ENVIRONMENTAL CONTAMINANTS ENCYCLOPEDIA

COPPER ENTRY

July 1, 1997

COMPILERS/EDITORS: 

ROY J. IRWIN, NATIONAL PARK SERVICE

WITH ASSISTANCE FROM COLORADO STATE UNIVERSITY

STUDENT ASSISTANT CONTAMINANTS SPECIALISTS:

MARK VAN MOUWERIK

LYNETTE STEVENS

MARION DUBLER SEESE

WENDY BASHAM

NATIONAL PARK SERVICE 

WATER RESOURCES DIVISIONS, WATER OPERATIONS BRANCH

1201 Oakridge Drive, Suite 250

FORT COLLINS, COLORADO 80525 
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since there are so many different "standard methods"

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and various private groups. What some laboratory and

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fact, the interagency task force on water methods

concluded that [1014]:

It is the exception rather than the rule that

water-quality monitoring data from different

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scientifically sound basis, and that...

No nationally accepted standard definitions exist

for water quality parameters. The different

organizations may collect data using identical or

standard methods, but identify them by different

names, or use the same names for data collected by

different methods [1014].

Differences in field and laboratory methods are also

major issues related to (the lack of) data comparability

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and air. For additional information on data variability,

see Laboratory and/or Field Analyses section below. 

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Although the editors of this document have done their

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listing of other entries (other topics) covered. 

See the separate file entitled REFERENC for the identity

of numbered references in brackets. 

HOW TO CITE THIS DOCUMENT: As mentioned above, for

critical applications it is better to obtain and cite the

original publication after first verifying various data

quality assurance concerns. For more routine

applications, this document may be cited as:

Irwin, R.J., M. VanMouwerik, L. Stevens, M.D.

Seese, and W. Basham. 1997. Environmental

Contaminants Encyclopedia. National Park Service,

Water Resources Division, Fort Collins, Colorado.

Distributed within the Federal Government as an
Electronic Document (Projected public availability

on the internet or NTIS: 1998).
Copper (Cu, CAS number 7440-50-8)

Brief Introduction:

Br.Class: General Introduction and Classification Information:

The chemical element copper is a reddish metal [280].

Copper is widely distributed in nature in the elemental

state, in sulfides, arsenites, chlorides, and carbonates;

Copper is only superficially oxidized in air, sometimes

giving a green coating of hydroxy carbonate and hydroxy

sulfate [366]. 

Copper exhibits oxidation states of +2 (the most common,

forming Cu(II) compounds), and +1 (Cu(I), stable only in

aqueous solution if part of a stable complex ion) [280].

A few compounds of copper(III) are also known [280].

Copper is listed by the Environmental Protection Agency

as one of 129 priority pollutants [58]. Copper is a

toxic pollutant designated pursuant to section 307(a)(1)

of the Clean Water Act and is subject to effluent

limitations (40 CFR 401.15, 7/1/88) [609]. 

Copper sulfides have gotten quite a bit of attention in

environmental toxicology related to their tendencies to

bind copper in the sediments and the relationship of

sulfides to acid mine drainage. The primary ores of

copper are chalcopyrite (CuFeS2) and chalcocite (Cu2S)

[495].

Br.Haz: General Hazard/Toxicity Summary:

Bionecessity:

Although copper in water is a hazard to many

aquatic organisms, minute amounts of copper in the

diet are needed for human, plant, and animal

enzymes (serving as enzyme activators)

[173,180,280,951]. Copper is an important trace

element in plant metabolism [180].

Potential Hazards to Fish, Wildlife, Invertebrates,

Plants,and other Non-Human biota:

Although an essential dietary element for some

plants and animals, high concentrations of copper

in water can be toxic to fish and other aquatic

species [25,83,366]. Elevated concentrations of

copper in water are particularly toxic to many

species of algae, crustaceans, annelids, cyprinids,

and salmonids [180]. 
Copper can be toxic in large quantities, especially

to lower organisms such as bacilli, fungi, and

algae [280]. Copper's aquatic toxicity of often

due to disruption of internal ion balance [177]

(Confirmed by David Mount, National Biological

Service, Columbia, MO, personal communication,

1994).

