to other areas or conditions.
Most toxicity studies do measure such parameters as pH and hardness,
which are important in that they determine the degree and nature of
copper complexation. Certain complexes have been identified that are
apparently more toxic than others. The cupric ion is the most prevalent
form of copper at lower pH values (6 or less) and is also thought to be
the most toxic. Unfortunately, few bioassays are conducted in midly
acidic water in order to test this assumption.
As a result of the many variables that influence the
results of copper toxicity bioassays, the data discussed below can provide
only a rough estimate of copper concentrations that can be expected to
have adverse effects on aquatic life. The implications of these variables
will be discussed further in the consideration of risk (Section VII).
37
-------
2. Freshwater Organisms
a. Chronic/Sublethal Toxicity
Copper is an essential micronucrient for biota, but there is a fine
line between the concentrations at which it is beneficial and the levels
at which it becomes toxic. Low concentrations of copper can cause a wide
variety of reactions in aquatic organisms, ranging from behavioral changes
to growth inhibition and physical deformity. Although copper in small
quantities (e.g., less than 20 ug/L.) may not be fatal to fish, it can pose
a threat to the species as it has been shown to diminish reproductive
potential in the laboratory.
Folmar [1976, as cited in Tracer Jitco, Inc. (TJI, 1977)] has observed
an avoidance reaction to concentrations of 0.1 ug/L. copper (hardness,
89.5 mg/L) by the rainbow trout (Salmo gairdneri). while Sprague e_t a-1.
(1965, as cited in TJI, 1977) have reported a similar response by Atlantic
salmon (Salmo salar) to 2.4 ug/L copper (hardness, 20 mg/L). Sublethal
effects on freshwater fish have been reported for concentrations ranging
from 9 ug/L to 1000 ug/L. Physiologic effects include accumulation of
mucous on the gills (resulting in a "cough" response), changes in gill
ATPase activity and olfactory response, and a loss of ability to regulate
water balance. These concentrations of copper can alter behavior, as
well as inhibit reproduction, migration, and growth. Data on sublethal
effects are outlined in Table 15.
Data on the sublethal effects of copper on freshwater invertebrates
are much more limited, and can be summarized as follows. Cheng and
Sullivan (1977) tested the osmoregulatory effects of copper sulfate in
the snail (Biomphalaria glabrata), and found that concentrations as low
as 60 ug/L caused a large influx of water into the tissues, resulting in
death with 12 to 48 hours. A copper sulfate concentration of 14.8 ug/L
inhibited growth in the snail (Physa integra) and the scud (Gamroarus
Pseudolimneus), and suppressed feeding in the snail (Campelona decisum)
(Arthur and Leonard, 1970).
Chronic toxicity of copper has been examined by several investigators
Sauter £t al. (1976) have reported a 60-day chronic exposure to 5 ug/L ,
which reduced the growth of brook trout (Salvelinus fontinalis) embryos
and larvae in soft water. In other 60-day tests, chronic values of less
than 40 ug/L copper have been reported for the rainbow trout (Salmo
gairdneri) and white sucker (Catastomus commersoni) in soft water
(^45 mg/L CaC03 hardness) (McKim et £l., 1978). Effects due to chronic
exposure have been observed for catfish (Ictaulurus punctatus) at concentra-
tions of less than 20 ug/L copper in soft water (32 to 51 mg/L hardness).
Chronic values for the snail and scud and other invertebrate species range
from 6.1 ug/L to 49.0 ug/L.
88
-------
TABLE 15. SUBLET1IAL EFFECTS OF COPPER ON FRESHWATER FISH
CO
20
!!!l"r
0.1
2.4
5
8.4
U
0
Species
Rainbow Trout
(Saluo galrdncri)
Atlantic Salmon
(Sal DIO salar)
Colio Salmon
(Oiicorhynchus klsutch)
11 rook Trout
(Salvellnus fontlnalls)
fathead Minnow
(Pimephalcs promelas)
Colio Salmon
(Oncorhynchiis klsutch)
Rainbow Trout
(Salmo Kalrdiierl)
Compound
CuSOi,
c,«o4
CuCl2
foll<
CuSOi,
CuSO,,
CuCl2
foil
CuSO,,
Hardness
(niK/L)
89.5
20
89-99
1
wed by field
45
31
89-99
1
wed by field
90
pll/Temp (°C)
8.0/-
-/15-17°
6.8-7.9/12°
est
7.65/8.5°
7.1/19-25°
6.8-7.1/12°
est
7.7/IJ.O"
Test
Durut iou
1 hr
**
1 mo
48 hr
11 mo
1 DIO
1 mo
10 sec-
per 2
mln. .
Test
Type
flow-
thru
flow-
thru
field
flow-
thru,
nominal
flow-
thru
measured
field
per-
f us ion
of ol-
factory
organs,
measured
Effects
Avoidance behavior
Avoidance behavior
Reduced downstream
migration
Significant In-
crease In cough re-
sponse, Increased
activity, less
aggressive feeding
LCSO! prevented
spawning, retarded
growth & eex de-
velopment of
survivors
Decrease in gill
ATPase activity
Decreased survival
in seawater
Threshold reduction
in olfactory bulbar
response to L-serinc
Reference
Folmar (1976)
is cited In TJI
1977)
iprague. et al.
(1965), as 'cited
in TJI (1977)
l.orz and
tcl'herson
(1976)
Drummond et j»l.
(1973). as cited
in TJI (1977)
Mount and
Stephun (1969)
Lorz and
McPherson (1976)
lara et al.
(1976)"
-------
TABLE 15. SUBLETIIAL EFFECTS OF COPPER ON FRESHWATER FISH (continued)
Couc
I'K/l.
27
32.5
36
70
|UO
162
Spue lea
Brown Bullhead
(Ictalurus nebulosus)
Urouk Trout
(Salvclinus fnntlnalls]
(yearlingti)
Zebrafish
(Brachydanlo rcrlo)
(eggs)
Rainbow Trout
(Sulruo ^alrdneri)
Kalnbow Trout
(Sal mo galrdneri )
Bluet-Ill Sunflsli
(l.epomls macrocltlrus)
(juveniles)
Compound
CuSO,,
CuSO,,
CuSO^
CuSO,,
CuSO,,
CtiSOi,
lardness
(cnp./L)
202
45.5
16(alk.)
60
365
A3
pll/Temp (°C)
7.6/varJed
7.5/10.6°
-/26°
7.8/15°
1 -/10°
7-8/20-27°
Tent
Duration.
600 day
8 mo
—
48 hr
40 day
22 no
Test
Type
static,
measured
f low-
tli 01,
measured
as dis-
solved Ci
static.
measured
flow-
thru.
measured
static
flow-
thru>
measured
as total
Cu
effects
leer, in plasma
jlutamic oxa-
loacetlc trans-
amlnase (PGOT)
Decreased survival
slighly decreased
growth
Suppressed hatching
nervous system
ma 1 f o rma 1 1 one
Increased cough
frequency
Initial depression
of feeding and
growth, followed
by acclimation
Reduced survival.
Inhibited spawning
retarded growth
Reference
McKlm. et al
(1970), as cited
in TJI (1977)
McKlu and
Benolt (1974)
Ozoh (1979)
Sellers et al.
(1975)
Lett et al.
(1976)"
Benoit (1975)
VO
O
-------
TABLE 15. SUBLETHAL EFFECTS OF COPPER ON FRESHWATER FISH (continued)
Cone
I'B/I.
1. 000
180
1 .000
Species
Striped Bass
(Koccus saxatills)
(juveniles)
Sea-water acclimated
Fresh-water acclimated
fathead Minnow
(Plumules promelas)
Striped Bass
(Koccus saxati lls)
Compound
CuSO,,
CuSO,,
CuSOi,
Hardness
dun/1.)
30
148-340
-
pll/Tenip (°C)
-17.5°
7.6-O.G/2--30"
-/19.0"
Tent
On rat Ion
10 day
acclim-
ation
S oiin
exposun
9 mo.
15 mln
Test
Type
static.
nominal
static,
nominal
Kf fecta
Overall loss of
ability to regu-
late water balance
Lost weight, incr.
scrum Na
Gained weight ,tlecr.
serum Na
Complete inhibition
of spawning
Expansion of plasma
volume
Reference
Courtols (1976).
aa cited in TJI
(1977)
Brunga ej aj.
(1976)
Courtols and
Meyerlioff (1975)
-------
b. Acute Toxicity
Acute coxicity is defined as toxicant-induced mortality over a short
period, generally within 96 hrs. Although fish are more likely to be
exposed to concentrations resulting in chronic or sublethal effects, run-
off from a tailings dump or an industrial discharge can temporarily result
in levels high enough to cause fish kills.
The acute effects of copper have been extensively studied for a wide
variety of freshwater fish. "LC^Q values for 24- to 96-hr exposures varied
from 10 yg/L for Chinook salmon (Oncorhynchus tshawytscha) (hardness = 13
mg/L)to more than 10,000 ug/L (hardness = 200 mg/L) for the bluegill
sunfish (Lepomls macrochirus) . in addition to all salmonid species, the
fathead' minnow (Pimephales promelas) appears to be more susceptible to low
concentrations of copper than other freshwater species tested.
The available data are outlined in EPA (1979) , and have been condensed
in Table 16. While it is apparent that toxicity is to some degree species-
dependent, there are numerous other factors contributing to variability
that will be discussed in Part 5 of this section.
LC-Q values for freshwater invertebrates range over several orders of
magnitude, from 5 ug/L (hardness of 66 mg/L CAC03) for Daphnia hyalina to
9,300 ug/L (hardness of 50 mg/L CAC03) for snail (Amnicola lycorias). Other
particularly sensitive species include the scud ( Gamma rus ps eudolimnaeus )
and the midge (Chironomous sp.), with 96-hours LC5Q values of 20 ug/L and
30 ug/L, respectively. For a complete summary of existing data, the reader
is referred to Table 2 in U.S. EPA (1979).
Copper concentrations from 1 yg/L to 8,000 ug/L have been shown to
inhibit the growth. or photosynthesis of various freshwater plant species.
Among the most susceptible are the alga species Chlorella pyrenoidosa- and
C_. regularis , and the diatom, Nitzschia palea. Other data on freshwater
plants are listed in Table 5 in U.S. EPA (1979).
3. Marine Organisms
Relatively little research has been conducted on the toxicity of
copper to marine vertebrates. EPA (1979) contained no information on
chronic or sublethal effects in their review. Birdsong e_£ al. (1971, as
cited in EPA, 1979) found 96-hr LC$Q values of 360, 380 and 410 ug/L for
the Florida pompano (Trachinotus carolinus). Embryos of the summer flounder
(Paralichthys dentatus) were found to be more susceptible, with median
lethality occurring after 96 hours of exposure to 38 ug/L (Cardin e_t_ al. ,
1978, as cited in U.S. EPA, 1979).
In tests of copper toxicity for saltwater invertebrates, the clam
(Veneruois decussata) was among the most sensitive organisms, exhibiting
reduced burrowing activity and increased mortality at a copper concentra-
tion of 10 ug/L over a 90-day exposure period. (Stephenson and Taylor,
1975) . Saliba and Krzyz (1976) observed a decrease in "he growth raca
of the brine shrimp (Artemia salina) at a concentration .of LO ug/L copper
92
-------
TABLE 16. ACUTE TOXICITIES OF COPPER FOR FRESHWATER FISH1
Tocal Copper
Concentration Hardness (mg/L)
(ug/L) Species as CaCO, -
10- 190 Chinook Salmon 13- 182
(Oncorhynchus tshawytscha)
15.72- 3672 Cutthroat Salmon 18- 205
(Salmo clarki)
17- 1,100 Rainbow Trout 21- 371
(Salmo gairdneri)
23- 2,336 Fathead Minnow 20- 360
(Pimephales promelas)
32- 125 Atlantic Salmon 8- 20
(Salmo salar)
36- 1,250 Guppy 20-87.5
(Poecilia reticulata)
36- 2,900 Goldfish 20- 40
(Carassius auratus)
43- 780 Coho Salmon 20- 99
(Oncorhynchus kisutch)
50- 4,300 Striped Bass 53-68.4
(Morone saxatilis)
' 100 Brook Trout 45
(Salvelinus fontinalis)
150- 6202 Bluntnose Minnow 194- 324
(Pimephales notatus)
180- 5702 Brown Bullhead 200- 303
(Ictalurus nebulosus)
230- .330 Golden Shiner 36
(Notemigonius chrysoleucas)
290- 3402 Stoneroller 200- 318
(Caapostoma anomalum)
310- 1,0502 Creek Chub 200- 316
(Semotilus atromaculatus)
320 Blacknose D*ce 200
(Rhinichthys atratulus)
320- 6302 Rainbow Darter 200- 318
(Etheostoma caeruleum)
350- 375 Flagfish 1,270
(Jordanella floridae)
1 Taken from Table 1, U.S. EPA (.1979)
2 Dissolved copper
3 Rao ec al. (1975) as cited in TJI (1977)
93
-------
TABLE 16. ACUTE TOXICITIES OF COPPER FOR FRESHWATER FISH (Continued)
Total Copper
Concentration Hardness (mg/L)
Species as CaCO-
1 Taken from Table 1, U.S. EPA (1979)
2 Dissolved copper
3 Rao et al. (1975), as cited in TJI (1977)
4253- 810 Carp 53- 55
(Cyprinus carpio)
5902- 850 Orangethroat Darter 200- 318
(Etheostoma spectabile)
610 Johnny Darter 316
(Etheostoma nigrum)
6302- 1,900 Striped Shiner 200- 318
(Notropis chrysocephalus)
660-10,200 Bluegill Sunfish 20- 318
(Lepomis macrochirus)
840- 860 Banded Killifish 53- 55
(Fundulus diaphanous)
1,432 Rock Bass 24
(Ambloplites rupestris)
2,400- 2,700 Pumpkinseed 53- 55
(Lepomis gibbosus)
2,600- 3,700 Channel Catfish 36
(Ictalurus punctatus)
6,000- 6,400 American Eel 53- 55
(Anguilla rostrata)
6,200- 6,400 White Perch 53- 55
(Morone americanus)
94
-------
over 13 days. Behavior and development in the coral (Echinometra mathaei)
were adversely affected at 20, 30, and 50 ug/L in a study by Heslinga
(1976, as cited in TJI, 1977). Other chronic and sublethal effects are
described in Table 17.
According to the data compiled in U.S. EPA (1979), the LC$Q values
for marine invertebrates ranged from 9 ug/L for the calanoid copepod
fAca^gia tonsa) (Sosnowski and Gentile, 1978, as cited in U.S. EPA, 1979),
to 600 ug/L for shore crab (Carcinus maenas) larvae (Connor, 1972, as
cited in U.S. EPA, 1979). Other particularly sensitive species include
American lobster (Homarus americanus) larvae with median lethality at
48 ug/L (Johnson and Gentile., 1979), and the soft-shelled clam (Mya
arenaria) with a 96-hr LC$Q of 39 ug/L. The available data are summarized
in Table 9 in U.S. EPA (1979).
Most of the marine plants tested for copper toxicity were micro-
algae, which responded to high copper levels with decreased rates of
growth and photosynthesis. U.S. EPA (1979) refers to the £€50 value for
plants, which is the effective concentration at which photosynthesis or
growth is inhibited by 50%. The lowest ECso value reported was 5 ug/L,
for the alga species Thalassiorsiria pseudonana (Erikson, 1972, as cited
in U.S. EPA, 1979) and Scripsiella faeroense (Saifullah, 1978, as cited
in U.S. EPA, 1979). A study of copper toxicity to 18 species of marine
algae by Berland et_ al. (1976, as cited in TJI, 1977) indicated that
dinoflagellates are more sensitive as a group than diatoms. Other marine
.algae data are listed in Table 11 in U.S. EPA (1979).
4. Other Studies
In order to understand the effects of low copper concentrations on
a natural ecosystem, a series of experiments was conducted unde~r con-
trolled field conditions in marine waters in British Columbia. A descrip-
tion of the system used can be found in Menzel and Case (1977). These
CEPEX (controlled ecosystem pollutant experiment) investigations focused
on population responses to copper as reflected by changes in biomass
productivity, activity, taxonomic diversity and other parameters. Table
18 describes the responses of various species groups as reported by five
different studies. The results indicated that aqueous copper concentra-
tions between 5 ug/L and 50 ug/L had a measurable impact on the biotic
communities and that the responses varied by species. Moreover, the
copper-sensitive species were commonly replaced by more tolerant species.
5. Factors Affecting the Toxicity of Copper
Numerous variables in a natural aquatic environment may strongly
influence the availability and toxicity of copper to biota. Various
chelating, complexing, and precipitating agents may bind with copper
so that it is made unavailable for uptake. The hardness, alkalinity,
and salinity of the water affect copper toxicity because of(alkali and
alkaline metal-copper)antagonism and carbonate complexing. In addicion,
other water parameters such as temperature pH, and other heavy metal
concentrations may modify the effects of copper.
95
-------
TABLE 17. CHKONIC/SUBLETUAL EFFECTS OF COPPER ON MARINE INVERTEBRATES
•nuc .
I'K/I-
10
10
20
JO
50
>100
Mil
300
5.000
Species
Clam
(Venerupls decussatu)
Urine Shrimp
(Arterola sullna)
Coral
(Ucliinomutra uiathaei)
H
ii
Mud Snail
(Nussarius obsolctus)
Mussel
(Mytilus edulls)
it
C.miaclo
(U:ilanus crenatus)
— i
(Larvae)
Compound
CuSOi,
CuSOi. and
Cn(Cll2COOII)2
CuCl2
II
• 1
CuCl2
CuCl2
CuSOi,
Salinity
ppt
VJO
37.5
32.6 35.0
II
II
25
^30
33
>ll Temp (°C)
-/15°
-/21-2/
8.2-8.5/28°
II
II
-/20°
8.0-8.2/10°
-/-
Test
•Jurat ion
90 day
13 day
42 hr
24 lir
10 inn
72 lir
15 l.r
1 hr
1 5 Din
Test
Type
Static
Static
Static.
Nominal
•i
ii
Static,
Measurei
an dis-
solved
Cu
Static
Static
Kffecta
Mortality; reduced
burrowing activity
Decrease In groutli
rate
Irregular .retarded
growth
Loss of rJ£lil'i:i&
response, adherence
to wall, and
response to light
25Z decrease In
fertilization
50-75Z decrease in
oxygen consumption
Decreased respir-
ation
Decreased heart-
beat rate
Larvae unable to
settle
Reference
Stephenson and
Taylor (1*7S)
Saliba and Krzyz
(1976)
lesllnga (1975>).
is cited In T.IT
(1977)
••
n
Maclnnes and
ri.urnberg (1973)
as cited In TJI
(1977)
Scott and Major
(1952). as cited
in TJI (1977)
II
eyeflnch and Mott
(1948), as cited
In TJI (1977)
v£>
ON
-------
TABLE 18 REPORTED RESULTS FROM CEPEX STUDIP.S
5. 10, 50
5, 10, 50
5. 30
JO, 50
5, 10, 50
Species
Zooplankton
Response
Ho definable effect (>80% reduction on z.p.
abundance In both control and copper
treated system)
Ctenophores and medusae Lower numbers than in control
Copepods
(paeudocalanus,
Calanus, Euphasla. and
Pleurohrachia)
Bacteria (heterotrophs)
Algae
Reduced activity and reduction in egg and
fecal pellet production
Increase in numbers and activity due to re-
lease of available organic carbon from
copper-sensitive species
Change in species composition; replacement
of sensitive species with more resistent
species
Source
Gibson and Grice (1977)
Gibson and Grice (1977)
Reeve ct al.(1977)
Vaccaro et al. (1977)
Thomas and Seibert (1977)
5, 10, 50
Phytoplankton
Initial inltibition of growth until replace-
ment by resistant species
Harrison et_ al. (1977)
-------
Of all the uncertainties surrounding the validity of copper toxicity
bioassays, the complexity of the chemistry of aqueous copper is perhaps
the most significant. Many substances, both organic and inorganic, may
bind with copper (see Chapter IV) and perhaps render it inactive as a
toxicant (Brown, 1968). Chelating agents such as pyrophosphate are partic-
ularly effective in this respect (Manahan, 1972). Many such compounds are
synthetic in origin and may be found as pollutants in water bodies; their
presence can actually mitigate the toxic effects of copper. Zitco e_c_ al.