Copper sensitivity demonstrated by phytoplankton

and zooplankton can vary seasonally in ways not

explained by concentrations of dissolved organic

carbon or hardness. Ceriodaphnia dubia at times is

less sensitive to copper toxicity than are other

pond organisms and therefore should not be used to

set copper standards (Robert Winner, University of

Wyoming, personal communication).

In western watersheds affected by metals, fish

kills are often associated with runoff and

rainstorm events. Metals responsible for toxicity

are often copper and zinc, whose toxicity and/or

mobility are enhanced by the depressions of pH,

hardness/alkalinity, and dissolved organic carbon

that typically accompany these events (David Mount,

National Biological Service, Columbia, MO, personal

communication, 1994).

Large fish are often 2.5 to 3 times more resistant

to copper than juveniles [25]. As most adult fish

are able to tolerate relatively high concentration

of copper for short periods of time, the critical

effect of copper is its greater toxicity to younger

fish [302].

Temperature produces complex effects, but elevated

thermal levels increase fish sensitivity to Cu.

Moreover, death of fish is not related to a

specific Cu level accumulated by any one of several

tissues normally examined, as may be the case of

zinc and Cd. This may be due to differential

accumulation of different species of Cu (that is,

toxic and non-toxic Cu species). Alternatively, in

whole body uptake studies, non-specific epidermal

binding of Cu might mask the specific binding

occurring in a target organ prior to death [488].

Increased salinity and increased hardness protect

fish from copper (Cu) poisoning; however, pH,

alkalinity, organic level, temperature, fish size,

and other factors also play important roles in Cu

poisoning of fish. Generally, the greater the

hardness, alkalinity, salinity, organic level, pH,

and fish size, the more resistant fish are to Cu

[488]. 
Although hardness is widely recognized to affect

aquatic toxicity of metals (for example, hardness

seems somewhat protective of rainbow trout related

to copper and zinc toxicity), pH often has the

largest effect on metals toxicity [25,39]

(Confirmed by David Mount, National Biological

Service, Columbia, MO, personal communication,

1994).

For many metals, alkalinity is sometimes a more

important co-factor for toxicity than hardness (Pat

Davies, Colorado Division of Wildlife, personal

communication, 1997). A water's alkalinity

directly affects the toxicity of copper to aquatic

life, which generally is augmented at lower

alkalinities [375,383]. However, recent (1992)

data suggests hardness may not be as important for

toxicity of copper to aquatic life as is implied in

the EPA Gold Book [302]; using currently available

water chemistry data it is not possible to

accurately predict copper toxicity in water,

especially chronic toxicity (Robert Winner,

University of Wyoming, personal communication). 

As most adult fish are able to tolerate relatively

high concentration of copper for short periods of

time, the critical effect of copper is its greater

toxicity to younger fish [302]. 

Some researchers believe that negative effects of

copper on fish are more likely the result of

toxicity of high concentrations in water than

toxicity from intake of prey containing copper

[25]. However, in all animals studied, continued

ingestion of copper in excess of dietary

requirements led to some accumulation in tissues,

particularly the liver and kidneys [180]. Fish

living or foraging in contaminated sediments may

accumulate it directly from the sediments [95].

Excess copper accumulation can lead to copper

toxicosis and cell damage [180].

In water, copper acts synergistically with other

common urban contaminants such as ammonia, cadmium,

mercury, and zinc to produce an increased toxic

effect on fish [26,47]. Sublethal concentrations

adversely affect minnow fry survival and growth

[57].

Sorensen provided a chapter on copper in a 1991

book on metal poisoning in fish [488]. Generally,

fresh-water species are more sensitive to metals

than are marine species; however, this is not true
in cases of Cu-poisoning in fish. Reasons for

equal sensitivity of markedly different species has

not been elucidated. Nor have explanations been

given for the pronounced species-specific

differences in Cu accumulation levels, which seem

to involve capability for iso-metallothionein

synthesis and hepatic storage of Cu [488].

 

Copper sulfate was one of the first weed killers,

used as long ago as 1882 [492].