(1973) found that the incipient lethal level of copper for Atlantic salmon
(Salmo salar) was increased from 25 ug/L to 110 ug/L with the addition of
10 pg/L humic acid to the test medium, and to 240 ug/L with the addition
of 10 ug/L fulvic acid. Sprague (1968) also observed mitigative effects
for brook trout (Salvelinus fontinalis) using nitrilotriacetic acid (NTA) ;.
survival in a solution of 50 ug/L copper was prolonged from 10 hr to 47 hr
with the addition of 50 ug/L NTA. Similarly, when Shaw and Brown (1974)
added NTA to copper sulfate solutions, the LC^Q for rainbow trout (Salmo
gairdneri) increased from 140-ug/L to 500 ug/L. In a copper toxicity test
with the clam (Venerupis decussata), Stephenson and Taylor (1975) added
excess (1.0 ug/L) ethylenediaminetetra acetic acid (EDTA) to a solution of
100 ug/L copper. Clams in 100 ug/L copper solution alone did not survive
beyond 50 days, while those in 100 ug/L copper and 1.0 mg/L EDTA exhibited
no signs of toxicosis.
•
Geckler gt al. (1976) added copper directly and continually to a
stream, and the toxicity of the contaminated stream water was tested in
bioassays with a number of warm water species. These authors found that
copper was much less toxic in this stream water than would have been pre-
dicted .based on its hardness (330 mg/L CaC03> and that the toxicity of
copper in this stream water varied over a 5-month period. For rainbow
darter, a 24-hr LCso ranged from less than 4.9 mg/L to 18 mg/L copper.
The study concluded that the variable toxicity of copper in this stream
was due to the effluents of an upstream sewage treatment plant; presumably
the organic constituents were forming copper complexes, thus reducing
toxicity.
Organic ligands apparently detoxify the cupric ion by occupying one
or both valences so that the copper loses its ability to be absorbed or
metabolized. However, the effect of inorganic complexing, particularly
with carbonates, on copper toxicity is not as well understood. Shaw and
Brown (1974) reported that copper toxicity is related to the cupric ion
and aqueous copper carbonate together. Andrew £t_ al. (1977) found that
toxicity is related only to the cupric ion, and stated that Shaw and
Brown's interpretation does not account for differences observed in waters
of widely differing alkalinity. Howarth and Sprague (1978, as cited in
Chakoumakos e£ al., 1979) concluded that CuOH+ and Cl^OH)*"1" are also
toxic, in addition to the cupric ion.
In any event, the inverse relationship between water hardness (and
calcium-associated alkalinity) and copper coxicity is a well-documented
phenomenon, which essentially has two aspects. Inorganic complexing in
the form of carbonates and hydroxides, which reduces Che concentracion of
free cupric ion, is maximized in hard alkaline wacer. Conversely, a low
pH and sofc wacer reduce carbonate complexing and increase che propora-
cion of free ionic copper. The ocher factor apparencly affecting toxicicy
is calcium concencracion, which is also relaced co wacer hardness.
98
-------
Hard water has high concentrations of calcium, which competes with copper
for absorption and metabolism in biota and thus effectively reduces
copper toxicity. Although this interaction is largely hypothetical,
it has been implicated for other heavy metals such as zinc (Matthiesson
and Brafield, 1977).
In seawater, copper decreases in solubility as it mixes with relatively
high concentrations of sodium, calcium, magnesium, and other light metals
(U.S. EPA, 1979). However, copper adsorbed onto particles tends to be
released in estuarine conditions. (See Environmental Fate, Chapter IV.)
The only study found in which the effects of salinity on copper toxicity
were tested was by Jones e_t al. (1976, as cited by TJI, 1977), using the
polychaete Nereis diversicolor. They found that resistance to copper
was least at 5 ppt and 34 ppt salinity (the lowest and highest salinities
used).
Studies by Smith and Heath (1979) and Rehwoldt e_£ al. (1972) on a
total of seven species of freshwater fish indicate that temperature varia-
tions between 5° and 30°C have no significant effect on copper toxicity.
The presence of other chemicals may also influence the effects of
copper on aquatic organisms. Calamari and Marchetti (1973) tested the
effects of ionic and nonionic surfactants on the toxicity of copper to
rainbow trout. The two ionic surfactants (sodium alkylbenzene sulfonate
and sodium laurylbenzene sulfonate) acted synergistically with copper .so
that the toxicity was increased. Andrew et_ aJU (1977) found that the
inorganic chelating agent pyrophosphate increased copper perchlorate
solubility, but actually decreased its toxicity to Daphnia magna.
Orthophosphate decreased both solubility and toxicity.
In waters that are polluted with copper from mining or industrial
activities, other heavy metals are often found as well. Lead, mercury,
cadmium, and zinc are all toxic to varying degrees, and have some similar
effects on aquatic life. The interaction of two heavy metals was studied
by Ozoh and Jacobson (1979), who exposed zebra ciclid (Cichlasoma
nigrofasiciatum) eggs to concentrations of 0, 16, and 32 ug/L of copper
and zinc, alone and in combinations. They found that the synergy of
copper and zinc interfered more with hatching and normal growth than
comparable concentrations of a single metal. Lorz et_ al. (1978) observed
that coho salmon (Oncorhynchus kisutch) exposed to copper (10 yg/L) or
copper:zinc (10:400 ug/L) solutions did not feed as well as when exposed
to zinc (400 ug/L) alone.
The interactions between heavy metals are not always synergistic,
however. A study by Roales and Perlmutter (1974) provides evidence of
mutual suppression by methylmercury (HgCH3) and copper when combined in
solution. At low to moderate concentrations of copper (20-90 ug/L), the
blue gourami (Trichogastar trichooterus) experienced lower mortality when
methylmercury was added. Similarly, Ozoh (1979) found that the presence
of lead ions reduced the hatching inhibition and abnormal development
effects of copper in the zebrafish (Brachvdanio rerio).
99
-------
Although only the toxic effects of cooper have been described in this
section, in some cases copper at low concentrations can be beneficial
to aquatic life* aside from its role as a micronutrient. Ozoh and
Jacobson (1979) observed greater hatching success in zebra ciclid eggs
in 16 ug/L copper than in lower concentrations. They attributed the
lower mortality to the fungicidal and bactericidal effects of the copper
ions.
6. Conclusions
According to the literature surveyed, the lowest concentration of
copper at which adverse effects have been observed in an aquatic organism
is 1 Ug/L, which caused a growth lag in the freshwater alga, Chlorella
pyrenoidosa. (It should be noted that 1 ug/L or higher is the background level
of copper in many areas.) The lowest "chronic value" reported is 5 Ug/L,
for the brook trout (Salvelinus fontinalis) in soft water. Acute effects
appeared with exposure to 10 ug/L for the Chinook salmon (Oncorhynchus
kisutch). The salmonids as a group are the most sensitive freshwater
fish, in addition to the fathead minnow (Pimephales promelas). Daphnia
hyalina was the most sensitive of the freshwater invertebrates tested,
with a 96-hr LC5Q of 5 ug/L. Other sensitive species are the scud
(Gammarus pseudolimnaeus), with a chronic value of 6.1 Ug/L, and the midge
(Chironomous sp). Thus the concentration at which acute and chronic
effects may occur for a variety of freshwater species is 10 ug/L or less,
according to the laboratory studies surveyed.
Marine toxicity data were limited, and the lowest reported LC^Q concen-
tration was 28 ug/L for summer flounder (Paralichthys dentatus)
larvae. Among invertebrates, the clam (Venerupis decussata) was the
least resistant to copper, with adverse effects reported at 10 ug/L.
The calanoid copepod (Acartia tonsa) and the soft-shelled clam (Mya
arenaria) are also comparatively sensitive to copper. The lowest EC5Q
value recorded was 5 ug/L, for the alga (Thalassiosira pseudonana).
An overview of the data suggests that in many cases the stage of
the life cycle is an important factor in a species resistance to copper.
Generally speaking, adults and eggs were less susceptible to copper than
larvae and juveniles.
The toxicity of copper is strongly influenced by a number of environ-
mental factors. Complexing, chelating, and precipitating agents, both
organic and inorganic, generally decrease the toxicity of copper by bond-
ing, which, renders it unavailable for metabolism. In general, however,
copper toxicity (particularly of inorganic complexes) increases as water pH
and hardness decrease.
Other heavy metals often occur with copper, which hinders further
any efforts to isolate the effects of an individual parameter. Laboracory
studies indicate that zinc and copper are synergistic, while lead and
methyl mercury are antagonistic to copper toxicosis.
100
-------
In summary, general concentration ranges can be established at which
certain effects are seen in the laboratory. However, these ranges are not
rigidly defined, and may overlap as a result of differences among species
or environmental variables.
• <5 ug/L This represents the detection limit for some copper
measurements. Few adverse effects have been observed
at this level even in the softest water (some algae
are exceptions).
• 6-20 ug/L Sublethal effects as a result of an acute or chronic
exposure have been reported for sensitive species at
the upper end of this range and in very soft water.
Lethal effects have been reported for sensitive salt-
and freshwater invertebrates (the latter in very soft
water) and for some algae.
« 20-60 ug/L This range is reported as chronically and acutely •
toxic far a wide range of species in very soft water;
sublethal effects for many species have been reported
for this range in soft and moderately hard water
(200 mg/L CaC03).
• 60-120 Some lethal effects for sensitive species have been
ug/L reported in moderately hard and hard water in this
range, and less sensitive species show effects in
soft water (vertebrate and invertebrate); sublethal
effects ^for less sensitive species have also been
observed in this range.
• 120-300 Only the most tolerant species tested in hard water
Ug/L can consistently survive these concentrations. How-
ever, LC5Q values have been reported as high as
10,000 ug/L
• >300 ug/L Values in this range reported toxic to a large variety
of species in all but the hardest water.
B. EXPOSURE OF BIOTA TO COPPER
1. Introduction
Copper is a relatively abundant metal in the earth's crust, and
occurs naturally in small concentrations in most fresh and saltwater
bodies. Levels of copper in undisturbed environments are determined
largely by the composition of the local substrate, which varies geo-
graphically.
Human activities such as mining and manufacturing have substantially
increased the amount of free copper in the environment by removal from
ore and through emissions in various forms (see Section III). Copper
is also intentionally distributed through its use in agriculture and
as an algicide. New York City maintains a .059 yg/L copper concentra-
tion in its reservoirs for its algicidal properties (NRC, 1977), although
levels as high as 1 mg/L are commonly used elsewhere.
101
-------
The toxic effects of copper are significantly modified by numerous
factors, including pH, hardness, and the concentration of complexing
agents or other heavy metals. While toxicity probably decreases with
increasing salinity, copper adsorbed onto particulates in freshwater
may be. released upon contact with saltwater-, e.g., in an estuary. These
factors were discussed in Section IV.
2. Monitoring Data
The extensive data provided by STORET indicate that copper is a
frequently measured parameter, and that significant concentrations are
found in many regions of the U.S. In reviewing the data on minor river
basins, only basins where ten or more copper samples had been taken were
considered. Of the many variables that influence copper toxicity, only
pH-and hardness data were obtained, and so the effects of other factors
cannot be assessed. Moreover, the STAND program (with which the data
were retrieved) does not list individual station locations, and thus there
is no indication of which pH and hardness measurements correspond to
which copper measurement, except where data on individual stations were
retrieved. Measurements of total copper (instead of dissolved copper)
were used for the analysis because more monitoring data were available.
Table 19 shows that "copper concentrations are high in certain minor
river basins. Mean concentrations greater than 50 yg/L are found in
areas of the Southeast and in the Ohio, Lower Mississippi, Gila, Spokane
and Sacramento Rivers. For these areas, the majority of observed concentra-
tions were less than 50 yg/L. Furthermore in many of these locations 10%
or more of all observed concentrations exceeded 120 yg/L. This appears
to indicate that a small number of high concentrations skew the mean
concentration upward so that the calculated mean is not representative
of typical concentrations found.
In order to examine this issue further, data were retrieved from the
sampling stations in three minor basins with unusually high copper levels.
Of the 125 copper measurements taken at various sampling stations along
the Sacramento River in the California Basin, all of the high values were
found at one station (Spring Creek below Debris Dam): all 17 samples taken
at this station exceeded 1400 yg/L. Unfortunately, water hardness and pH
were not measured at Spring Creek.
At eleven of the 24 sampling stations in the Gila River (Colorado
River Basin), at least one copper measurement exceeded 250 yg/L, which
could represent a harmful exposure level even in the hard water normally
found in the area. At many stations, the hardness and copper measure-
ments varied significantly during the sampling period (1978); these
variations could be due to changes in discharge volume, seasonal stream
flow, or other factors.
Among the 33 sampling stations in Zone 4 of the Delaware River (in
the North Atlantic Basin), high copper levels were found primarily at
Contrary Creek and in the Wilmington area. At the former station, more
than 50% of 211 total copper measurements taken over a 15-mcnth period
102
-------
were above 60 yg/L. Over 50% of the samples taken had a pH of less
than 6, and the water was generally soft. However, the level of copper
reported for an individual station ranged from 10 ug/L to 1,000 ug/L.
These data indicate that high concentrations of copper can be either
localized (so that mean levels for an entire basin may be skewed by a few
stations) or widespread. Assessing copper exposure in a specific area,
therefore, required examining station data instead of relying on
summaries of data for river basins.
3. Ingestion
No studies were found that described the uptake of copper by aquatic
animals via ingestion. From the data discussed in Section IV, biomagni-
fication through the food chain apparently does not occur, since tissues
of higher level organisms do not have greater copper residues than those
of lower-order biota.
4. Fish Kills
Table 20 provides information on the location and activities associ-
ated with fish kills attributed to copper between 1971 and 1977. Since
many of the fish kills occurred in the presence of other metals and
chemicals, it is not possible to isolate the effects of copper in the
field. Moreover, the synergy between heavy metals may have increased
the overall toxicity in many cases. Both game and non-game fish were
affected by high levels of copper and other chemicals. No single indus-
try was responsible for the majority of the reported discharges, and
the kill events were distributed fairly evenly across the country.
In addition to the fish kills shown in Table 20, numerous fish
kills have occurred as a result of copper sulfate use as an algicide.
Though some of these appear to have resulted from misapplication, the
circumstances of many incidents are unknown.
5. Conclusion
Because of the chemistry of aqueous copper and the nature and volume
of data examined, it is difficult to draw firm conclusions about exposure
levels, either on a regional or local level. Exposure levels are of con-
cern where.soft water, low pH, or higher copper levels (or a combination of
these)occur. Such exposure may be seasonally variable, or related to point
or non-point sources. As previously discussed, monitoring data can only
be used to assess exposure potential rather than actual exposure, as infor-
mation on the concentrations of organic and inorganic ligands is often
lacking.
103
-------
TABLE 19. COPPER OBSERVATIONS IN U.S. MINOR RIVER BASINS - 1978
River Basin Mean Cu >50% of Cu >102 of Cu >50Z of Hardness
Major/Minor Name >50 ug/L >60 ug/L >120 ug/L Measurements <50 aq/L
*
*
2/3 Delaware R. - Zone 1
2/5 Delaware R. - Schuylkill
2/6 Delaware R. - Zone 2
2/7 Delaware R. - Zone 3
2/3 Delaware R. - Zone 4
3/7 Yadkin & Pee Dee Rivers * *
3/8 Catawba - Wateref, etc. Res. * * *
3/9 Edisco - Combahef R. * * *
3/13 Savannah R. * * *
3/3I1 Apalachicola R. *
3/32 Choctawhatchee R. * *
3/43 Pearl R. * *
4/3 French Broad R. * *
4/7 Duck R. * *
4/8 Tennessee R. *
5/9 Big Sandy R. *
5/18 East Fork, White R. *
5/21 Ohio R. * *
6/4 L. Erie Shore, Maumee R. to
. Sandusky R. * *
7/2 Hudson Bay, Rainy River *
7/13 Chicago Calumet R. - Des Plaines R. *
9/12 Lower Missouri R. from Nlobrara R. *
10/11 Lower Mississippi R. - Yazoo R. * *
10/16 Lower Red R. — below Denison * *
10/19 Atchafalaya R. * * *
10/20 Calcasieu R. * *
10/21 Lower Mississippi R. *
11/4 Gila R. * *
12/1 Sabine R. * * *
L2/2 Neches R. * * * *
L3/2 Clark Fork - Pend Oreille R. * *
13/3 Spokane R. * *
14/41 Central CA Coastal *
14/51 Santa Clara R. * *
14/9 Sacramento R. * * *
15/7 Great Salt Lake *
fewer than 10 measurements at this station.
SOURCE: STORET
104
-------
TABLE 20. DATA FOR COPPER-RELATED FISH KILLS, 1971-1977
Location
Lake Hamilton,
Arkansas
Roaring Brook,
Connecticut
Clark Fork
River, Montana
Black River,
Utah
Little Squaw
Creek, Calif.
Little Squaw
Creek, Calif.
Little, Squaw
Creek, Calif.
Chadahem River,
New York
Mill Creek,
Washington
Clinch River,
Virginia
Diablo Cove,
California
Housatonic
Estuary, Conn.
Pond to E.
Providence
reservoir, R.I.
Big Blue River,
Indiana
Tributary to
M. Fork, Ellchorn
Creek, Kentucky
Source
Metals production
(general)
Unreported
Mining (power dam
draw down)
Metals production
(electroplating)
Mine tailings
(abandoned)
Mine tailings
(abandoned)
Mine tailings
(abandoned)
Metals production
(electroplating)
Cleaning Waste
Power plant
Power plant
(condenser tubes)
Metals production
Metals production
Metals production
(plating)
Metals production
Chemicals Number of
Implicated Fish Killed
Cr, Zn, Cu, 14,940
Ni, CN
Phenol, Cu, Zn 300
Cu, Zn, Fe
CN, Cu
Cu
Cu
Cu
CN, Cu
Pb, Zn, Cu
Cu
Cu
Ni, Cu, Zn
2,000-3,000
59
10
100
25
100
6,000
4,000
8,000
Cu, possibly ?
Zn
Cu, Ni, Cr
Cu, Zn
333
9,602
Source: Data files, Monitoring and Data Support Division, Office of
Water Planning and Standards, LT.S. Environmental Protection Agency
105
-------
REFERENCES
Andrew, R.W., K.E. Biesinger, and G.E. Glass. ,1:977. Effects of inorganic
complexing on the toxicity of copper to Daphnia/magna. Water Research
11:309-315.
Arthur, J.W. and E.N. Leonard. 1970. Effects of copper on Gammarus
pseudolimnaeus, Physa integra, and Campeloma decisum in soft water.
J. Fish Res. Bd. Can. 27(7):1277-1283.
Bartlett, L.. and F.W. Rabe. 1974. Effects of copper, zinc, and cadmium
on Selenastrum capricornutum. Water Research 8^:179-185.
Benoit, D.A. 1975. Chronic effects of copper on survival, growth, and
reproduction of the bluegill (Lepomis tnacrochirus). Trans. Amer. Fish
Soc. 104(2):353-358.
Black, G.A.P., D.J. Hinton, C. Johnston, and J.B. Sprague. 1975.
Annotated List of Copper Concentrations Found Harmful to Aquatic Organisms.
Department of the Environment, Fisheries and Marine Service, Technical
Report No. 603.
Brown, V.M. et^ al. 1974. Aspects of water quality and the toxicity of
copper to rainbow trout. Water Research J3:797-803.
Brown, V.M. 1968. The calculation of the acute toxicity of mixtures of
poisons to rainbow trout. Water Research jZ: 723-733.
Brungs, W.A., J.R. Geckler, and M. Gast. 1976. Acute and chronic
toxicity of copper to the fathead minnow in a surface water of variable
quality. Water Research l.p_:37-43.
Brungs, W.A., R.W. Carlson, W.B. Horning II, J.H. McCormick, R.L. Spehar,
and J.D. Yount. 1977. Effects of pollution on freshwater fish. J.
Water Pollutant Control Fed. 49_(b): 1425-1493.
Bryan, G.W. 1976. Some aspects of heavy metal tolerance in aquatic
organisms, In Effects of Pollutants on Aquatic Organisms, A.P.M. Lockwood
(Ed.), Cambridge, Cambridge University Press.
Calamari, D. and R. Marchetti. 1973. The toxicity of mixtures of metals
and surfactants to rainbow trout (Salmo gairdneri Rich.)'. Water Research
7_: 1453-1464.
Chakoumakos, C., R.C. Russo and R.V. Thurston. 1979. Toxicity of copper
to cutthroat trout (Salmo clarki), under different conditions of alkalinity,
?H, and hardness. Environ. Sci. Technol. 13(2):213-19.
106
-------
Cheng, T.C. and J.T. Sullivan. 1977. Alterations in the osmoregulation
of the pulmonate gastropod Biomphalaria glabcata due to copper.
J. Invert. Pathol. 29/1):101-104.
Courtois, L.A. and R.D. Meyerhoff. 1975. Effects of copper exposure on
water balance. Bull. Environ. Contain. Toxicol. 14(2) ;221-224.
Eisler, R. 1977. Acute toxicities of selected heavy metals to the
softshell clam, Mya arenarla. Bull. Environ. Contain. Toxicol. 17_(2):
137-144.
Gachter, R., K. Lum-Shue-Chan, and Y.K. Chau. 1973. Complexing capacity
of the nutrient medium and its relation to inhibition of, algal photo-
synthesis by copper. Schweiz, Z. Hyd. 35(2);252-261.
Geckler, R. W.B. Horning, T.M. Neiheisel, H. Pickering, E.L. Robinson
and C.E. Stephan. 1976. Validity of Laboratory Test for Predicting
Copper Toxicity in Streams. U.S. EPA, Environmental Research Laboratory-
Ouluth, Office of Research & Development.
Gibson, V.R. and G.R. Guice.- 1977. Response of macro-zooplankton popula-
tions to copper: controlled ecosystem pollution experiment. Bull. Mar.
Sci. .27:85-91.
Kara, T.J., Y.M.C. Law, and S. MacDonald. 1976. Effects of mercury and
copper on the olfactory response in rainbow trout, Salmo gairdneri. J.
Fish Res. Bd. Can. _33_: 1568-1573.
Harrison, W.G., R.W[. Eppley, and E.H. Renger. 1977. Phytoplankton nitro-
gen metabolism, nitrogen budgets, and observations on copper toxicity:
controlled ecosystem pollution experiment. Bull. Mar. Sci. 27(1);44-57.
Hartung, R. 1973. Biological effects of heavy metal pollutants in water.
Adv. Exper. Med. Biol. 40_:161-72.
Johnson, M.W. and J.H. Gentile. 1979. Acute toxicity of cadmium, copper,
and mercury to larval American lobster Homarus americanus. Bull. Environ.
Contain. Toxicol. 22:258-264.
Judy, R.D., Jr.. 1979. The acute toxicity of copper to 'Gammarus fasiatus
say, a freshwater amphipod. Bull. Environ. Contain. Toxicol. 21.;219-224
Kobot'yev, V.G. , V.I. Kapkov, Ye.G. Ruishadze, N.V. Turunina, and N.A.
Shidlovskaya. 1975. The toxic effect of copper complexes on algae.
Gidrobiol. Zh. (Eng. transl.) ll(5):33-38.
Kleerekoper, H., G.F. Westlake, and J.H. Matis. 1972. Orientation of
goldfish (Carassius auratus) in response to a shallow gradient of a 'sub-
lethal concentration of copper in an open field. J. Fish. Res. 3d. Can.
29(1):45-54.
107
-------
Lorz, H.W., R.H. Williams, and C.A. Fustich. 1978. Effects of Several
Metals on Smelting of Coho Salmon. U.S. Environmental Protection Agency,
Report No. EPA-60013-78-090.
Lorz, H.W. and B.P. McPherson. 1976. Effects of copper or zinc in fresh
water on the adaptation to sea water and ATPase activity, and the effects
of copper on migratory disposition of coho salmon (Oncorhynchus kisutch).
J. Fish Res. Bd. Can. 33_(9):2023-2030.
Lett, P.F., G.F. Farmer, and F.W.H. Beamish. 1976. Effect of copper on
some aspects of the bioenergetics of rainbow trout (Salmo gairdneri).
J. Fish. Res. Bd. Can. 33_: 1335-1342.
Manahan, S.E. 1972. Environmental Chemistry. Boston: Willard Grant
Press.
Matthiesson, P., and A.E. Brafield. 1977. Uptake and loss of dissolved
zinc by the stickleback Gasterostreus acuteatus L. J. Fish Biol. 10;399.
McKim, J.M., J.G. Eaton, and G.W. Holcombe. 1978. Metal toxicity to
embryos and larvae of eight species of freshwater fish - II: copper.
Bull. Environm. Contain. Toxicol. 19:608-16.
McKim, J.M. and D.A. Benoit. 1970. Effects of long-term exposures to
copper on survival, growth, and reproduction of brook trout (Salvelinus
fontinalis). J. Fish Res. Bd. Can. 28(5):655-62.
McKim, J.M. and D.A. Benoit. 1974. Duration of toxicity tests for
establishing 'ho effect" concentrations for copper with brook trout
(Salvelinus fontinalis). J. Fish. Res. Bd. Can. 31(4);448-451.
Menzel, D.W. and J. Case. 1977. Concept and design: controlled eco-
system experiment. Bull. Mar. Sci. 27:1-4.
Mount, D.I. and C.E. Stephan. 1969. Chronic toxicity of copper to the
fathead minnow (Pimephales promelas) in soft water. J. Fish. Res. Bd.
Can. 26_(9): 2449-57.
Okazaki, R.K. 1976. Copper toxicity in the pacific oyster Crassostrea
gigas. Bull. Environm. Contain. Toxicol. 16_(b) : 658-64.
Overnell, J'. 1975. The effect of some heavy metal ions on photosynthesis
in a freshwater alga. Pest. Biochem. Physiol. 5_: 19-26.
Ozoh, P.T.E. and C.O. Jacobson. 1979. Embryotoxicity and hatchability
in Cichlasoma nigrofasciatum (guenther) eggs and larvae briefly exposed
to low concentrations of zinc and copper ions. Bull. Environm. Contain.
Toxicol. 22^:782-86.
Ozoh, P.T.E. 1979. Malformations and inhibitory tendencies induced to
Brachydanio rsrio (Hamilton-Buchanan) eggs and larvae due co exposures
in low concentrations of lead and copper ions. Bull. Environm. Concam.
Toxicol. 21:668-675.
108
-------
Raymont, J.E.G. and J. Shields. 1963. Toxicity of copper and chromium
in the marine environment. Air Water Pollut. .7(415):435-443.
Reeve, M.R., J.C. Gamble, and M.A. Walter. 1977. Experimental observa-
tions on the effects of copper on copepods and other zooplankton:
controlled ecosystem pollution experiment. Bull. Mar. Sci. 27(1);92-104.
Rehwold, R., L. Lasko, C. Shaw, and E. Wirhowski. 1973. The acute
toxicity of some heavy metals ions toward benthic organisms. Bull.
Environm. Contain. Toxicol. 10(5);291-94.
Rehwoldt, R., L.W. Menapace, B. Norric, and D. Alessandro. 1972. The
effect of increased temperature upon the acute toxicology of some heavy
metal ions. Bull. Environm. Contain. Toxicol. 8^91-95.
Roales, R.R. and A. Perlmutter. 1974. Toxicity of methylmercury and
copper, applied singlely and jointly, to the blue gourami, Trichogaster
trichopterus. Bull. Environm. Contain. Toxicol. 12(5) ;633-639.
Sauter, S., K.B. Bukton, K.J. Macek and S.R. Petrocelli. 1976. The
Effects of Exposure to Heavy Metals on Selected Fresh Water Fish. Report
to tne U.S.'Environmental Protection Agency, Environmental Research
Laboratory, Office of Research & Development, Duluth, Minnesota.
Saliba, L.J. and R.M. Krryz. 1976. Acclimation and tolerance of Artemia
salina to copper salts. Mar. Biol. 38:231-238.
Sellers, C.M., A.G. Heath, and M.L. Bass. The effect of sublethal concentra-
tions of copper and zinc on ventilatory activity, blood oxygen and pH in
rainbow trout (Salmo gairdneri). Water Research 2:401-408.
Shaw, T.L. and V.M. Brown. 1974. 'The toxicity of some forms of copper
to rainbow trout. Water Research 8/.377-82.
Smith, M.J. and A.G. Heath. 1979. Acute toxicity of copper, chromate,
zinc, and cyanide to freshwater fish: effect of different temperatures.
Bull. Environm. Contam. Toxicol. 2_2_: 113-119.
Solbe, J.F. de L.G., and V.A. Cooper. 1976. Studies on the toxicity of
copper sulphate to stone loach Noemachilus barbatulus (L.) in hard water.
Water Research 10_:523-527.
Sprague, J.B. 1968. Promising anti-pollutant chelating agent NTA protects
fish from copper and zinc. Nature (London) 220:1345-1346.
Stephenson, R.R. and D. Taylor. 1975. The influence of EDTA on the
mortality and burrowing activity of the clam (Venerupid decussata)
exposed to sub lethal concentrations of copper. Bull. Environm. Contam.
Toxicol. 14(3):304-308.
109
-------
Sugiura, K., S. Sato, and M. Goto. 1976. Toxicity assessment using an
aquatic microcosm. Chemophere 2_: 113-118.
Sunda, W. and R.R.L. Guillard. 1976. The relationship between cupric
ion activity and the toxicity of copper to phytoplankton. J. Mar. Res
34(4):511-529.
Thomas, W.H. and D.L.R. Seibert. 1977. Effects of copper on the dominance
and the diversity of algae: controlled ecosystem pollution experiment.
"Bull. Mar. Sci. 27(1):23-33.
Tracor Jitco, Inc., TJI. 1977. Chapter VI. Environmental Fate and
Effects: Copper. Draft report to Monitoring and Data Support Division,
Office of Water Planning and Standards, U.S. Environmental Protection
Agency.
U.S. Environmental Protection Agency. 1978. Reports of fish kills, 1971-
1977. Data files, Monitoring and Data Support Division, Office of Water
Planning and Standards.
U.S. Environmental Protection Agency (U.S. EPA). 1979. Ambient water
quality criteria: copper. Criteria and Standards Division, Office of
Water Planning and Standards.
Vaccaro, R.F., F. Azam, and R.E. Hodson. 1977. Response of natural
marine bacterial populations*to copper. Controlled ecosystem pollution
experiment. Bull. Mar. Sci. 27:17-22.
Yopp , J.H., W.E. Schmid, and R.W. Hoist. 1974. Determination of Maximum
Permissible Levels of Selected Chemicals that Exert Toxic Effects on
Plants of Economic Importance in Illinois. Report to Illinois Institute
of Environmental Quality.
Zitco, P., W.V. Carson, and W.G. Carson. 1973. Prediction of incipient
lethal levels of copper to juvenile Atlantic'salmon in the presence of
humic acid by cupric electrode. Bull. Environm. Contam. Toxicol. 10(5):
265-271.
110
-------
VI. --EFFECTS OF AND EXPOSURE TO COPPER—HUMANS
A. HUMAN TOXICITY
1. Introduction
Copper is an essential trace element in human and an-i^ai, nutrition.
The total body content of copper in a hypothetical 70-kg adult ranges
between 100 tag and 150 mg (Ulmer, 1977). Liver, brain and kidney are rich
in copper, but one-third of the body store of copper is in muscle tissue
(Venugopal and Luckey, 1978).
As an essential component of key metalloenzymes, copper plays a
vital role in numerous biochemical and physiological functions in higher
animals. Most importantly, copper is involved in hematopoiesis, main-
tenance of vascular and skeletal integrity, and the structure and func-
tion of the central nervous system (O'Dell, 1976). Copper is also
essential to iron utilization, is involved in the physiology of taste
and smell, and functions in enzymes for energy production (Oster and
Salgo, 1977; Venugopal and Luckey, 1978). Included among these cupro-
enzymes are cytochrome c oxidase, tyrosinase, ceruloplasmin, monoamine
oxidase and dopamine 3-hydroxylase (O'Dell, 1976).
a. Coooer Deficiency
Animals deficient in copper exhibit anemia, vascular abnormalities,
abnormal keratinization and depigmentation of hair, abnormalities in
bone formation, myocardial fibrosis, demyelination of the central nervous
system, gastrointestinal disorders, difficulties in parturition and
neonatal ataxia (Vuori e_t al., 1978).
Newborn rats born to dams fed diets low in copper (0.5 mg/kg in the
diet) were severely anemic and almost entirely non-viable. The copper-
deficient-offspring showed a high incidence of skeletal anomalies and
many had abdominal hernias; one-fourth of the offspring were affected
with edema and a characteristic subcutaneous hemorrhage (O'Dell et al.,
1961). Maternal copper deficiencies have also been shown to result in
central nervous system abnormalities in lambs and guinea pig neonates
(O'Dell ec al., 1961).
Due to the relative abundance of copper in man's diet and its slow
rate of excretion, the concept of copper deficiency in man was not widely
accepted until recently. During the last decade, copper deficiency has
been reported in small, premature infants (<1500 g) (al-Rashid and
Spangler, 1971), in malnourished infants alimented exclusively by the
intravenous route (Karpel and Peden, 1972), as well as in adults wich
aialabsorpcion disorders (Dunlap at al. , 1974) . Serum copper and
ceruloplasmin (the major plasma copper orotain) drop and anemia,
-------
leukopenia and neucropenia often rasulc (Ulmer, 1977; Graham and Cordano,
1976). Ceruloplasmin is believed to be necessary for the normal flow of
iron from cells to plasma (Lee _et_ al., 1976; Iwanska and Strusinska,
1978).
In humans, a sex-linked fatal disorder known as Henkes's syndrome
results from a defect in the intestinal transport of copper. Affected
male infants exhibit kinky, depigmented hair (due to defect in copper-
linked disulfide bond formation), physical and mental retardation with
widespread degeneration of the brain, and hypothermia; death generally
occurs within the first few years of life (Ulmer, 1977; NRG, 1977).
There are other inherited metabolic diseases characterized by poor '
pigmentation and/or hair abnormalities suggesting that biochemical path-
ways involving copper enzymes are impaired. The metabolic defects in
the varieties of albinism are in the pathways from tyrosine to melanin,
and some forms of the disease involve differences in the copper enzyme
tyrosinase (Oster and Salgo, 1977).
A more detailed discussion of the various manisfestations of copper
deficiency in both man and animals may be found in Graham and Cordano
(1976), NRC (1977), O'Dell et. al. (1961), Oster and Salgo (1977), and
Vuori et al. (1978).
2. Metabolism and Bioaccumulation
The average adult ingests between 2 mg and 5 mg of ionic copper
daily (Ulmer, 1977). Approximately 30% of ingested copper is absorbed
from the stomach, duodenum and jejunum; the unabsorbed copper
is passed directly into the bowel. Effective net absorption, however,
only about 5% due to excretion of copper into bile; biliary copper is
bound to protein, and this complex is not reabsorbed (Frommer, 1977;
Venugopal and Luckey, 1978). Copper absorption is influenced by a
number of factors including its chemical form; the presence of competing
ions such as zinc, iron, cadmium or molybdate in the diet; or the presence
of certian amino acids and/or phytate (Venugopal and Luckey, 1978).
The absorption of copper salts from sites of parenceral injection
is gradual, depending upon the solubility of salt. Absorption of copper-
containing dusts via the lungs is similar. Absorption through the skin
is minimal (Venugopal and Luckey, 1978).
Absorbed copper is present in serum as an exchangeable loose complex
with serum albumin and as a firmly bound, copper metalloprotein, cerulo-
plasmin. The copper-albumin complex transports copper across membranes
and distributes it to soft tissues. Ceruloplasmin formed in the liver,
has a number of functions and appears to be a storage depot for copper.
Ceruloplasmin accounts for 95% of Che copper found in human plasaa
(Scheinberg and Stainlieb, 1960; Linder, 1977; Venugopal and Luckay,
1978).
-------
Oral or intravenous administration of "radiolabeiled copper.in
humans is followed within 4 hrs by a transient rise in serum radio-
activity that corresponds to the albumin fraction and is succeeded by a
slower secondary rise corresponding to the release of newly synthesized
ceruloplasmin from the liver (Adelstein and Vallee, 1961).
la mammals, the major excretory pathway of absorbed copper is via
the bile (802), with an additional 157, passed directly into the bowel.
Small amounts are also excreted in urine (2-4%) and sweat (Adelstein
and Vallee, 1961; Goodman and Gilman, 1975; Graham and Cordano, 1976).
Human breast milk contains 10-70 ug/100 ml (Spector, 1956).
An efficient homeostatic mechanism for copper exists in man. In
addition to the liver, the primary organ regulating copper metabolism,
the intestinal mucosa, acts as a regulatory barrier to the absorption
of excessive copper and for the release of copper into intestinal fluids
(Venugopal and Luckey, 1978).
Mean concentraions of copper in serum of healthy men and women are
in the 80-150 ug/100 ml range (Cartwright and Wintrobe, 1964; Spector,
1956). Several conditions have been shown to influence serum copper
levels; serum copper is elevated during pregnancy (Chez et al., 1978),
in women taking oral contraceptives (Shifrine and Fisher, 1976), and
with the administration of hormones (Adelstein and Vallee, 1961; Johnson
j|t al., 1969; Meyer .et. al., 1959). Serum copper is also elevated in
several types of cancer including bronchogenic carcinoma; squamous cell
carcinoma of the larynx; and cervical, breast and bladder cancer (Schwartz,
1975).
The highest tissue levels of copper are found in liver, heart,
kidney and pancreas (2-5 mg/100 g dry tissue)(Vuori et al., 1978).
Although females have lower concentrations of copper in tissue than
males, the differences are not significant. The pancreas and skeletal
muscles show a continuous decline in copper concentration with increasing
age while the liver and kidney show decreasing concentrations up to
maturity, then level off (Vuori et al., 1978).
Additional information on the metabolism, storage and excretion of
copper by man and experimental animals can be found in Scheinberg and
Sternlieb (1960), Adelstein and Vallee (1961), and NRC (1977).
3. Animal Studies
a. Carcinogenicity
An increase in occupational lung cancer among copper miners and
smelters has been noted (Kuratsune et al.., 1974; Tokudome and Kuratsune,
1976; Newman e_t_ al_., 1975) hue appears to be related to prolonged axposura
co arsenic rather than to copper itself. Mortality from lung cancer among
copper smelters was positively related co workers exposed to ore containing
U.J
-------
high levels of arsenic or co vorkers who had been involved in smeltering
processes used prior Co World War II (Tokudome and Kuratsune, 1976).
Reports on the effects of dietary copper on carcinogenesis and
tumor growth have been varied. Elevated serum copper levels have been
reported in humans with osteosarcoma (Fisher _et_ al., 1976); Hodgkin's disease
(Mitta and Tan, 1979); bronchogenic carcinoma; squamous-cell carcinoma
of the larynx, and cancer of the bladder and cervix, and breast (Schwartz,
1975).
Fisher and co-workers (1976) noted elevated levels of serum copper
in individuals with primary or metastatic osteosarcoma. The most
elevated serum copper levels and the highest ratio of serum copper to
serum zinc were found in patients with the more advanced disease
(metastatic) and the poorest prognosis. However, in patients who were
clinically tumor-free following amputation of osteosarcomatous limbs,
serum copper levels were normal. In a later study (Shifrine and Fisher,
1976), these authors attempted to determine whether a similar elevation
occurred in ceruloplasmin. They noted that the ratio of serum copper
to ceruloplasmin was constant but that the concentration of ceruloplasmin
was significantly increased in sera of patients with osteosarcoma com-
pared with the sera of normal healthy individuals (30 mm2vs. 52 mm2 for
controls). Presumably, the increased level of ceruloplasmin in patients
with osteosarcoma is the reason for the elevated serum copper value noted
in the earlier study.
Mitta and Tan (1979) also found elevated serum levels of copper in
children with Hodgkin's disease; the highest levels were found in children
diagnosed at the more advanced stages of the disease. Following treatment,
however, serum copper was not a reliable measure of recurrence.
Similarly, Seto ^jt al. (1978) found serum copper was augmented two
to six times among rabbits with squamous-cell carcinoma as compared with
animals with benign skin papillomas.
On the other hand, Santoliquido_et_al. (1976) found no significant
difference (p >0.9) in the copper concentration of 20 samples of malig-
nant and. noncancerous breast tissue (range 0.4-2.21, mean 0.96 vs. range
0.05-5.1, mean 0.94 ug/g wet tissue for noncancerous tissues).
Luthra e£ al. (1975, 1978) have monitored 2603 registered users of
copper intrauterine devices (IUD) for periods up to 36 months for
dysplastic lesions of the cervix or precancerous lesions. Only those
women who had been followed up + 2 mo. of scheduled follow-up were in-
cluded for analysis. To date, a total of 153 women have been followed
for 36 months of continuous copper-IUD use, 397 women for a period of
24 months. In a total of 2603 women examined, 95 dysplasia cases have
been aoted (56 initial and 39 developed during use). Out of these 95
cases, 59 ciouid be followed up. Mora than 33% of these cases regressed
co normalcy while 10 cases (17%) persisted as dysplasia. To date, no
114
-------
dysplastic case.has progressed--to-cancer during Che short study period.