 Resistance/Development of Tolerance:

Populations of organisms chronically exposed to

chemical pollutants may develop increased tolerance

to those pollutants [177,493]. Many of the aquatic

issues related to tolerance, interactions with

other metals, and/or indirect impacts related to

copper were summarized by Rand and Petrocelli

[177]. 

In some Colorado settings, net spinning caddisflies

were shown to be more sensitive to predation when

copper is present (Will Clements, Colorado State

University, personal communication). Thus, direct

toxicity is only one of the many types of impact

which copper can have on aquatic life, and some of

the indirect forms of impact relate to tolerance

mechanisms.

Absorption of dietary copper in higher animals is

apparently regulated in part by metallothioneins

(low molecular weight proteins containing high

levels of cysteine) [180]. Increased synthesis of

metallothionein in response to copper exposure may

help animals acquire a somewhat increased tolerance

of this metal [180]. 

Some grasses around copper polluted areas are

copper tolerant [366].

Potential Hazards to Humans:

Copper poisoning or deficiency problems are rare in

humans [173].

 

It is generally agreed that copper itself is less

toxic than its salts (Browning, E. Toxicity of

Industrial Metals. 2nd ed. New York: AppletonCentury-Crofts, 1969. 147) [609].

The fumes and dust cause irritation of the upper

respiratory tract, and will also cause irritation

of the eyes, nose and throat [609]. Fumes from the
heating of metallic copper can cause nausea,

gastric pain, & diarrhea in humans (International

Labour Office. Encyclopedia of Occupational Health

and Safety. Vols. I&II. Geneva, Switzerland:

International Labour Office, 1983. 547) [609].

Copper sulfate was used as one of the first food

colors, and copper gluconate is still used as a

food additive [492].

The ATSDR Toxicological Profile for Copper (1990)

(ATSDR/TP-90/08) summarizes human health effects of

copper [979]. In humans, some oral intake of

copper is necessary for good health, but massive

doses can cause problems, especially for children

[979]. Due to lack of time, not all of the

important highlights of the ATSDR document [979]

have been summarized herein.

Br.Car: Brief Summary of Carcinogenicity/Cancer Information:

Information from the Integrated Risk Information System

(IRIS) OF EPA 1996 [893]:

Evidence for classification as to human

carcinogenicity; weight-of-evidence classification:

Classification: D; not classifiable as to

human carcinogenicity 

BASIS: There are no human data, inadequate

animal data from assays of copper compounds,

and equivocal mutagenicity data. 

HUMAN CARCINOGENICITY DATA: None. 

ANIMAL CARCINOGENICITY DATA: Inadequate. 

According to the ASTDR, in humans copper is not known to

cause cancer [979].

Br.Dev: Brief Summary of Developmental, Reproductive,

Endocrine, and Genotoxicity Information:

The large number of Cu-containing enzymes and

glycoproteins in fish probably accounts for the diversity

of biological effects--effects spanning practically every

system evaluated in the teleost (that is, group

consisting of fishes with bony skeletons and rayed fins).

Hematology is altered, as is respiratory and cardiac

physiology. Copper-induced histological alterations are

found in the gill, kidney, hematopoietic tissue,

mechanoreceptors, chemoreceptors, and other tissues
[488]. 

Reproductive effects are noted at low levels of Cu and

include blockage of spawning, reduced egg production per

female, abnormalities in newly-hatched fry, reduced

survival of young, and other effects. From most studies,

growth and survival are affected at higher Cu levels than

are reproductive changes. Copper poisoning of surface

waters is considered hazardous to teleost life in those

ecosystems; levels of 4 ppb can severely alter migratory

and other behaviors. In view of the chronic

bioaccumulation of Cu and the many effects observed in

Cu-exposed fish, revision of existing water quality

standards for Cu seems prudent [488].

Highly localized deposits of hepatic and renal copper

have been observed in monkeys with copper IUDs and in

control monkeys. Both copper and inert material IUDs have

been observed to increase plasma copper levels. This may

be explained by the observation that stress or

inflammation alone can result in increased serum copper

levels [25].