Further follow-up is currently underway.
The suppressive effect of copper on chemically-induced carcinogene-
sis in animals has been widely reported. Yamane and Sakai (1973) reported
that concurrent administration of 0.5% copper acetate with the carcinogen
3'-nethy1-4-(dimethylamino) azobenzene (3'-Me-DAB) in the diet of female
Wistar rats for 7 months inhibited 3'-Me-DAB-induced heptocarcinogenesis.
The incidences of liver tumors were 39, 0, and 0% for 3r-Me-DAB, copper
alone or the combination, respectively.
Kamamoto e_t_ al. (1973) also found that the addition of 0.25% cupric
acetate to'the diet of male Wistar rats for a minimum of 12 weeks,
inhibited the induction of ethionine-induced hepatomas. Yamane et_ al.
(1976, 1977) found that the inhibitory activity was due to the direct
interaction of copper with the rate of in vivo ethylation of rat liver
t-RNA and DMA by ethionine.
Petering and co-workers (1967) observed that both the anti-tumor
activity and the toxicity of 3-ethoxy-2-oxobutyraldehyde bis (thiosemi-
carbazone) in rats bearing Walker 256 nitrogen-mustard-resistant carcino-
sarcoma was directly dependent on the dietary intake of cupric ion.
Copper in the absence of drug was without effect.
In diets containing either 1 mg/kg copper (deficient) or 800 mg/kg
copper (excessive), little difference was found in the induction of liver
tumors in rats fed the carcinogen acetylaminofluorene (AAF) in the diet
for 6 months, although the incidence of tumors at other sites was
diminished. Similarly, the incidence of dimethylnitrosamine-induced
hepatic neoplasms in rats on either copper deficient or excessive diets
was unaffected. Kidney neoplasms, however, were absent on an excess
copper-containing diet compared with an incidence of 57% in copper-
deficient, dimethylnitrosamine-treated animals. No kidney neoplasms
were present in control animals (Carlton and Price, 1973).
Burki and Okita (1969) also reported the addition of copper sulfate
(198 mg/L) to the drinking water of mice had no effect on the incidence
of 7,12-dimethylbenz (o)-anthracene-induced lymphomas or tumors of the
lung and breast.
Thus, no experimental evidence exists to suggest that ingestion or
localized absorption of copper is tumorigenic in either man or experi-
mental animals. Indeed, several studies indicate that the administra-
tion of copper may inhibit tumor development. The significance of
elevated serum copper levels in various types of cancer is unclear and
remains to be elucidated.
b. Mutasenesis
Some indicacions of aucagenic effaces of copper have been reported
(Demerec _2t .al. . 1951; Law, 1938; Magrshikovskaja, 1936; Loeb at al. ,
115 '
-------
1977; Casto _§£_ al., 1979). Demerec and co-workers (1951) noted an
increase in back-mutations from screpcomycin dependence co nondependence
in Escherichia coli exposed co solutions of copper sulfate for three
hours but only at concentrations which produced less than 5% survivors.
For example, at a concentration of 0.00075% CuSC^, 2.4% of the cells
survived; mutation frequency was 40.5 mutants per 103 bacteria compared
to 5.1 mutants per 103 bacteria in controls.
Law (1938) and Magrzhikovskaja (1936) have both demonstrated the
capability of copper sulfate to increase the rate of lethal mutations
in Drosophila melanogaster. Injection of a 0.1% solution of CuSOu. and
treatment of fertilized eggs with a concentrated aqueous solution of
10 .minutes resulted in a mutation rate of 1 in 86.4 compared with 0 in
507 for controls (Law, 1938).
Loeb and co-workers (1977) found that copper ion at two or more
concentrations increased the infidelity of DNA synthesis in vitro by
more than 30 percent and scored copper as a positive mutagen. Infidelity
during DNA synthesis may result in mutations.
Casto _et_ al. (1979) recently noted that copper (.05-0.6 mM) also
enhanced the transformation frequency of Syrian hamster embryo cells
by a simian adenovirus, SA7. Hamster cells were either treated for
18 hrs prior to virus inoculation or 5 hrs after inoculation for a
period of 48 hrs. Enhancement ratios of 2.2 and 16.2 were recorded for
0.08 mM CuSO^ and 0.38 mM C^S, respectively.
Negative findings were reported by Nishioka (1975) for a 0.05 M
solution of CuCl2 tested in a rec assay with Bacillus subtilis, strains H17
(Rec+) and M45 (Rec-).
In summation, information on the mutagenicity of copper is equivocal.
Enhanced transformation of hamster embryo cells by a simian adenovirus
is seen in the presence of copper and increased lethal mutations noted
in Drosophila, but only at high concentrations. Bacterial assays are
either negative or show mutagenic activity only at concentrations toxic
to the bacterium. Further work is needed to clarify the mutagenic
nature of copper, particularly in mammalian cells.
c. Adverse Reproductive Effects
Copper, when implanted into the uterus, is known to exert a con-
traceptive effect in both humans and experimental animals (Oster and
Salgo, 1975; Hasson, 1978). Although the exact mechanism through which
copper exerts its contraceptive action is unknown, the action is localized
and implantation of the blastocyst does not occur (Ferm, 1976).
Chang and laturn (1970) demonstratad chat blastocysts briefly exposed
co copper wire _in vitro vera able Co develop when placed 'in normal
uceri. However, biastocysts in copper-containing ucari disappeared before
imolantacion occurred.
-------
Subsequently, Brinster and Cross (1972) found chat copper was coxic
co Che embryo. Exposure of two-celled mouse embryos in culture for 72
hrs co concentrations of 2.5 x 10" s M CuCl2 and higher was lethal,
whereas embryos exposed co lower concentrations developed into biasco-
cysts. In addition to killing the embryos, the-higher concentrations
of copper appeared co dissolve the zona pellucida of a few embryos.
Cuadros and Hirsch (1972) observed that the presence of metallic
copper in the uterine cavity of rats or monkeys stimulated the local
exudacion of polymorphonuclear leukocytes. This mobilization may inter-
fere with the maturation or survival of newly fertilized eggs.-
Microscopic examination of uterine tissue from rats, rabbits and
monkeys surgically implanted with copper intrauterine devices for 52
weeks revealed no lesions attributable to copper (Youkilis e_t_ al., 1973).
• I
With respect to teratogenic effects, there is no evidence to suggest
that intrauterine copper has a teratogenic effect on the exposed fetus
(Hasson, 1978). Copper rings placed in the uteri of rats, hamsters
and rabbits after implanation and left in situ throughout gestation did
not produce teratogenic effects in the fetuses of those test animals
(Chang and Tatum, 1973). In rats, however, insertion of a 5-7-mm copper
ring into one horn of the uterus on day 6 of gestation increased the
percentage of resorbed embyos (59.6%) compared with platinum-wire-
implanted controls (25%) or untreated controls (13.9%). The average
number of implantation sites and number of live fetuses were also
decreased (i.e., 5.3, 6.0 and 6.5 implantation sites, and 2.3, 5.5 and
5.2 live births, respectively). The percentage of absorbed fetuses was
found to increase in direct proportion to the length of time the copper
wire was left in situ (Chang and Tatum, 1975).
In. one animal study, intravenous injection of copper salts in
pregnant golden hamsters (Cricetus auratus) on day 8 of gestation
resulted in an increase in embryonic resorptions, as well as the appear-
ance of developmental malformations in surviving offsprings (see Table
21). Copper in chelated form (copper citrate) was considerably more
embryopathic than uncomplexed copper (copper sulfate) although embryo-
cidal activities were similar. Malformations of the heart, especially
ectopia cordis, appear to be a specific teratogenic effect of copper,
particularly of the citrate complex. This may be the result of greater
binding of uncomplexad copper to sites in the maternal system and thus
its relative unavailability to the developing fetus (Ferm, 1976; Perm
and Hanlon, 1974).
Thus, copper exerts a localized contraceptive effect when implanted
in the uterus. The exact mechanism of action is unclear but implantation
of the blastocyst does not occur. Although toxic to the embryo, there
is no evidence to suggest intrauterine copper is ceratogenic. A single
study did report developmental inaifonnations in hamsters injected intra-
venously with high levels of copper on che eighth day of gestation.
117
-------
TABLE 21. EFFECT OF COPPER SALTS ON EMBRYONIC DEVELOPMENT IN THE IIAMSTEU
Dose
1.4; vel
(iiH|Cti/kg)
us Co|>|>er Sulfate
2.13
4.25
7.5
10. 0
,_. as (;«>|>per Citrate
H
00 0.25-1.5
i. a
2.2
4.0
No.
Mothers
Treated
16
3
3
2
13
6
8
2
No. No.
Gestation Living
Sacs Embryos (%)
210
49
30
maternicidal
172
81
99
maternicidal
155
7
0
-
143
48
65
_
(74)
(14)
(0)
(83)
(59)
(66)
No.
Resorp-
tions
55
42
22
-
29
33
34
„
(26)
(86)
(74)
(16)
(41)
(34)
No.
Abnormal
Embryos (%)
12 (6)
4 (8)
-
-
4 (2)
14 (17)
35 (35)
_
Co 111rola (deminerallzed water)
0.5-1.0
ml/lOOg
10
125
115 (92) 10 (8)
0 (0)
SOUKCE: Ferin and llunlon, 1974.
-------
d. Other Toxicological Effects
There is a vide margin of saiecy between copper deficiency and
copper toxicosis in mammalian species, with the relative toxicity based
on the efficiency of absorptive and excretory mechanisms (Venugopal and
Luckey, 1978). Among mammals, copper toxicosis is more prominent in
ruminants than nonruminants due to the interactions of copper, molybdenum
and sulfate in ruminants; in nonruminants, the interactions of iron and
zinc with copper predominate (NRC, 1977).
The acute oral toxicity of copper salts in laboratory animals ranges
between 140 mg and 300 mg/kg depending on the salt; an oral mean lethal
dose (LDjo) of 31 mg/kg, however, has been reported in guinea pigs (RTECS,
1977). Acute copper poisoning in mammals produces tachycardia, hypoten-
sion, hemolytic anemia, oliguria, uremia, coma, cardiovascular collapse
and death (Venugopal and Luckey, 1978). Acute inhalation of copper
produces congestion of nasal mucous membranes and ulceration and perfora-
tion of the nasal septum (Venugopal and Luckey, 1973). A list of acute
LDjg values for various copper compounds is presented in Table 22.
Over prolonged periods of time, laboratory animals can tolerate up
to 100 times the normal dietary intake of copper. Excessive intake of
copper (about 300 to 500 times normal intake) by mammals leads to accumu-
lation of copper in tissues, saturation of hepatic copper binding sites,
and necrotic hepatitis. The extent of accumulation and subsequent toxicity
depends upon the species; the dietary levels of zinc, iron, molybdate and
sulfate; and the efficiency of the animals' excretory mechanisms (Venugopal
and Luckey, 1978).
In rats, levels in excess of 250 mg copper/kg diet are required to
produce toxicosis, and normal hepatic copper levels are maintained until
a diet extremely high in copper (1000 mg/kg diet) is reached (NRG, 1977).
Hepatic and renal necrosis have been observed in both rats and mice exposed
to excessive copper levels (Lai and Sourkes, 1971; Vogel, 1960). Boyden
et_ al. (1938) noted that rats fed 500 mg copper/kg diet as copper sulfate
for 4 weeks were normal and exhibited good growth. At 1000 and 2000
mg/kg diet, growth and food intake were markedly depressed and spleen
and liver copper levels at 4 weeks were markedly increased. Rats fed
4000 mg copper/kg diet died within 1 week.
e. Copper-Metal Interactions
The toxic effects of metals are often complicated by mutual biological
antagonism of one metal with another at some functional site. For example,
dietary zinc, copper and iron are so related that the balance of these
nutrients is important in determining the metabolic effects of each other
(Task Group on Metal Interactions, 1978).
The known antagonistic effects of cadmium on copper metabolism are
probably due, at least in part, co inhibition of copper absorption
(Campbell ana Hills, 1974; Task Group on Metal Interactions, 1973).
119
-------
TABLE 22. ACUTE TOXICITY OF COPPER COMPOUNDS
Comoound
Copper metal
Copyer(I) chloride
Copper (II) chloride
Copper citrate
Copper hydroxide
Copper oxide
Copper sulfate
Species
Mouse
Human
Rat
Rat
Mouse
Guinea pig
Mouse
Rat
• Human
Rat
Human (child)
Human
Rat
Mouse
Route
intraperi toneal
oral
oral
oral
oral
oral
intraperitoneal .
oral
oral
oral
oral
oral.
oral
intraperitoneal
LD. (me/kg)
3.5
50 LDLo1
265
140
190
31
7.4
1580
200 LDLo2
470
200 TDLo
50 LDLo
300
7
Lowest published lethal dose.
2
Lowest published toxic dose (systemic effects).
SOURCE: RTECS, 1977
120
-------
High levels of zinc -interfere-with-copper^absorption in rats (Van
Campen and Scaife, 1967) while increases in the zinc to copper ratio
increase plasma cholesterol levels in rats (Klevay, 1973).
Increases in dietary copper from 1 tag. to 20 mg/kg diet were found to
enhance the severity of lead toxicity in young male rats (Carklewski
and Forbes, 1977).
A complete discussion of these complex interactions is beyond the
scope of this report but has been reviewed in detail by the Task Group
on Metal Interactions, 1978; Magos, 1976; Sandstead, 1976; and Parizek,
1976. There are nq available data on the relationship between intakes
of copper, zinc and iron and the effects of cadmium in human populations
(Task Group on Metal Interaction, 1978) but there is no question that
the effects of copper are modified to some extent in the presence of
other metals.
4. H"™^n Studies
Copper toxicosis is rare in man. This is attributable to three
factors: copper is an essential element in human nutrition, it is
incompletely absorbed from the gastrointestinal tract; and milligram
quanitities of ionic copper trigger an emetic action in man, thus pre-
venting serious systemic toxicity. Exposure to copper generally occurs
either by ingestion, inhalation, direct skin contact or from copper intra-
uterine devices.
a. Ingestion
Fatal copper poisoning is rare in man due to the emetic properties'
of copper, as well as the metallic taste. Acute copper poisonings have
occurred, however, following ingestion of acidic food or drink that was
in prolonged contact with the metal or ingestion of a large quantity
(several grams) of a copper salt where vomiting failed to occur (NRC,
1977). For example, a 44-year-old woman with a partial gastrectomy
failed to vomit 10 ml of a 10% solution of copper sulfate (*• 400 mg Cu )
given to her as an emetic. Despite gastric lavage, the woman died 6
days later with respiratory, renal and hepatic failure, hemolytic anemia
and gastrointestinal hemorrhage (Stein et_ a±., 1976). On the other
hand, Walsh and co-workers (1977) reported the survival with treatment
of an 18-month-old boy who ingested approximately 3 § of copper sulfate
(nv 1200 mg Cu"*"*) . Renal tubular damage and hemolytic anemia appeared
during the acute phase of poisoning, but the child appeared "clinically"
well within 5 days.
Chugh _§£ al. (1977) also reported acute renal failure in 11 of 29
suicidal patients wich acute copper sulfate poisoning (ingested between
1 g and 50 g). Incravascular hemolysis appeared to be the chief factor
responsible for renal lesions in these patients and, despite dialysis,
only 5 of 11 patients recovered.
1 71
-------
It Is believed chat the mishandling of copper following its accumu-
lation by high copper intake would produce similar symptoms as are observed
in patients with Wilson's disease, a hepatolenticular degenerative disorder
of copper metabolism. This disease, inherited as an autosomal recessive
trait, is characterized by a two-phase process involving passive accumu-
lations of copper in the liver over an extended period followed by the
sudden release of this stored copper, generally described as the hemolytic
crisis. Symptoms include tremor, ascites, psychosis, slurring of speech,
and eventual hepatic necrosis and schlerosis of the corpus striatum, brain
trauma and death (Bremner, 1974; Venugopal and Luckey, 1978).
b. Inhalation
"Vineyard sprayer's disease" is known to occur in workers exposed
to fungicidal sprays containing copper sulfate. Pulmonary copper depo-
sition, as an apparently local effect, occurs in the lungs of vineyard
workers after years of exposure. Blue areas of the lung, noted at
autopsy, suggest the presence of excess copper. Hepatic lesions are
also present, including focal or diffuse swelling and proliferation of
Kupffer cells, histocytic or sarcoid-like granulomas, liver fibrosis
and cirrhosis (Pimental and Menezes, 1977).
•
c. Dermal Exposure
A case of acute copper poisoning resulting from the absorption of
copper sulfate from burned dermal tissue was reported by Holtzman e_t al.,
1966. A 5-1 /2-year old girl burned over 30-40% of her body developed
icterus, oliguria and hemolytic anemia within 24 hrs of the seventh
debridement with copper sulfate crystal over a 9-week period. Her serum
ceruloplasmin and copper rose to 86 mg/100 ml and 540 ug/100 ml,
respectively. Treatment with fresh whole blood and chelating agents
cleared the symptoms within 24 hrs, but serum levels of copper and
ceruloplasmin remained moderately elevated for 6 months after treatment.
Although relatively uncommon, dermal contact with copper can provoke
allergic skin reactions in some individuals. Contact dermatitis has been
reported following contact with copper-containing jewelry (Saltzer and
Wilson, 1968), dental cement (Martindale, 1977), and copper wire (Forstrom
et al., 1977).
Eczematbus-type dermatitis has also been reported from uterine
contact with copper intrauterine devices (Barkoff, 1976; Dry et al.,
1978). Barkoff (1976) reported that a 24-year-old woman developed
severe acute urticaria, joint pain and marked angioedema secondary to a
copper intrauterine contraceptive device inserted 1 month previously.
Allergy to copper was proven by scratch tests with 17, copper sulfate
solution. The condition cleared subsequent to removal of the device.
122
-------
d. Copper Intrauterine Devices (lUD's)
In that the experience with copper-concaining lUD's is of relatively
limited duration (10 years), definitive assertions cannot be made con-
cerning long-term effects. However, at present there is no evidence to
indicate that copper lUD's adversely affect future fertility, or that
they increase carcinogenic or teratogenic risks in humans. The local,
systemic and contraceptive effects of copper lUD's have been widely
studied and are extensively reviewed by Hasson (1973), and Oster and
Salgo (1975, 1977).
Hagenfeldt (1972) reported that the average loss of copper from a
copper IUD (200 mm2) was 50 Ug/day and further, that only the endometrial
copper levels were elevated and that these returned to normal within the
first cycle following removal of the device. Other investigators have
noted no elevation of serum copper levels in users of copper lUD's
(Anteby e_£ al., 1978; Elstein and Daunter, 1973).
Menstrual blood collected from women using copper ITJD's contains
about one-half of the total copper lost from the device during 1 month
(Oster and Salgo, 1975). Thus, approximately 750 Ug of copper per month
are retained and presumably absorbed into the circulation. Although this
is only a small fraction of ingested.dietary copper, possibly retention
over the years or decades a woman is likely to use intrauterine devices
could produce some adverse effects in susceptible individuals.
To date, only a few births have occurred in women who retained a
copper IUD throughout pregnancy; the infants appear normal (Tatum, et
al., 1976; Hasson, 1978). However, involuntary pregnancies with a copper
IUD in utero have a greater chance of ending in spontaneous abortion.
Tatum e_t al. (1976) noted the incidence of spontaneous abortion more
than doubled (54%) in 157 women who elected to retain IUD in situ when
compared with 118 women who either expelled or had the device removed
(23%). Tatum's data also suggested an increased risk of having an
ectopic pregnancy in women who had worn a copper-T device for more than
2 years. Only one anomaly (berri'gn fibroma of the vocal cords) was found
in 166 infants born of women who conceived while using a copper-IUD and
who continued the pregnancy with the device in situ (Tatum e_t. al., 1976).
A summary of the outcome of pregnancies with copper lUD's followed
to termination is presented in Table 23.
5. Overview
Copper is an essential nutrient for man and animals and plays a
vital role in numerous biochemical and physiological functions. Since
most human diets contain an over-abundant supply of copper, human
copper deficiency is axcramely rara.
123
-------
TABLE 23. OUTCOME OF PREGNANCIES WITH COPPER lUD's FOLLOWED TO TERMINATION
Induced
No. Abortions
Non-Induced Abortions (%)
Soontaneous Ectooic Stillbirth
Live-
Births Source
57 32 (56%) 44
374 198 (53%) 30
773 465 (60%) 37
0
5
56 ' • Snowden, 1975
65 Stewart ejc al.
1975
53 Tatum e_t al.
1976
SOURCE: Adapted from Hasson (1978)
-------
In man, approximately 30% of ingested copper is absorbed, but
because copper is excreted into bile, which is not reabsorbed, effective
net absorption is about 5%. Roughly 95% of ingested copper is eliminated
in the feces (70% ingested but unabsorbed; 25% biliary excretions of
absorbed copper), with small amounts excreted in urine and sweat.
There is no experimental evidence to suggest that copper is a
carcinogen and it may in fact, inhibit some types of chemically induced
tumors in laboratory animals. Some indications of mutagenicicy have
been reported for copper but generally at toxic concentrations. Further
work is needed to clarify this issue.
Copper, when implanted into the uterus, exerts a contraceptive
effect in both humans and experimental animals. The release of copper
is localized, although some degree of systemic absorption of copper
occurs. There is no evidence to suggest that intrauterine copper is
either teratogenic or impairs future fertility in humans. A single
study noted increased embryonic resortions and developmental malforma-
tions in surviving offspring of hamsters injected intravenously with
copper salts on day 8 of gestation.
lexicological studies with nonruminant animals indicate little
toxicity except at dietary levels far in excess of normal intake.
Depending on the salt, acute oral LDsg values for most species range
from 140 mg/kg to 300 mg/kg. Copper toxicosis in humans in also unusual
and is generally linked to suicidal ingestion of large quantities of
copper or to individuals with genetic defects in copper metabolism.
B. HUMAN EXPOSURE
1. Introduction
The previous section on the effect of copper on humans indicates
that it has a very low order of toxicity. In fact, most discussions
regarding human exposure to copper emphasize deficiency, as opposed to
effects resulting from large doses. As a result, this section will not
go into great detail in estimating copper exposure to various subpopu-
lations. It will attempt to provide order to magnitude estimates for
exposure to copper through various routes.
2. Ingestion
a. Food
NRC (1977) has reviewed the copper content of various foods exten-
sively, as this subject has been looked into in some detail. Foods
particularly high in copper include oysters, organ meats, and dried
legumes. Holden e_c al. (1979) recently surveyed the copper intakes of
12 subjects. They analyzed composites- of self-3elected diets, including
beverages and drinking water over a 14-day period. The overall mean
125
-------
daily intake was 1.0+0.1 mg, well below che suggested U.S. Recommended
Daily Allowance (RDA). of 2 mg. The highest daily intake reported was
2.41 mg, although none of the diets contained oysters or organ meats.
These results are shown in Table 24, along with other data reported on
copper intakes. It is apparent from these data that consumption is
generally less than 2 mg/day, although persons consuming diets with
liver consumed 7.6 mg copper/day.
The addition of 15 mg/kg copper to livestock feed is allowed by
FDA and is a common practice. However, the feedstock may already con-
tain adequate levels of copper. This practice may result in the accumu-
lation of copper in animal livers, especially sheep, swine and poultry
(NRC, 1977). These authors also point out that baby food made from
liver containing 550 ppm copper (wet weight) would result in an exposure
of 15 mg per 1-oz serving. The prevalence of this exposure is'unknown.
b. Drinking Water
Levels of copper in drinking water depend on levels in water supply,
treatment efficiency, and the use of copper in the distribution system.
Concentrations vary geographically, as well as by water type (hard vs.
soft), water temperature, and length of time standing in pipes. In
general, higher concentrations are found in areas with soft water
(Schroeder e_t al. , 1966). The U.S. DHEW (1970) reported that the maximum
concentration reported in 2595 distribution samples was 8.35 mg/L copper.
However, only 1.6Z of the samples exceeded the recommended drinking water
standard of 1 mg/L and the mean concentration was 0.134 mg/L.
The study conducted by Holden et_ al. (1979) included drinking water
in the calculated intake, although drinking water concentrations may have
been low in the area of the test. It is unknown whether the other surveys
shown in Table 24 included drinking water; however, they probably did not
Therefore, a mayinnnn exposure of 24 mg copper/day could occur, resulting
from consumption of a diet high in copper-rich foods and from drinking
water very high in copper. Such an exposure would appear to be limited
to a very small subpopulation. A more general ingestion exposure would
be in the range of 1-4 mg/day.
3. Inhalation
EPA (19-79) has reviewed the potential for copper exposure through
inhalation. A survey of ambient air concentration in rural and urban
communities showed concentrations of 0.01 ug/m3 and 0.257 ug/m3, respec-
tively (National Air Pollution Control Administration 1968 as cited in
EPA, 1979). Concentrations in areas where high concentrations would be
expected such as near smelters, are 1-2 ug/m3 (EPA, 1979). Thus, a
maximum inhalation exposure would be .04 mg/day, considerably lower than
ingestion exposure.
125
-------
TABLE 24. DIETARY INTAKES OF COPPER REPORTED IN THE LITERATURE
Intake
(tng/day) Type of Diet
0.34 self-selected
(24-hr)-
0.91 self-selected
1.0 self-selected
1.04 self-selected
1.2 Non-institutional
diets
1.5 diets (no liver)
1.8-2.1 balance study
1.9 institutional
diet
2.4 self-selected
3.8 diet composites
7.6 diets (with liver)
Number of
Subjects
Reference
4 female White (1969)
1 female Tipton et_ al. (1966)
11 male, Holden ec al. (1979)
11 female
36 female Tipton et_ al. (1966)
12 female Guthrie and
Robinson (1977)
12 female Guthrie and
Robinson (1977)
11 female Robinson et_ al. (1973)
12 female Guthrie and
Robinson (1977)
12 female Guthrie (1973)
1 male Zook and Lehman (1965)
11 female Guthrie and
Robinson (1977)
SOURCE: Holden et al. (1979)
127
-------
4. Medical Exposure
Exposures to copper have been reported for persons applying copper
sulfate to large areas of burned skin. Such incidents vere described
in the preceding section and appear to be rare.
Persons receiving dialysis have also been exposed to copper,
primarily due to high levels in source water or equipment problems.
While these incidents appear to be rare, an exposure of 5 mg over a 7-hr
dialysis-day has been reported (Blomfield ££ &1., 1969). Using a maximum
tap-water level of 1 mg/L, these authors calculated potential exposure
of 240 mg, using a 240-L volume for dialysis. However, this exposure
assumes a total uptake of copper by the blood, which is probably unlikely.
' Most of the equipment problems with dialysis were reported 10 or so years
ago, and a literature search did not uncover any more recent problems.
Therefore, it is not clear whether these problems have been assumed to
be insignificant or more likely, equipment has been improved to reduce exposure
A more common exposure route is through the use of copper lUD's.
It has been shown that a 200-mm2 copper device releases 50 yg copper/day
as cupric ions in free or complexed form (Hagenfeldt, 1972). As discussed
in the previous section, about one-half of the released copper is lost in
menstrual blood. The resultant exposure of approximately .025 mg/day
cannot be directly compared with ingestion exposure since presumably
this release is available for absorption.while only about 5% of ingested
copper is absorbed. However, increased serum copper levels due to the
use of copper ITJD's have not been reported.
5. Conclusions-
Food is the primary source of copper for most people; however, con-
tributions from drinking water may be important in a few locations. In
general, exposure would be in the range of 1-4 mg/day. Persons eating
diets comprised of copper-rich foods and/or living in areas with high
drinking water levels would receive higher copper exposures up to 24
mg/day. In addition, dialysis patients, as well as copper IUD users,
may receive slightly higher exposure to copper.
-------
REFERENCES
Adelatein, S.J. and B.L. Vallee. 1961. Copper metabolism in man. New
Engl. J. Med. 265:892-97.
al-Rashid, R.A. and J. Spangler. 1971. Neonatal copper deficiency.
N. Engl. J. Med. 285:841-43.
Anteby, S.O., H.A. Ben Bassat, S. Yarkoui, Y. Aboulafia and E. Sadousky.
1978. The effect of intrauterine devices containing zinc and copper on
their levels in serum. Fertil. Steril. 29(1):30-34.
Barkoff, J.R. 1976. Urticaria secondary to-a copper intrauterine
device. Int. J. Dermatol. 15(8);594-95.
Bloomfield, J., J. McPherson, and C.R.P. George. 1969. Active uptake
of copper and zinc during haemodialysis. B. Med. J. ,1(650):141-145.
Boyden, R., V.R. Potter and C.A. Elvehjem. 1938. Effect of feeding
high levels of copper to albino rats. J. Nutr. 15:397-402.
Bremner, I. 1974. Heavy metal toxicities. Quart. Rev. Biophys.
2(1):75-124.
Brinster, R.L. and P.C. Cross. 1972. Effect of copper on the
preimplantation mouse embryo. Nature 238:389-99.
Burki, H.R. and G.T. Okita. 1969. Effect of oral copper sulfate on
7,12-dimethylbenz anthracene carcinogenesis in mice. 3r. J. Cancer
^3(3):591-96.
Campbell, J.K. and C.F. Mills. 1974. Effects of dietary cadmium and
zinc on rats maintained on diets low in copper. Proc. Nutr. Soc.
33(1):15A-16A.
Carlton, W.W. and P.S. Price. 1973. Dietary copper and the induction
of neoplasms in the rat by acetylamlnofluorene and dimethylnitrosamine.
Food Cosmet. Toxicol. 11(5):827-40.
Cartwright,'G.E. and M.M. Wintrobe. 1964. Copper metabolism in normal
subjects. Am. J. Clinical Nutr. 1.4:224-32 as cited in Vuori et al.,
1978.
Casto, B.C., J. Meyers and J.A. DiPaolo. 1979. Enhancement of viral
transformation for evaluation of the carcinogenic or mucagenic potential
of inorganic metal salts. Cancer Research 39: 193-198.
Caudros, A. and J.G. Hirsch. 1972. Copper on intrautarine devices
stimulates leukocyte exudation. Science 175:175-76.
Cerkiewski, F.L. and 3..M. Forbes. 1977. Influence of dietary copper
on lead coxiciiry in che young aale rac. J. Mutr. 107(1):143-^6.
129
-------
Chang, C.C. and H.J. Tacum. 1970. A study of the antifertility effect of
intrauterine copper. Contraception JL:265 as cited in Hasson, 1978.
Chang, C.C. and H.J. Tatum. 1973. Absence of teratogenicity of intrauterine
copper wire in rats, hamsters and rabbits. Contraception 2/413 as cited in
Hasson, 1978.
Chang , C.C. and H.J. Tatum. 1975. Effect of intrauterine copper wire on
resorption of fetuses in rats. Contraception 11(1);79-84.
Chez, R.A., R.I. Henkin, and R. Fox. 1978. Amniotic fluid copper and zinc
concentrations in human pregnancy. Obstet. Gynecol. 52(1);125-27.
Chugh, K.S., B.K. Sharma, P.C. Singhal, K.C. Das, B.N. Datta. 1977. Acute
renal failure following copper sulfate intoxication. Postgrad. Med. J.
53(615):18-23.
Demerec, M., G. Bertani, J. Flint. 1951. A survey of chemicals for muta-
genic action on E_. coli. Am. Nat. 85; 119-36.
Dry, J., F. Leynadier,-A. Bennani, P. Piquet and J. Salat. 1978. Intra-
uterine copper contraceptive devices and allergy to copper and nickel
(letter). Ann. Allergy 41_(3): 194.
Dunlap, W.M., G.W. James III and D.M. Hume. 1974. Anemia and neutropenia
caused by copper deficiency. Ann. Intern. Med. J30_:470-76 as cited in Graham
and Cordano, 1976.
Elstein, M. and 3. Daunter. 1973. Copper absorption from I.U.C.D.s Brit.
Med. J. 2.: 776.
Ferrn, V.H. 1976. Teratogenic effects and placental permeability of heavy
metals. Curr. Top. Pathol. 62;145-51.
Ferm, V.H. and D.P. Hanlon. 1974. Toxicity of copper salts in hamster
embryonic development. Biol. Reprod. 11(1);97-101.
Fisher, G.L., V.S. Byers, M. Shifrine and A.S. Levin. 1976. Copper and
zinc levels in serum from human patients with sarcomas. Cancer 37(1);356-63.
Forstrom, L., R. Kiistala, K. Tarvainen. 1977. Hypersensitivicy to copper
verified by test with 0.1% CuSO, . Contact Dermatitis 3_(5) :280-ai.
Frommer, D.J. 1977. Biliary copper excretion in nan and the rat. Digestion
15(5):390-96.
130
-------
Goodman, L.S. and A. Gilman. 1975. The Pharmacological Basis of
Therapeutics. Fourth Edition. The MacMillan Company, Collier-MacMillan
Canada Limited, Toronto, pp. 1409-10.
Graham, G. and A. Cordano. 1976. Copper deficiency in human subjects.
Chap. 22 in: Trace Elements in Human Health and Disease, Vol. 1, Zinc
and Copper. A.S. Prasad, ed. Academic Press, New York, pp. 363-372.
Guthrie, B. and M.F. Robinson. 1977. Daily intake of manganese, copper,
zinc, and cadmium by New Zealand women. Br. J. Nutr. ^3(3:55 as cited in
Holden et al. (1979).
Guthrie, B.E. 1973. Daily dietary intake of zinc, copper, manganese,
chromium, and cadmium by some New Zealand women. Proc. Univ. Otago
Med. School. ,5_1:47 as cited in Holden et. al. (1979).
Hagenfeldt, K. 1972. Intrauterine contraception with the copper-T
device. I. Effect on trace elements in the endometrium, cervical mucus
and plasma. Contraception ji:37-54.
Hasson, H.M. 1978. Copper lUDs. J. Reprod. Med. 20(3):139-54
Holden, J.M., W.R. Wolf, and W. Mertz. 1979. Zinc and copper in
self-selected diets. J. Am. Diet. Assoc. 75:23-28.
Holtzman, N.A., D.A. Elliot, R.H. Heller. 1966. Copper intoxication
Report of a case with observations on ceruloplasmin. N. Engl. J-. Med.
275:347-52.
Iwanska, S. and D. Strusinska. 1978. Copper metabolism in different
states of erythropoiesis activity. Acta. Physiol. Pol. 29(5);465-74.
Johnson, N.C., T. Kheim, and W.B. Kountze. 1959. Influence of sex
hormones on total serum copper. Proc. Soc. Exper. Biol. and Med. 102:
98 as cited in Adelstein and Vallee (1971).
Kamamoto, Y., S. Makiura, S. Sugihara, Y. Hiasa, M. Aral, and K. Ito.
1973. The inhibitory effect of copper on DL-ethionine carcinogenesis
in rats. Cancer Res. 33:1129-35.
Karpel, J.T. and V.H. Peden. 1972. Copper deficiency in long-term
parenteral nutrition. J. Pediat. J30:32-36 as cited in Graham and
Cordano, 1976.
Klevay, L.M. 1973. Hypercholesterolemia in rats produced by an increase
in the ratio of zinc to copper ingested. Am. J. Clin. Nutr. 26:1060-68.
Xuracsune, M., S. Tukodome, T. Shirakusa, M. Yoshida, Y. Tokumicsu,
T. Hayano, and M. Seira. 1974. Occupational lung cancer among copper
smelcars. Inc. 'J. Cancer 13(4):552-58.
131
-------
Lai, S. and T.L. Sourkes. 1971. Deposition of copper in rat tissues - The
effect of dose and duration of administration of copper sulfate. Toxicol.
Appl. Pharmacol. 20;269-83.
Law, L.W. 1938. The effects of chemicals on the lethal mutation rate in
Drosoohila melanogaster. Proc. Nat. Acad. Sci. 24;546-50.
Lee, G.R., D.M. Williams, G.E. Cartwright. 1976. Role of copper in iron
metabolism and heme synthesis. Chap. 23 in: Trace Elements in'Human Health
and Disease. Vol. 1, Zinc and Copper, A.S. Prasad, ed.Academic Press, New
York, pp 373-90.
Linder, M.C. 1977. Iron and copper metabolism in cancer, as exemplified
by changes in ferritin and ceruloplasmin in rats with transplantafale tumors.
Adv. Exp. Med. Biol. 9:2:643-64.
Loeb, L.A., M.A. Sirover, L.A. Weymouth, O.K. Dube, G. Seal, S.S. Agarwal
and E.Katz. 1977. Infidelity of DNA synthesis as related to mutagenesis
and carcinogenesis. J. Toxicol. Environ. Health 2_: 1297-1304.
Luthra, M.K., A.B. Mitra, G. Bhinder, P. Bhatnagar and N.C. Saxena. 1975.
Surveillance for carcinogenesis in women using copper intra-uterine device
for contraception. Indian J. Med. Res. _63_(12): 1787-93.
Luthra, U.K., A. B. Mitra, A.K. Prabhaker, P. Bhatnagar and S.S. Agarwal.
1978. Role of copper IUD in cervical carcinogenes'is: A follow-up of 36
months. Indian J. Med. Res. 68_: 78-83.
Magos, L. 1976. "The role of synergism and antagonism in the toxicology
of metals". Chapter Cl, pp 491-97 in: Effects and Dose-Response Relation-
ships of Toxic Metals. G.F. Nordberg, ed. Elsevier Scientific Publishing Co.,
Amsterdam.
Magrisukovskaya, K.V. 1936. Bull. Biol. Med. Exp., I. as cited in Law, 1938,
Martindale; The Extra Pharmacopoeia. 1977. Twenty-seventh edition. A.
Ware, ed., The Pharmaceutical Press, London, pp 893-95.
Meyer, B.J., A'.C. Meyer and M.K. Horwitt. 1959. Effect of tri-iode
thyronine on serum copper and basal metabolism in schizophrenic patients.
Arch. Gen. Psychiat. l_:374-78 as cited in Adelstein and Vallee, 1961.
Mitta, S.K. and C. Tan. 1979. Serum copper levels (SCL) in children with
Hodgkin's disease (HD). (Meeting abstract) Proc. Am. Assoc. Cancer Res.
2£:382.
Nacional Air Pollution Control Administration. 1963. Air quality daca from
che National Air Surveillance Necvorks and contribution of Scata and Local
networks. 1966 ed. NAPLA ?ubl., APTD-58-9. As cicad in EPA (1979).
132
-------
Newman, J.A., V.E. Archer, G. Saccomanno, M. Kuschner, 0. Auerbach,
R.D. Grondahl and J.C. Wilson. 1976, Histologic cypes of bronchogenic car-
cinoma among members of copper-mining and smelting communities. Ann. N.Y,
Acad. Sci. 271:260-68.
Nishioka, H. 1975. Mucagenic activities of metal compounds in bacteria.
Mutat. Res. 31: 185-89.
(National Research Council). 1977. Copper. PB 279307, 115 pp.
National Academy of Sciences, Washington, D.C.
O'Dell, 3.L., B.C. Hardwick, and G. Reynolds. 1961. Mineral deficiencies
of milk and congenital malformations in the rat. J. Nutr. 73;151-57.
O'Dell, B. 1976. "Biochemistry and Physiology of copper in vertebrates".
Chap. 24 in: Trace. Elements in Human Health and Disease, Vol. 1, Zinc and
Copper, A.S. Prasad, ed. Academic Press,- New York, 1976.
Oster, G. and M. Salgo. 1975. The copper intrauterine device and its
mode of action. N. Engl. J. Med. 293:432-38.
Oster, G. and M.P. Salgo. 1977. Copper in mammalian reproduction. Adv.
Pharmacol,, Chemother. 14:327-409.
Parizek, J. 1976. "Interrelationships among trace elements". Chapter C2,
pp 498-510 in: "Effects and Dose-Response Relationships of Toxic Metals.
G.F. Nordberg, ed. , Elsevier Scientific Publishing Co., Amsterdam.
Petering, H.G., H. H. Buskirk and J.A. Grim. 1967. The effect of dietary
mineral supplement on the rat on the antitumor activity of 3-ethoxy-2-
oxybutyraldehyde bis(thiosemicarbazone) . Cancer Res. 27:1115-21.
Pimental, J«C. and A. P. Menezes. 1977. Liver disease in vineyard sprayers.
Gastroenterology 72(2) ; 275-83.
Robinson, M.F., J.M. McKenzie,. C.D. Thomson, A.L. vanRi j . 1973. Metabolic
balance of zinc, copper, cadmium, iron, molybdenum, and selenium in young
New Zealand women. Br. J. Nutr. _30:195 as cited in Holden ££ al . (1979).
RTECS (Registry of Toxic Effects of Chemical Substances). 1977. Vol. II.
E.J. Fairchild, R.J. Lewis, Sr., and R.L. Tatkon, eds. U.S. DHEW, NIOSH
78-104-B.
Saltier, E.I. and J.W. Wilson, 1968. Archs. Derm. 9^:375 as cited in:
Martindale, 1977.
Sandstead, H«H, 1976. "Interactions of cadmium and lead with essential
minerals". Chap. C3, pp 511-26 in: Effects and Dose-Response Relationships
of Toxic Metals. G.F. Nordberg, ed., Elsevier Scientific Publishing Co.,
Amsterdam.
Saatoliquido, P.M.,. S.W. Southwickand J.K. Olwin. 1976. Trace mecal levels
in cancar of the 'breast. Surg, Gynecoi. Obstec, 142(1) : 65-70.
Scheinbers, H. and I. Sternlieb. i960. Copper secaboiisn. Pharmacol.
Rev, 12_:355-31.
133
-------
Schroeder, H.A., A.P. Nason, I.H. Tipton, and J.J. Salassa. 1966.
Essential trace metals in man: copper. J. Chron. Dis. 19;1007-1034
Schwartz, U.K. 1975. Role of trace elements in cancer. Cancer Res.
34:3481-87.
Seto, A., H. Tokuda, ?. Ito. 1978. Malignant conversion of Shope
papillotnas and associated changes of serum ceruloplasmin in domestic
rabbits. Proc. Soc. Exp. Biol. Med. 157(4);694-96.
Shifrine, M. and G.L. Fisher. 1976. Ceruloplasmin levels in sera from
human patients with osteosarcoma. Cancer 38(1);44-48.
Snowden, R. 1975. Pelvic inflammation, perforation and pregnancy
outcome associated with the use of lUDs. In: Analysis of Intrauterine
Contraception, pp. 139-46. North Holland Publishing Co., as cited in
Hasson, 1978.
Spector, W.S. 1956. Handbook of Biological Data: Prepared under the
direction of the Committee on the Handbook of Biological Data - Division
of Biology and Agriculture, the National Academy of Sciences, the National
Research Council. Philadelphia, Saunders, 408 pp. as cited in Adelstein
and Vallee, 1961.
Stein, R.S., D. Jenkins and M. Korrs. 1976. Death after use of cupric
sulfate as emetic. JAMA Z35_:801 (letter.)
Stewart, W.C., F.B. O'Brien, C. Nisson et al. 1975. Multiclinic
evaluation of Gravigard (Cu7) intrauterine contraception. In: Analysis
of Intrauterine Contraception, pp 149-53, North Holland Publishing
Co., as cited in Hasson, 1978.
Task Group on Metal Interaction, Scientific Committee on the Toxicology
of Metals. 1978. Factors influencing metabolism and toxicity of metals:
A consensus report. International Association on Occupational Health.
Environ. Health Perspect. 25:3-41.
Tatum, H.J., F.H. Schmidt and A.K. Jain. 1976. Management and outcome
of pregnancies associated with the copper-T intrauterine contraception
device. Am. J. Obstet. Gynecol. 126:869-74.
Tipton, I.H., P.L. Stewart, and P.G. Martin. 1966. Trace elements
in diets and excreta. Health Phys. _12_:1683 as cited in Holden et al.
(1979).
Tokudome, S. and H. Kuratsune. 1976. A cohort study on mortality
from cancer and other causes among workers at a metal refinery. Int.
J. Cancer r?(3):310-17.
Ulaer, D.C. 1977. Trace Zlanencs. N. Zngl. J. Med. 297(6)318-11.
-------
U.S. Department of Health Education and Welfare (U.S. DHEW). 1970.
Community Water Supply Study. Public Health Service, Environmental
Health Service, Bureau of Water Hygiene.
U.S. EPA. 1979. Ambient water quality criteria: Copper. Criteria
and Standards Div., Office of Water Planning and Standards.
Van Campen, D.R. and P.U. Scaife. 1967. Zinc interference with copper
absorption in rats. J. Nutr. 91:473-76.
Venugopal, 3. and T.D. Luckey. 1978. Metal Toxicity in Mammals. 2.
Chemical toxicity of metals and metalloids. Plenum Press, New York,
pp 24-32.
Vogel, F.S. 1960. Nephrotoxic properties.of copper under experimental
conditions in mice, with special reference to the pathogenesis of the
renal alterations in Wilson's disease. Amer. J. Pathol. 36:699-711.
Vuori, E., A. Huernan-Seppala, and J.O. Kilpio. 1978. Biologically
active metals in human tissues. I. The effect of age and sex on the
concentration of copper in aorta, heart, kidney, liver, lung, pancreas
and skeletal muscle. Scand. J. Work Environ. Health £(2):167-7S.
Walsh, P.M., F.J. Brosson, M. Bayley, J. McReynolds and B.J. Pearson.
1977. Acute copper intoxication. Pathophysiology and therapy with a.
case report. Am. J. Dis. Child. 131(2):149-51
White, H.S. 1969. Inorganic elements in weighed diets of girls and
young women. J. Am. Dietet A. ^4:38 as cited in Holden .ejt al. (1979).
Yamane, Y. and K. Sakai. 1973. Suppressive effect of concurrent
administration of metal salts on carcinogenesis by 3'-methyl-4-
(dimethylamine)azobenzene, and the effects of these metals on aminoazo
dye metabolism during carcinogenesis. Gahn 64(6):563-73.
Yamane, Y., K. Sakai, and S. Kojima. 1976. Mechanism of the suppressive
effect of basic cupric acetate on rat liver carcinogenesis caused by
ethionine. Gann 67:295-302
Yamane, Y., K. Sakai, M. Shibata and K. Chiba. 1977. Suppressive effect
of copper on ethylation of rat liver DNA with ethionine in vivo. Gann
68(5):713.
Youkilis, G.J., R.G. McConnell, R.D. Hemm and J.M. Andress. 1973.
Toxicity studies of a copper-containing intrauterine device in several
laboratory animal species. Toxicol. Appl. Pharmacol. 25(3);463-64.
Zook, E. and J. Lehman. 1965. Total diet study: Content of ten
minerals—aluminum, calcium, phosphorus, sodium, pocassium, boron,
copper, iron, aanganesa, and aagnesium. J. Assoc. Off. Agric. Chea.
_i3:350 as cicad in Holden ji£ a_l. (1979).
135
-------
VII. RISK CONSIDERATIONS
A. BIOTA
The risk of copper exposure for aquatic biota varies widely from
location Co location. The potential for exposure to acutely toxic con-
centrations may occur when very high concentrations of copper are re-
leased into a water body, such as when chemical wastes are spilled or
discharged. In such cases,'the effects on aquatic life may be localized
with the degree of impact dependent upon the nature of the receiving
water body (dilution volume, availability of complexing agents, etc.).
For large regions of the country, chronic exposure can be anticipated
in areas in which certain conditions (or combinations of conditions).
prevail, i.e., acidic or soft water, high copper levels, and sensitive
species. Table 25 lists the major river basins in which the potential
risk of adverse effects is greater because of high copper levels or soft
water. It is likely, however, that risk is limited to a member of very
localized areas within these larger basins.
Based oh laboratory studies, species of aquatic biota appear to
vary considerably in their sensitivity to harmful effects of copper.
As a group, the salmonids are probably the species mot sensitive to
aqueous copper, exhibiting toxicosis when exposed to copper concentra-
tions of 10 ug/L in soft water. However, some warmwater fish such as
the fathead minnow are also susceptible to relatively low concentrations
of copper (23 ug/L in very soft water). Based on STORET monitoring data,
they are exposed to total copper levels at least this high in many parts
of the regions in which they are found. Aquatic vertebrates tend to be
most sensitive to copper in the embryo and larval stages, and most re-
sistant as eggs and adults. The daphnids appear to be particularly'
sensitive to copper. Certain species of Chlorella algae are the most
sensitive of the plant species tested.
The data presented previously in Sections IV and V concerning the
effects of and exposure to copper suggest that there is a widespread
potential in the U.S. for exposure to harmful levels of copper. However,
conclusions cannot be reached about the risks of copper exposure on the
basis of monitoring data and laboratory toxicity studies alone.. Although
the environmental fate of copper has been discussed previously (in Section
IV), it is important to review certain aspects of environmental pathways
and chemical characteristics of copper in order to understand the im-
plications of these factors for risk to biota.
Toxicity studies have made it apparent that some species of copper
are responsible for the observed effects and others are not. Toxicity
to some algae and invertebrates has been shown to be a function of
cupric ion activity (Jackson and Morgan, 1978; Anderson and Morel, 1978;
Andrew jat. al. , 1977; and Van den 3er» e_c al. , 1979). Shaw and Srown (197^)
related the toxicity of copper Co Cu-" and CuC03° for rainbow urouc.
137
-------
TABLE 25. RIVER BASINS WITH FACTORS CONTRIBUTING TO RISK FOR AQUATIC ORGANISMS
River Basins with Soft Water
New England
Northern California
Pacific Northwest
Southeast (except Florida)
River Basins with High Aqueous Copper Concentrations*
Lower Colorado 36%
New England 23%
Western Gulf 18%
Southeast 17%
Upper Mississippi 17%
Rio Grande and Pecos 14%
River Basins with High Copper, Concentrations in Sediment**
Hawaii 67%
Souris and Red of North 35%
Lower Colorado 20%
Great Lakes 19%
Upper Mississippi 19%
New England 16%
Mid Atlantic 15%
* Percentage of samples exceeding 100 ug/L coca! copper
** Percentage of samples exceeding 100 tag/kg cocal coppe:
Source: 5TOR2T (1970-1979)
123
-------
Brown e£ al. (1974) reported that the toxic effects of copper could be
mitigated through the addition of various types of organic materials.
Howarth and Sprague (1978), as well as Chakoumakos et al. (1979), con-
cluded that the copper ion, as well as the hydroxy complexes, are toxic
to cutthroat trout and rainbow trout. Thus, it is clear that some forms
of copper are not toxic to aquatic organisms. However, it has not been
determined which additional species are toxic besides the cupric ion.
In addition, it has generally been assumed that suspended copper is not
available or toxic, since it would be either strongly adsorbed or
complexed. (Shaw and Brown, 1974; Brungs et al. 1976).
The monitoring data reported here are for total copper. The levels
measured may bear little relation to the results of laboratory toxicity
studies for a number of reasons. First, only a portion of total copper
is present in the dissolved form. Stiff (1971) found that 12-57% of-
the copper in various British rivers was in the dissolved phase, although
Perhac (1974) reported 92.3% of the total copper in the dissolved phase
in three streams in Tennessee. The particulate forms would include per-
haps the oxide, sulfide, 'and malchite precipitates, in addition to insol-
uble organic complexes and copper adsorbed onto clays and other solids.
Table 26 shows the distribution of copper measurements from STORET for
dissolved and total copper in the United States. Though the data are
not definitive since they cover all observations for copper in the U.S.
over a period of years, and were not necessarily measured concurrently,
they indicate that dissolved levels tend to be consistently lower than
total levels for copper and suggest that the streams examined by Perhac
may be exceptional rather than the norm.
Second, the dissolved portion of the copper may be complexed to vari-
ous degrees. The equilibria affecting copper in natural waters have been
examined by numerous authors (Stiff, 1971; Sylva, 1976; Andrew et al..
1977; Anderson and Morel, 1978; Jackson and Morgan, 1978). Various re-
sults have been calculated and measured for different conditions and
equilibrium constants, but all models reveal the same general trend.
Figure 18 shows calculated copper speciation in a relatively hard fresh
water. As shown, in the absence of an organic chelator, the free cupric
ion is predominant at low pH; however, its importance drops off rapidly
above pH 6.3 and the monocarbonate or the dihydroxide complex become
predominant. In the presence of excess NTA, the cupric ion is never sig-
nificant and organic complexes predominate below pH 8. At higher pH the
hydroxide complex is predominant (Elder and Home, 1978). Though other
authors predict that carbonate complexes will be more important (Sylva,
1976), free copper is only clearly significant in acid waters with little
potential for organic complexing.
The question remains as to what extent of che copper is complexed by
organic material in natural waters. Gachter a_t_ al. (1978) looked into
129
-------
TABLE 26. DISTRIBUTION OF LEVELS OF DISSOLVED AND TOTAL COPPER FROM STORE!
MONITORING DATA~~~
Observations in concentration range (%)
Form of Coooer 1-10 ug/L 10-100 ug/L 100-1000 ug/L
Dissolved 63 19 4
Total . 41 44 10
Note: this table indicates that most of the measurements of dissolved
copper have been in the range of l-10ug/L. Measurements of total
copper are distributed much more heavily in the range of 10-100ug/L.
Source: STORET (1970-1979)
140
-------
Cu(OH)9
CutCOj)'
CuCO/
678
«•) pH
(\uloioncu: ElUor and Home (1978).
10
b.)
6 9
PH
10
FIGURE 18. CALCULATED COPPER SPECIATION IN A RELATIVELY HARD FRESH WATER
WHERE CONCENTRATIONS OF INORGANIC CARBON = 10 23 M AND
CALCIUM = 10 26 M. (a) IN ABSENCE OF ORGANIC CHELATION AND (b) IN
PRESENCE OF EXCESS NTA (iNTAl |o|a| » [Cu] ,o,a|)
-------
this question in some detail. They found that copper added, to lake
water was 65-70% associated with molecules having a molecular weight of
greater than 1000. At a total dissolved copper concentration of 5x10'%
(1.45 ug/L) , the concentration of free ion is about S.SxlO"11*! (1.6xlO~3
ug/L). Stiff (1971) examined the forms of copper added to various river
waters at a concentration of 800 ug/L. In seven locations, the free
copper represented 0.1-1.3% of the added copper; carbonate represented
5-54% of the total, and amino acid complexes represented 16-73%. Humic
complexes and other unidentified forms of copper were sometimes observed.
In two river waters to which no additional copper had been added the
following distribution was observed:
Concentrations (ug/L)
Amino Acid Inert Humic Hexanol
Cu CuC03 Complex Complex Extractable
River Thames
(Lea Marston) 1.8 34 48 n.d. n.d.
Tributary of 0.5 2 106 n.d. 12
R. Churnet
Source: Stiff (1971)
McCrady and Chapman (1979) also investigated the importance of the
copper ion in several river waters. All of the samples had a pH of
greater than 7.5, low suspended solids, and low total organic carbon.
Hardness ranged from 26 mg/L CaCO-j to 132 mg/L CaC03, with one exception
(326 mg/L CaC03). As expected, the river with the hardest water had the
lowest percentage of copper ion (0.45%) as compared with total copper.
The rest of the rivers showed a ratio of 1-10%.
The chemical speciation of copper in natural waters has implications
for the interpretation of laboratory toxicity data. For some inverte-
brates, effects appear to be due to the cupric ion. The evidence pre-
sented above suggests that the free copper ion in situations where it
has been measured is usually less than 2% of the total dissolved copper.
In addition, dissolved copper aay represent less then 60% of the total
copper reported.
In laboratory studies, water is filtered and the concentration of
dissolved organic sactar is usually low. Thus, the importance of the
cupric ion and other possibly toxic inorganic complexes would be mich
142
-------
greater Chan in many natural waters as is shown in Figure 13 and in the
work done by Ga'chter et. al. (1978). In addition, it has been shown that
some algae secrete copper complexing agents (Swallow ec, al., 1978;
McKnight and Morel, 1979) and thus this capacity would be lost in filter-
ing.
The importance of the copper ion in reconstituted water and well
water that might be used in the laboratory was-examined by McCrady and
Chapman (1979). These authors found that reconstituted soft water con-
tained 9% Cu2"1" and hard water 1.4J Cu2+. The copper ion comprised 36%
of the total copper in well water. This greater importance is due to
the lower pH (7.0) and the softness (25mg/L CaC03) of the well water.
Comparing laboratory data and field data,therefore.requires the
consideration of numerous factors, i.e., pH, hardness, the presence of
suspended solids, and the availability of organic complexing materials.
In a hypothetical example based on the information presented above
(Elder and Home, 1978) a total copper concentration of about 100 mg/L
in relatively hard water in the presence of excess chelating agents
(compared with copper), at a pH of 7, the cupric ion could represent
about 0.2% of the total, and inorganic complexes about 1% of the total
(dissolved copper). In the absence of organic chelation, as occurs in
the laboratory, and at the same pH, the cupric ion represents about 8%,
as does Cu(OH)2°; 01(0)3)° represents about 90%. At a pH of 6, however,
the carbonate complex represents about 10%, while the cupric ion repre-
sents about 90% of the total dissolved copper. Thus, this explains why
hardness is often inversely correlated with the toxic effects of copper
in the laboratory. However, it may be that hardness does not affect
toxicity in the presence of organic complexing material. In addition, in
the presence of organic complexes, copper may be more toxic to some
species at a higher pH due to the formation of hydroxy complexes, which
may themselves be toxic.
Unfortunately the extent of organic copper complexing is not well
documented in the field. It is apparent that without consideration of
the chemistry of copper, estimates of risk to biota are unrealistic.
Table 19 identifies locations in which copper concentrations are high and
water is soft, so that the cupric ion is more predominant. If the loss
of effective copper to particulate forms and soluble complexes is not
considered, copper appears to present a risk to.aquatic organisms in
many locations in the U.S. The extent to which these toxic effects are
mitigated in particular locations identified by complexation and ad-
sorption is unknown and would have to be studied specifically. In the
absence of these more definitive data, however, it can be stated chat
the greatest risk exists in areas with high total copper, soft water,
low concentrations of suspended solids and dissolved organic matter, and
wich a low pH.
Although regions vich high average levels of copper and/or so: t
water have been identified, "he specific sources of copper in chese
areas have not. The materials balance deveiooed in Section III
143
-------
identified suspended sediment, urban runoff, copper sulfate use, and POTW's
as important contributors of copper to the aquatic environment. However,
it is difficult to correlate the sources of copper with high ambient copper
levels without extensive investigations of specific areas. Numerous indus-
trial operations discharge copper, including electroplating plants, copper
wire mills, pulp and paper plants, steam electric power plants, and plants
engaged in brass production, and machinery manufacture. In addition, aban-
doned and active metal mines can be a source of copper to the aquatic en-
vironment. These latter sources are most likely to be important in
localized areas.
In order to examine further the questions of sources of copper re-
leases and the actual risk to aquatic biota, several situations were
examined for which high concentrations of copper have been reported.
The goal of this investigation was to determine the representativeness
of the STORET data; the types of copper sources; and the availability
of fish kill, biological productivity studies, or other studies that
could serve to identify the actual impacts on aquatic biota. The areas
chosen were the upper Sacramento River, the Coeur D'Alene River, the
Gila River, and the Delaware River. The first three locations are areas
with active or abandoned copper mines, while the Delaware River is bordered
by areas that are heavily populated and highly industrialized. The approach
to these investigations and specific results are detailed in the Appendix.
Several conclusions can be drawn from this investigation of four case studies,
First, the degree to which the data found in the local areas were repre-
sentative of STORET data appears to be variable. Data generated through
state, local, or university studies may or may not be entered on STORET.
Less important; but worth noting, is the fact that a significant time
lag frequently appears to exist between data availability and its appear-
ance in STORET.
Second, when examined for individual stations, STORET data did ap-
pear to represent the general conditions believed to exist in each of
the four minor river basins. This reinforces the theory that the high
average copper concentrations reported for some major river basins —
or even minor river basins — are more likely the result of a small num-
ber of very high concentrations, than an indication of typical ambient
conditions.
The results also point to the importance of the dilution volume and
the nature o-f specific receiving waters in determining the risk potential.
For example, in the South Fork of the Coeur D'Alene River, with high
heavy metal concentrations due largely to abandoned mines and oast mining
practices, salmonids are believed to survive spawning runs at periods of
high river flow. However, under normal flow conditions, fish failed to
survive more than a few hours in river-based cage studies. In Arizona,
water is so alkaline that even though strains do not have large dilution
volumes, copper and other heavy aetais in acid :aine drainage uncaring
these straams ara pracicicatad out of solution within shcr- distances of
:he sourca.
-------
The above examples point to"an" additional very important point con-
cerning the representativeness of STORE! data: unless STORE! data are
available for stations in fairly close proximity of each other, it is
difficult to define or describe the significance and extent of risk po-
tential. Several additional conclusions can be drawn with respect to
risk:
• Portions of several minor basins examined contained copper
concentrations that could be considered chronically, if not
acutely, toxic to a number of species. Yet, sensitive fish
species are known to exist in such locations (for example, in
the Sacramento River below Keswick Reservoir; in Coeur D'Alene
Lake). Unfortunately, decades of heavy metal releases and
habitat modification would make it difficult to assess any.
alterations in such populations or aquatic communities attri-
butable solely to copper. However, under seasonally variable
conditions, fish kills continue to occur in some locations.
« Much historical data is represented by "total" copper measure-
ments. Measurements of dissolved copper are becoming more
routine, and studies to address certain aspects of the fate
of discharged heavy metals are being done or considered in
some of the locations examined here.
• The sources in the Gila, the Coeur D'Alene, and the Sacra-
mento River Basins appear to be primarily abandoned mines
and tailings piles, though some active mining is still oc-
curring in some locations. Sources in the Delaware River
Basin have not been identified specifically, but include
metal plating operations, pipe manufacturers, power plants,
steel industries, and POTW's receiving industrial inputs.
The relative magnitude of these sources was not determined.
• In all of the case study examples, copper was not the only
contaminant of concern, or even the most significant one.
Zinc, cadmium and iron are most frequently mentioned as
other contaminants of waters affected by mining wastes and
drainage; a wider range of organic and inorganic contaminants
is present in the Delaware River.
la summary, the case studies verified the importance of understand-
ing the nature and flow volumes of waters being examined, as well as the
nature of sources, in understanding the potential significance
and extent of risk due to a contaminant. In the case of copper, there
seems to be little likelihood that effects can be traced to this con-
taminant alone. The case studies reinforced the validity of the labora-
tory findings concerning the role of pH and hardness in modifying copper
toxicity. The significance of organic chelation, and specifics of copper
fata such as the significance of sediment adsorption or rasolubiiization
-------
potential, were not established in this effort. It is believed that
little empirical data are available on these subjects at this time.
In addition to the risks associated with areas such as those
described above, it is evident that fish exposed to copper sulfate used
as an algicide are at risk. It is likely, however, that this risk is
limited to situations in which the algicide is misused or to very
specific environmental conditions (e.g., low pH, soft waters, etc.).
B. HUMANS
Except in massive acute doses, copper is virtually nontoxic to man.
This results from the following factors, which have been described in
the preceding section:
(1) emetic effects limit oral toxicity;
(2) only about 5% of oral dose is absorbed;
(3) humans generally possess good homeostatic mechanisms; and
(4) absorption through the skin is minimal.
Table 27 summarizes levels producing adverse effects in mammals.
There is no experimental evidence that copper is tumorigenic, although
some indications of mutagenic effects have been reported. Teratogenic
effects have primarily been investigated for the purposes of evaluating
exposures to copper IIJD's. Hamsters have exhibited teratogenic effects
and fetal resorption following exposure to high concentrations of copper.
However, no evidence exists to suggest that teratogenic effects are
associated with the use of lUD's over 10 years of experience with the
product.
Table 28 summarizes estimated copper exposure levels for humans.
It is apparent that these exposure levels are well below effects level
shown in Table 27. Since the effects due to copper appear to be pri-
marily related to acute exposure, these exposures do not appear to
represent a risk, since the lowest reported.oral lethal dose of copper
was 50 mg/kg.
A small subpopulation of humans suffers from a metabolic deficiency
involving passive accumulation of copper and sudden releases. This group
must reduce copper intake drastically and may be treated with chelating
agents to reduce copper availability.
Table 28 also indicates that renal dialysis patients have the po-
tential for exposure to high levels of copper. It should be noted that
this exposure is probably overestimated due to the worst-case assumptions
made. However, this type of exposure aay be of concern since it is in-
travenous. For comparison, only 5*« of ingested copper is absorbed.
146
-------
TABLE 27. ADVERSE EFFECTS OF COPPER ON MAMMALS
Lowest Reoorted Effect Level
Adverse Effect
Teratogenesis
Mutagenesis
Ernes is
Lowest Oral
Lethal Dose
Median Oral
Lethal Dose
Species
Human
Hamster
Hamster
'Hamster
Hamster
Escherichia
coli
Compound
Cu-IUD
CuSO^
Copper
citrate
CuS04
Copper
citrate
CuS04
mg/kg Inciden'ce
Metal %
—
2.131 IV
Day 8
1.8 IV
Day 8
2.131 IV
Day 8
0.251 IV
Day 8
.003 mg/ml2
—
6
17
26
16
—
No Apparent
Effect Level
50 ug/day
for 3 yr
<0.25 mg/kg
Cu metal
.002 mg/ml
Cu metal
coli
Human —
Human CuSO/
10
50
Rat
CuSO,
120
xLowest tested dose.
2Survival at this concentration, however, was less than 5%.
Source: See Section VI
-------
TABLE 28. HUMAN EXPOSURE TO COPPER
Exposure
Route
Ingescion
Food
tug (metal)
/kg (body weight) Population
mg/day^ /day Exposed
IUD
1-4 0.01-0.06
7.6 OJ.1
Drinking
Water ' 0.3 0.004
17
0.2
Inhalation .04 0.0006
Dialysis 5 0.07
240 3.4
0.5 0.0008
large (U.S.)
smaller
large
very small
very small
very small
very small.
large
Comment
based on analysis
of various diets
based on diet
containing liver
based on mean
concentration of
2595 distribution
samples (consump-
tion of 2 L/dayj
based on maximum
concentration of
2595 distribution
samples
based on maximum
concentrations
near smelters
reported exposure
exposure calcu-
lated assuming
tap water concen-
tration of 1 mg/L
and 240-L volume
for dialysis
measured release
rate
70-kg body weight with the exception of IUD exposure, for which a
60-kg body weight is assumed.
Source: See Section VI
148
-------
C. CONCLUSION
This section has described che nature and magnitude of risk of cop-
per exposure for humans and other biota. Aquatic organisms appear poten-
tially to be at risk in numerous locations in the United States, based on
monitoring data, toxicity data, and knowledge of the environmental condi-
tions that affect toxicity. Four areas were examined in more
detail, and the potential 'for risk was confirmed as a result of reported
fish kills, or reduced species diversity. In many of these areas high
copper concentrations appear to be associated wich abandoned mines or
tailings piles. Although releases from active mines have been largely
controlled, the releases from abandoned mines are much more difficult to
control. These releases are of particular concern due to the low pH as-
sociated with acid mine drainage.
However, the case studies showed that risk was not widespread
throughout the minor river basins examined, but limited to very localized
situations. Thus the risk to aquatic organisms is probably much more
limited than the list of minor river basins implies.
In other cases, the potential for risk appears-to be associated
with highly industrialized areas, such as the Delaware River. In such a
situation, specific contributors to risk cannot be identified without
detailed study of the area,since there are many sources such as plating
operations, iron and steel manufacture, pipe manufacture, and POTW's.
In addition, the use of copper sulfate as an algicide can represent
a risk to aquatic organisms, especially if the material is misapplied.
Numerous fish kills have been reported as a result of such incidents.
The information available indicates that copper does not represent
a significant risk to humans. Renal dialysis represents the largest po-
tential exposure. The general population is exposed to copper on the
order of 0.07 mg/kg/day, and the lowest reported oral lethal dose is
50 mg/kg.
149
-------
REFERENCES
Anderson, D.M. and F.M.M. Morel. 1978. Copper sensitivity of Gonyaulax
camarensis. Limnology and Oceanography 23(2):283-295.
Andrew, R.W., K.E. Biesinger, and G.E. Glass. 1977. Effects of inorganic
complexing on the toxicity of copper to Daphnia- magna. Water Research
11:309-315.
Brown, V.M., T.L. Shaw and D.G. Shurben. 1974. Aspects of water quality
and the toxicity of copper to rainbow trout. Water Research ,8(10):797-803.
Brungs, W.A., J.R. Geckler, and M. Cast. 1976. Acute and chronic
toxicity of copper to the fathead minnow in a surface water of variable
quality. Water Research 10:37-43.
Chakoumakos, C., R.C. Russo, and R.V. Thurston. 1979. Toxicity of
copper to cutthroat trout (Salmo clarki) under different conditions
of alkalinity, pH, and hardness. Environ. Sci. Technol.' 13(2) ;213-219.
Elder, J.F. and A.J. Home. Copper cycles and CuSO algicidal capacity
in two California lakes. 1978. Environmental Management _2(1):17-30.
Gachter, R., J.S. Davis, and A. Mares. 1978. Regulation of copper
availability to phytoplankton by macromolecules in lake water. Environ.
Sci. Technol. 12(13):1416-1421.
Howarth, R.S. and J.B. Sprague. 1978. Copper lethality to rainbow
trout in waters of various hardness and pH. Water Research 12:455-462.
Jackson, G.A. and J.J. Morgan. 1978. Trace metal-chelator interactions and
phytoplankton growth in seawater media: Theoretical analysis and com-
parison with reported observations Limnology and Oceanography, 23(2) ;
268-282.
McCrady, J.K. and G.A. Chapman. Determination of copper complexing
capacity of natural river water, well water and artificially reconstituted
water. 1979. Water Research 13:143-150.
McKnight, D.M. and F.M.M. Morel. 1979. Release of weak and strong
copper-complexing agents by algae. Limnology and Oceanography, ^4_(5) :
823-837.
Perhac, R.M. 1974. Water transport of heavy metals in solution and by
different sizes of particulate solids. (NTIS #P3-232 427.)
Shaw, L. and V.M. Brown. 1974. The toxicity of some forms of copper to
rainbow trout. Water Research 3:377-382.
150
-------
Stiff, M.J. 1971. The chemical states of copper in polluted fresh
water and a scheme of analysis to differentiate them. Water Research
.5: 585-599.
Swallow, K.C., J.C. Westall, D.M. McKnight, N.M.L. Morel, and F.M.M.
Morel. 1978. Potentiometric determination of copper complexation by
phytoplankton exudates. Limnol. Oceanogr. 23(3):538-542.
Sylva, B..N. 1976. The environmental chemistry of copper (II) in
aquatic systems. Water Research 10;789-792.
U.S. Environmental Protection Agency (U.S. EPA). 1979. STORET.
Van den Berg, C.M.G., P.T.S. Wong, and V.K. Chau. 1979. Measurement
of completing materials excreted from algae and their ability to ameliorate
copper toxicity. J. Fish Res. Board Can. 36(8);901-906.
151
-------
APPENDIX
FOUR CASE STUDIES — COPPER RISK TO AQUATIC ORGANISMS
I. APPROACH
The purpose of this appendix is to present descriptions of the
implications for risk due to copper in four river basins where copper
concentrations are high. The inclusion of this appendix was motivated,
in part, by the preceding risk assessment. That assessment showed
copper levels to be high, on the average, in a number of minor river
basins. Assessment of the potential fate of copper illustrated that
copper toxicity was likely to be dependent upon a broad range of poten-
tial ambient conditions, including pH, calcium carbonate hardness, and
the presence of organic complexing agents. Such conditions may be
natural or altered by anthropogenic inputs, and are likely to be vari-
able in individual drainages within a minor river basin. Thus, a closer
examination of several areas of high copper concentrations was warranted
in order to gain a better understanding of risk potential and documented
impacts.
The choice of the four rivers to be examined was based on copper
levels reported in STORET over the last five years, a desire to include
a range of water quality parameters, and a desire to include representa-
tions of municipal/industrial activities, as well as mining activities.
The final choices of the Upper Sacramento River, the Coeur D'Alene
River, the Gila River and associated drainage, and the Delaware River,
were admittedly somewhat arbitrary given the number of areas that might
have been included. The degree to which these four rivers are represen-
tative of risk potential in other drainages with high copper levels
would depend on the degree to which they resemble conditions found in
other drainages. No attempt was made here to assess such representa-
tiveness .
The scope for this appendix was limited to gaining a better under-
standing of copper fate and risk in four specific environments. The
approach was to identify several key federal, state, and in some cases,
university personnel who were well acquainted with water quality,
sediment and/or biological conditions in each of the four rivers
examined. Information was gathered through phone conversations with
such individuals on several or all of the following topics:
• The representatives of STORET data:
a) in terms of all of the data available;
b) in terms of its adeauacv so assess the situations that exist.
153
-------
• The cypes and nature of copper sources.
• The status of compliance and/or special problems.
• Fish kill, biological productivity or other aquatic
biological studies that serve to identify risk to copper.
• Knowledge of the fate of copper in the watershed or
water body, including resolubilization potential.
In the case of the Upper Sacramento River, additional, readily available
data from studies conducted in that drainage were made available to us.*
However, in most cases, case descriptions were developed on the basis of
the phone conversations held.
II. CONCLUSIONS
This section summarizes some general conclusions that can be drawn
from the four special cases described in the section that follows
(Section III). While a number of conslusions are neither surprising
nor unique to copper contamination, they have important implications for
understanding risk based solely on copper measurements.
• In not one case was copper the only contaminant of concern.
In fact, in all of the examples cited, the risk potential
of other toxicants was at least equally, if not more,
significant. In the three western areas where mining
activities or abandoned mines represent the major sources,
other heavy metals such as Zn, Cd, and Fe, were at least
as significant to any toxicity observed.
• There is no question that the dilution volume and the
nature of the receiving water has enormous implications
for risk. It becomes obvious that the proximity of water
samples to sources in combination with dilution volume are
important in the actual impacts observed. Source types or
the nature of sources are likely to be as important. The
result is that risk potential tends to be defined by a
number of coincidental parameters which, while generic
in nature, tend to be site-specific. Certainly flow
volume, ?H, the presence of complexing agents rank high
among factors.
• The special case studies did reinforce the role of pH
and the role of calcium carbonate hardness in copper
toxicity. Comparisons among the circumstances and
observed adverse effects for the three western examples
illustrate this.
''Additional data were also seat from Arizona, but proved -o be less
directly applicable to the drainages being examined.
154
-------
• Risk due to copper (with other heavy metals) was verified
in three of the areas examined. Conversely, examples
exist where seemingly high copper levels were not having
observable effects.
• Due to the highly variable conditions at each location,
generalizations cannot be made concerning the levels at
which effects have occurred. Levels of 1-7 mg/L (total
copper) in Spring Creek, California result in an area
nearly devoid of aquatic life. Levels of 20-100 ug/L
below Keswick Dam allow the presence of a local fishery,
including salmonids, although fish kills have occurred.
In the South Fork of the Coeur D'Alene River, concentra-
tions range from 0.04-1.0 mg/L total copper. Mortality
was observed in live box studies, however, salmonids
make successful spawning runs through this area.
• Subjects for which site-specific information was obtained
are listed below. In a number of cases, these may reflect
field research needs.
— Significance of organic chelators.
— Importance/impacts of sediment adsorption -and
resolubilization potential.
— Risks due to occasional "slugs" discharged.
— What happens at salt water/fresh.water interface,
especially with changes in psecies at that interface.
The following sections give a detailed report of information gathered for
each of the case studies.
III. NOTES FROM SPECIAL CASE STUDIES
A. CALIFORNIA; SACRAMENTO RIVER DRAINAGE, VICINITY OF SHASTA LAKE
AND KESWICK RESERVOIR
1. Representativeness of STORET Data
The copper data contained in STORET for the Shasta Lake, Keswick
Reservoir, Spring Creek Reservoir, and Sacramento River immediately below
these reservoirs is reportedly not representative of the amount of-data
that exists. Because of heavy metal pollution in this portion of the
Sacramento River drainage, there is a large amount of water quality data.
In specific studies, for example, copper and cadmium measurements have
been taken as frequently as twice a day. Much of this information,
however, is in the form of intarnai memo reports. This data, although
we have only seen a portion of it. presents a. picture of copper contamina-
tion essentiallv similar to the one oresented by the STORET daca retrieved.
155
-------
.We. were made aware of one problem, however, Evidently, dissolved
copper measurements'in the past have not always been made correctly (it
is not clear whether this applies only to state-generated data). Earlier
comparisons of total and dissolved metals indicated that a large percent-
age of copper remained in the dissolved phase even at higher pH's. This
prompted a recent (1979/1980) study of the relationship between total and
dissolved heavy metals in this drainage. Preliminary results indicate
that earlier dissolved metal measurements were, in fact, in error and
that dissolved metals are lower than total metal concentrations. Unfor-
tunately, copper analyses were not completed at the time of this writing,
and hence, not available.
2. Sources
Abandoned and operating mines, ore dumps, and naturally exposed
sulfide minerals are the sources of acid mine discharges in this area
with copper historically considered most significant. Acid mine waste
from the Spring Creek drainage, which flows into Keswick Reservoir,
represents the major source of toxic concentrations of copper and zinc
in the upper Sacramento River Basin (Finlayson and Ashuckian, 1979).
Abandoned mines also exist near Shasta Lake. One such example is
the acid mine drainage to Squaw Creek, a headwater to Shasta Lake.
3. Circumstances
A number of factors are important for understanding the circumstances
surrounding the problems with acid mine drainage in the upper Sacramento
River Basin. Metal mining activities began at the end of the 19th cen-
tury. Thus, problems with acid mine drainage are not new, and preceded
the construction of any impoundments on the upper Sacramento River.
However, it is generally believed that when Sacramento River streamflow
was not controlled, sufficient dilution existed to reduce waste concen-
trations from acid mine drainage to levels that were evidently tolerated
by fish.
The Shasta Dam and Keswick Dam were completed in 1944 and 1950,
respectively (see Figure 1). The effect of these dams was to reduce
flood flows into the Sacramento River, thereby increasing the propor-
tional contribution of acid mine drainage pollution in Spring Creyk.
As a result, numerous fish kills occurred below Keswick Dam in the
Sacramento River. To alleviate this problem, the Spring Creek Diversion
Dam was constructed in 1963 and releases of water from the resultant
reservoir controlled. The release schedules were based on assumptions
concerning seasonal dilution volumes available to reduce copper concentra-
tions from Spring Creek. The necessary dilution factors were based on
96-hour static bioassays with juvenile salmonids (Finlayson and Ashuckian,
1979; Finlayson and Wilson, 1979).
It is presently believed chat this original release schedule is r.oc
providing sufficient protection of resident and anadromous fish in the
130
-------
SPRING
lacatlen M«» CREEK
BOULDER
CREEK
S. H.
SPRING CREEK
SHASTA
LAKE
SPRING OUEK
RESERVOIR
P * 8
16
Figure 1. Location of Spring Creek drainage, Upper Sacramento
River basin, California.
SOURCE: Finlayson and Ashuckian, 1979.
157
-------
Upper Sacramento River, especially considering Che existence of life
stages more sensitive than juveniles and continuous discharge of waste.
Other heavy metals not considered in release schedules, especially zinc,
contribute to drainage toxicity, and the contribution of copper has
diminished somewhat due to copper cementation plants (for copper removal)
located in the Spring Creek drainage. This latter situation has likely
resulted in an increase in waste releases from Spring Creek, hence,
resultant zinc concentrations are higher in Keswick Reservoir since zinc
is not considered in present release calculations.
Water in this portion of the Sacramento drainage is relatively soft
(^40-70 mg/L hardness) so that one would not expect high levels of car-
bonate complexing with copper. Ambient pH is at least 7 but frequently
exceeds a pH of 8. In Spring Creek near the dam, the pH evidently
ranges around 3. Over the last couple of years, total copper measure-
ments for the area around Spring Creek Diversion Dam appear to have
ranged from slightly below 1 mg/L to over 6 or 7 mg/L. A maximum of
16 mg/L total copper was recorded in 1979, but appears to have been
extraordinarily high. Copper concentrations (total copper) below Keswick
Dam, in the upper portions of the Sacramento River, appear to range from
0.20 mg/L to around 0.10 mg/L, but more typically in the lower end of the
range (STORET; data from California Resources Agency).
From the data reviewed, it is evident that a significant amount of
dilution occurs when Spring Creek water enters Keswick Reservoir.
In situ dye studies and bench studies have also been done recently
(and are ongoing) to gain a better understanding of the fate of copper
and other heavy metals once they enter .the Keswick Reservoir. The dye
studies indicated that the metal-laden plume entering Keswick Reservoir
from Spring Creek hugs the western bank from where it enters, only touch-
ing the eastern bank in the area of the Keswick Dam. This pattern of
partial mixing is explained, in part, by the description of the Keswick
Reservoir as a slow moving river. Studies have also indicated that with
initial neutralization of the Spring Creek plume, iron and aluminum are
the first metals to come out of solution. In test water of approximately
Keswick Dam area pH and hardness (pH 6.5=7.6; 25 to 60 mg/L Ca C03),
dissolved copper averaged 38.2% of total copper measurements, and dis-
solved zinc averaged 80.7% total zinc (Finlayson and Ashuckian, 1979).
In any case, water quality analyses seem to indicate that significant
amounts of these heavy metals are left in the reservoir rather than
being discharged into the Sacramento River.
Sediment work has not been done yet in the Keswick Reservoir. A
study examining resolubilization potential may be conducted this year.
It is not believed that the Keswick Reservoir becomes anoxic during
warmer months.
4. !molocations for Risk
Because copper inputs into Spring Creek can be controlled, copper
concentrations do vary in the creek. Evidently, when copper (metal)
153
-------
concentrations are high, the creek appears to be devoid of life.
(Presumably, the pH is also low.) Fish may be found in the creek when
concentrations are low. It is here assumed that these would represent
recruits from other, non-polluted .sources, namely other tributaries to
Spring Creek Reservoir.
The west bank of the Keswick Reservoir, where the Spring Creek plume
follows the shore, has been described as looking like a desert. This is
in contrast to the eastern shoreline, which is lush with vegetation.
Fish do exist in the reservoir and are believed to avoid the more heavily
contaminated areas.
Fish kills have not been nearly as great a problem in Keswick
Reservoir as they have been in the Sacramento River just below Keswick
Dam. During the years prior to the construction of the Spring Creek Dam,
fish kills were numerous with several being very large (100,000 or more
fish). However, a large fish kill occurred below Keswick Dam in 1969,
when the ambient pH dropped to about 5.9.
It must be noted that while portions of the Sacramento River, near
the dam, have total copper concentrations in the 20-100 yg/L range, the
Sacramento River does support a fishery, including salmonids. By one
account, the King Salmon population in this area has declined to 30% of
what it was 20 years ago. However, the mining drainage situation has not
changed for the worse in that time. Rather, the decline is related to
the loss of upstream recruitment gravels with dam construction, droughts,
and lower dilution volumes due to retaining flood volumes behind the
Shasta Dam, especially prior to the Spring Creek Diversion Dam construc-
tion.
The result of recent studies in this area has led to the recommenda-
tion that discharges from Spring Creek be rescheduled to consider both
existing zinc and copper concentrations, and to reduce the Sacramento
River dissolved zinc and dissolved copper concentrations below 0.02 and
0.01 mg/L, respectively (Finlayson and Ashuckian, 1979).
Sources'of Information
1. Finlayson, B.J. and S.H. Ashuckian. 1979. Safe zinc and copper
levels from the Spring Creek drainage for steelhead trout in the
Upper Sacramento River, California. Calif. Fish and Game 65(2);
80-99.
2. Finlayson, B. and D. Wilson. 1979. Acid-mine waste: how it affects
king salmon in the Upper Sacramento River. Outdoor California 40(6);
8-12.
3. Selected water quality measurements in the Sacramento River near
Redding, CA. California Regional Water Quality Control Board -
Central Valley Region.
159
-------
4. Individuals contacted:
o Harry Schueller - California NPDES Program Director
(Ca WRCB)
o James Pedri - California Regional Water Quality Control
Board, Redding office.
o Brian Finlayson - California Dept. Fish and Game
160
-------
B. ARIZONA; GILA RIVER DRAINAGE
1.. Representativeness of STORE! Data
While not a surprising observation, the examination of site
specific conditions in this minor river basin pointed to the fact
that the data in STORE! may not be totally representative of condi-
tions that exist and/or data available in a given area. Three examples
from phone conversations concerning the Gila River Basin copper data
illustrate that an incomplete picture is being presented, which may
introduce biases into an assessment.
a) Evidently, more sampling has been done in locations in which
problems have been identified. While it is likely that this
situation is not unique to Arizona, it. would indicate that
the use of this data would bias, any conclusions about copper
exposure drawn from them. For example, the high copper
concentrations and acid conditions reported on the San Pedro
River likely represent areas directly impacted by acid mine
wastewater or runoff. According to three of the four people
contacted, such conditions are localized: the water in this
region is so alkaline that acid conditions are quickly
neutralized and copper, precipitated. The question remains
what portion or percent of this drainage area is similarly
impacted, and this is a very difficult question to answer
based on data that is available.
b) Water quality data for this region .that are in STORET at this
time represent only a portion of the available data. The
Arizona Department of Health Has done an assessment of water
quality in the Miami-Globe portion of the watershed. This
data is not in STORET yet, and the area represents one of
the more seriously impacted regions due to copper mining
related activities. Data collected by the Arizona Game &
Fish Department may not yet be in the STORET system, and a
comprehensive study on the Upper Gila completed by a group
at the University of Arizona (for the BLM) will likely not
be in the system until much later this year.
c) Arizona just recently changed its copper standard from one
based on total copper to one based on dissolved copper
measurements. Thus the preponderance of historical copper
measurements are for total copper (an observation made in
the progress of the exposure assessment). In an area where
water is alkaline especially, dissolved copper measurements
are crucial to an adequate understanding of aquatic exposure.
"Total copper" measurements should remain important as they
could be used to indicate downstream migration of copper.
While the above discussion applies only to the specific araa of Arizona
examined, some of che same observations also apply to che area examined
in California.
16 L
-------
2. Sources
Copper has been mined in this region for nearly 100 years. It is
possible chat background levels of copper in some areas of outcropping
are naturally elevated (>20ug/L), although these cannot be pinpointed
at this level of investigation for reasons discussed below.
. The copper is mined from open pits and by acid leaching. Signifi-
cant amounts of sulfide are present in the ore. Thus, acidity and
formation of copper sulfate are the consequence. NPDES permits are now
required for this process water, which is ponded to allow water to
evaporate. There apparently have been examples, recently, of heavy rains
(in this generally arid region) causing coffer dams to break or overflow.
Thus, this represents one, if a less frequent, source of copper.
In the opinion of both EPA Region 9 and State representatives, a
major source of copper is due to earlier mining practices. Abandoned
mines (open pit) and tailings piles (which can be 200-300 feet high)
are open to oxidation and erosion. One early and apparently frequent
practice was to place the tailings piles on the lowest land, often a dry
stream bed. (This practice still occurs in Mexico and may explain the
extremely high copper numbers observed in the area of that border.)
Thus, a major source of copper appears to be due to surface runoff, and
hence, not likely to be a problem easily solved. However, specific
causes for elevated copper concentrations at particular locations were
not pinpointed in this investigation.
3. Circumstances
In better understanding the implications of STORZT copper data, it
is important to note not only the copper sources but also circumstances
in this area of Arizona define its fate.
As noted above, the water in this region is highly alkaline and
natural waters contract relatively high levels of phosphates and carbon-
ates. Thus, acid leachate, runoff or pond overflow laden with copper
is rapidly neutralized, with copper being precipitated out and becoming
associated with either sediments or suspended material. Direct effects
on aquatic biota due to copper would appear to be a relatively localized
phenomena, with the extent being dependent upon flow volumes. This
latter situation was confirmed by agency personnel contacted.
The issue of stream flow volume is especially important as almost
all surface water in Arizona is allocated (for irrigation). Thus, major
portions of these streams, especially in the drier South, do not have
flow at least some of the year (we do not have many samples from STORET
in these areas).
In addition, in northern regions, streams have been impounded, wich
reservoirs representing drinking, irrigation water, and fishery (recraa-
tion) resources. Streams flowing inco these reservoirs do carry copper
-------
(and iron) laden silts. The deeper reservoirs stracify in wanner months
with the hypolimnion often becoming anoxic. Under these anerobic condi-
tions, copper, iron, and H£S are released in a soluble form. Based on
the conversations held, it does not appear that extensive investigations
concerning the risk potential of reported resolubilization have been
conducted.
Most of the fishery in Arizona is a "put and take" salmonid fishery
in the more perennial portions of the rivers and the reservoirs. Bass
and catfish have also been stocked- in the reservoirs, but these are
assumed to be reproducing populations.
Review of selected STORE! data indicate that, at least for some
locations, copper concentrations can be highly variable. For example,
at a number- of stations along the San Pedro River within the Gila
drainage, a wide variation in copper concentrations can be observed.
During several months in the late winter/early spring of 1978, the
following ranges of "total" copper concentrations were recorded for five
different locations:
30 to 300 ug/L copper,
210 to 6200 ug/L copper,
140 to 280 ug/L copper,
290 to 730 ug/L copper
5 to 2800 ug/L copper.
Similar observations can be made at several additional locations in the
Gila drainage. In some cases, -CaCO-j hardness and pH are similarly vari-
able. Such observations may be related to differences that are naturally
occurring (differences in river flow or leachate due to rainfall) or
direct discharges .from specific sources that are highly variable.
4. Implications for Risk
There are no fish kill data that we have been able to find. Unfor-
tunately, studies have not been conducted comparing fishery productivity
in impacted and non-impacted areas, although this is not surprising
considering the nature of the fishery. Tissue analyses are evidently
now being done by state personnel on a selected basis.
Below is a list of (verbal) evidence of the observed effects of
copper in this region.
a) In flowing streams in the immediate areas impacted by acid
copper runoff, etc., streams appear to have no algae or
other biota. The situation visibly improves downstream.
b) In some areas such as the one described above, trees in
the riparian habitat appear co be adversely effected by
"something," which may be copper. This niay be investi-
gated by Che Department of Game and Fish chis year. The
163
-------
concern over saline irrigation waters dominates water
quality considerations, and with the possible exception
of citrus production (related to Cu/Boron balance),
Cu has not been an issue.
c) There is some evidence that the resolubilized copper,
iron, manganese, and I^S in reservoirs may have impacts
on the usability of the recreational fishery. For example,
fish from Roosevelt Lake have been brought to state agency
personnel with darkened flesh (metallic flavor). .Final
Creek, polluted by mining activities, experienced a fish
kill in 1973 or 1974. While copper levels may have been
high, the fish kill was attributed to iron, manganese
and H2S.
One study was just completed at Arizona State University on diatom
populations in a stream contaminated from a mine seep (data not yet
available). It was observed that essentially only one species of diatom
inhabited the diatometers in the stream area near the mine seep. A
diverse diatom community reappeared on samplers further downstream.
Water quality data indicated a mean concentration of 20.9 mg/L dissolved
Cu from the mine seep, a mean concentration of 6.47 mg/L dissolved Cu
in the creek adjacent to the seep, and a mean concentration of .270 ug/L
dissolved Cu 1 km downstream. While data indicate effects of copper,
they represent only two 1-month samples, as the creek was dry the rest
of the time.
Sources of Information
Region 9 EPA
1) Ted Durst - in charge of NPDES permits for Arizona.
2) Phil Woods (Water Division) - in charge of Arizona.
Arizona Department of Game and Fish
3) Ken Hanks
Arizona Department of Health
4) Timothy Love
Arizona State University
5) Dr. Milton Ray Summerfeld
6) Andrew Lampkin (graduate student)
164
-------
C. IDAHO: COEUR-D'ALENE-SPOKANE RIVER DRAINAGE
1. Representativeness of STORET Data
Discussions with Idaho Department of Health and Welfare personnel
gave a somewhat more encouraging picture concerning the representative-
ness of STORE! data. They believe that much of the general survey data
collected on an annual basis is in STORET. Some specialized studies may
not be placed in the system.
2. Sources
Mining has been practiced in this area of Idaho for nearly a
century. Active mining, smelting, plating, as well as old tailings
and abandoned mine drainage, represent the major sources of copper
observed in surface waters in this system.
While state personnel believe that point source controls have
resulted in reduced loading from newer sources, there has evidently
not been a marked improvement in ambient concentrations in heavily
impacted streams such as the South Fork of the Coeur-D'Alene. Non-
point sources of copper and other heavy metals remain a real problem.
Two examples illustrate this situation:
•
a) Houses have been built on old tailings piles in some areas.
Even the groundwater may be impacted.
b) In some locations where tailing pond effluents are treated
sufficiently, the pond itself leaks, contributing significant
amounts of heavy metals to the adjacent river or stream.
3. Circumstances
The fact that water in rivers such as the Coeur-D'Alene are softer
and less well buffered than the Gila River is one major difference
between the circumstances affecting the significance of ambient levels
of copper in waters in Arizona and in Idaho. Other complexing agents
(such as organics) that might affect reduced copper toxicity are not
believed to be present in high amounts in rivers such as the South Fork
of the Coeur-D'Alene. Very low ambient pH has been a real problem in
the past, although ambient pH in this river reportedly remains in the
5-7 range now. Ambient pH in other portions of this drainage, the North
Fork of the Coeur-D'Alene for example, is typically greater than 7. The
water in this area is soft and relatively unbuffered (alkalinity <20 mg/L;
hardness <50 mg/L).
Small lakes are connected to the Coeur-D'Alene along its course, and
the river empties into Coeur-D'Alene Lake which then flows into the Spo-
kane River. According to agency personnel, dissolved oxygen is not a
real problem in chis drainage. The river has a stes? gradient and has
been channelized so chat the water remains well oxygenated. The lakes
165
-------
are not believed co become anoxic for any period of time. However,
Coeur-D'Alene Lake is becoming more eutrophic, thus anoxic conditions
could become more of an issue in the future.
While the reported water quality parameters appear to favor the
presence of soluble/toxic forms of copper (and other metals) in the
water column, studies done in the mid-seventies do show a high level
deposition of metals where the Coeur-D'Alene flows into lakes. Concen-
trations of metals in sediments decreases with distance from the stream
mouth. Metal concentrations are also lower in lake water and in the
Spokane River. Certainly dilution is likely a major factor in these
lower concentrations. The question remains .to what degree sediment
deposition and increased complexing of metals also play a role. Unfor-
tunately, studies on complexing or the potential for resolubilization
from sediments do not appear to exist.
STORE! data for this area, from 1978 and 1979, indicate very high
copper concentrations at several locations which appear to be discharge
(exact type, point or non-point source, etc., was not determined). Even
at these locations, total copper concentrations ranged from <40 Ug/L to
1 mg/L or more. The data from the South Fork of the Coeur-D'Alene
showed copper concentrations within a 10-50 ug/L range. By contrast,
data from Coeur-D'Alene Lake Idaho portions of the Spokane River indi-
cated "total" copper concentrations typically <10 ug/L.
While the above discussion focuses on copper fate in this drainage,
copper is not considered the major problem. In fact, concern over zinc,
cadmium and even iron place copper far down the list of problems con-
sidered significant in this drainage. It was acknowledged that while
copper could contribute to the problems observed, the concentrations of
other heavy metals were so high that it is difficult to isolate copper's
role in observed toxicity.
4. Implications for Risk
The effect of high concentrations of heavy metals in the South Fork
of the Coeur-D'Alene has been demonstrated. As recently as the Fall
1979, live box studies were conducted in the South Fork, and fish only
survived a few hours in the most severely impacted sections of the river.
Water quality measurements taken at the time of the in-stream bioassays
indicated extremely high levels of Zn (4,000 to 5,000 ug/L), Cd (10 to
25 ug/L), and Fe (perhaps 4,000 to 5,000 g/L). The contact in this
case did not recall copper measurements. Data retrieved from STORE!
indicate several copper measurement maxima in the mg/L range; unfortun-
ately, the summaries do not indicate the time of year these were taken.
Interestingly, the cause of fish death in the above-mentioned live-box
bioassays was believed to be iron-oxide floe formation on fish gills.
In spite of the above obvious toxicity of the South Fork, it has
been shown recently chat fish (importantly, salmonids) do aake success-
ful spawning runs chrough chis screech of river to the unpollucsd North
100
-------
Fork. Successful upstream migration is believed Co occur during
high flows, when heavy metals inputs are diluted.
While the STORE! data on copper collected for Coeur-D1Alene
Lake and the Upper Spokane River indicate a general reduction in
ambient copper concentration, ambient levels of heavy metals in a
large number of cases evidently exceed recommended maxima for water
as "soft" as is present here. Nonetheless, a significant fish popula-
tion, including salmonids, exists in this portion of the drainage.
Studies done in the mid-seventies indicated significant elevations
in heavy metals in the tissues of algae and periphyton, aquatic
macrophtes and fish, and on trees adjacent to the Spokane River. To
our knowledge, studies of the effects of such concentrations of
heavy metals, such as decreased productivity, have not been done.
Obviously, the acutely toxic effects of the heavy metals do not
exist.
A better understanding of the fate of copper and other heavy
metals in this drainage might be extremely helpful. Certainly, dilution
plays a role in terms of both seasonal and downstream reduced toxicity.
Reported high concentrations of heavy metals in lake sediments (both
Coeur-D'Alene Lake and lakes adjacent to the South Fork) indicate
(not surprisingly) that precipitation, sediment and/or suspended
solids adsorption of metals do play a role in removing heavy metals
even though ambient conditions do appear to favor soluble forms of
the metals. Unfortunately, the degree to which organics, colloids,
as well as inorganic substances in the water column may be acting to
reduce heavy metal toxicity is unknown. Similarly, the potential
from sediments has not been investigated.
Sources of Information
Region 10, EPA
Ron Kreitzenback (Water Quality)
Ray Peterson (Biota)
Idaho, Department of Health and Welfare
Lany Koenig (Industry Source Control)
Mike Smith (Special Water Studies)
iO/
-------
D. THE DELAWARE RIVER BASIN
1. Representativeness of STORET Data
The Delaware River/Estuary flows through or touches on five differ-
ent states. Hence, there are a large number of city, state and/or
federal agencies that collect data or support data collection efforts.
The Delaware River Basin Commission represents an interstate group that
also supports data collection.
Based on discussions with a representative sample of these various
authorities, it does appear that much of the water quality data collected
is entered in STORET, although at least in the case of the larger data
collection programs there may be as much.as a year's lag time between
collection and STORET entry.
In some cases, however, the data may be somewhat misleading due to
a variety of analysis techniques with various detection limits. Where
"Standard Methods" have been used, the detection limit is 10 ug/L; the
STORET data indicate that some analytical methods used have a detection
limit below 10 ug/L; and analytical methods used for copper measurements
for the Basin Commission have a 100 ug/L detection limit. Some of the
samples analyzed for the New Jersey Department of Environmental Protec-
tion may represent data of dubious quality because a laboratory did not
follow required procedures concerning holding times.
2. Sources
The Delaware River Basin contains areas of heavy population concen-
trations and industrial development. While no attempt was made here to
catalog sources and connect them directly to areas of higher copper
concentration, the types of sources are numerous. While concentrated
in more industrialized sections of the drainage, some sources are also
found in less developed areas. The types of sources include metal
plating industries, pipe manufacturing, effluents from power plants
using certain corrosion inhibitors, steel industries, and even from
copper pipes used in water systems. The latter source, while not likely
producing high concentrations of copper, can serve as a copper source due
to the slightly acid nature of the water. Industrial sources may dis-
charge independently or they may send effluents to a POTW. In the City
of Philadelphia, these two different routes are about equally represented.
3. Circumstances
The Delaware River/Estuary, as this designation implies, is a fairly
large freshwater river, becoming an increasingly saline-well mixed estu-
ary in its southern reaches.
Looking at STORET data from the Delaware Drainage, there ara a
number of samples where copper levels are reported at 100 ug/L. Assuming
that these all represent copper measured by a technique with a 100 ug/L
153
-------
detection limit, copper levels--in-mos-t-of-this drainage are 10 ug/L or
less. The exceptions appear to be in the heavily industrialized areas
(Trenton-Philadelphia corridor) and upstream near Martins Creek. With
few exceptions, total copper levels in this area fall in the <10 to
80 ug/L range (one measurement near Martins Creek was 170 ug/L Cu).
Very little sediment work has been done. None of the persons
contacted had an idea of what may be complexing heavy metals in this
drainage, as water is both fairly soft and somewhat acid.
4. Implications for Risk
Mo information on fish kills or other effects was uncovered. A
benthos survey has been done that indicates changes in diversity and
number in various portions of the river. It does not appear that this
had been tied directly to a particular contaminant, although this would
likely be impossible. From the discussions held, it is fair to conclude
that risk due to copper is of minor concern compared with other contam-
inants potentially and known to be present.
Sources of Information
Delaware River Basin Commission - Cy Gross
City of Philadelphia - Dennis Blair
New Jersey Department of Environmental Protection
Nick Binder - Basin Manager
Frank Takacs - Biologist
Robert Kotch - Water Quality/Data Collection
Paul Hamer - NJDEP, Bureau of Fisheries
Robert Ahlert - Bureau of Engineering Services at Rutgers University
169
------- |