Incubation of human spermatozoa with metallic copper is

found to bring about a significant fall in the percentage

of motile sperm in humans (Friberg, L., Nordberg, G.F.,

Kessler, E. and Vouk, V.B., eds. Handbook of the

Toxicology of Metals. 2nd ed. Vols I, II.: Amsterdam:

Elsevier Science Publishers B.V., 1986.,p. V2 247) [609].

For fathead minnows, the percentage of embryos with

abnormalities was greater at 338 and 621 ug/l total

copper concentration than at 204 ug/l total copper and

lower concentrations (Scudder BC et al; Aquat Toxicol,

AMST, 12 (2): 107-24, 1988) [609] (see W.Fish section

below for more information).

The data on the effects of cations such as copper,

cadmium, and chromium on the biochemical parameters in a

freshwater fish, Clarias batrachus, showed an increase of

the protein content in the liver, kidney, stomach,

intestine, testis, and ovary, and a decrease in the

muscle after copper and cadmium treatment. The

administration of copper and cadmium increased the

concentration(s) of free amino acids in all the fish

organs, whereas chromium did not change this

concentration(s) in the muscle. A decrease in dry wt, and

an increase in tissue permeability after these treatments

were recorded in all the organs studied. In general, the

above biochem parameters of the organs were affected by

treatments of the above cations in the following order:

cadmium > copper > chromium over control values of C

batrachus, and their effects were markedly pronounced in

the liver and kidney, followed by the intestine, stomach,
muscle, testis, and ovary in this species (Jana S, Sahana

SS; Physiol Bohemoslov 37, 1: 79-82., 1988) [609].

Br.Fate: Brief Summary of Key Bioconcentration, Fate,

Transport, Persistence, Pathway, and Chemical/Physical

Information:

Copper is tightly bound to ligand sites, containing

oxygen, sulfur, or nitrogen atoms on the protein [280].

Many higher organisms can conserve copper when it is

deficient and excrete it when an excess amount enters the

body [180]. Freshwater fish can regulate copper over a

wide range of ambient concentrations [180].

Highway runoff routed through a detention pond and then

a cypress wetland resulted in much higher sediment levels

of copper in the detention pond than in the wetland

[220]. The same study indicated that copper deposits

near the outlet of a freshwater wetland were lower than

those in the middle [220].

More research needs to be done on the toxicity,

mobilization, and bioavailability of copper in low

alkalinity and/or low pH waters [383].

Plants take up copper from soil [83].

When sulfide is present, as it is in estuarine sediments

rich in organic debris, it will combine with metals such

as copper, cadmium, zinc, and lead. The metal sulfides

that form are highly insoluble and will tend to be

sequestered in the sediments (Bender M, 1989, Heavy

metals in Narragansett Bay sediments. Maritimes, 33, 4:

5-7. Off. Mar. Programs, Mar. Resour. Build., URI

Narragansett Bay Campus, Narragansett, RI 02882-1197,

USA) [940].

In 1985, Hem updated a summary of many basic water

quality issues related to this element, including its

sources and species, solubility controls, and its

occurrence in natural water [190].

Environmental Fate Summaries from HSDB [609]:

AQUATIC FATE: Some copper complexes may be

metabolized /however/ there is no evidence that

biotransformation processes have a significant

bearing on the aquatic fate of copper. /Copper

salts and complexes/ [Callahan, M.A., M.W. Slimak,

N.W. Gabel, et al. Water-Related Environmental Fate

of 129 Priority Pollutants. Volume I. EPA-440/4 79-

029a. Washington, DC: U.S.Environmental Protection

Agency, December 1979.,p. 11-16].
TERRESTRIAL FATE: Factors affecting the balance

between copper in the parent rock & in the

derivative soil include the degree of weathering,

the nature & intensity of the soil formation,

drainage, pH, oxidation-reduction potential, & the

amount of organic matter in the soil. Since copper

in rocks is likely to be more mobile under acidic

than alkaline conditions, the relation of pH to

copper in the environ has been of great concern to

agriculturalists & biologists. Alkaline conditions

in the soil & the surface water favor precipitation

of copper. Acid conditions promote solubility of

copper, increase the concentration(s) of ionic

copper, & thereby change the microorganism & other

aquatic animal populations, depending on tolerance

for various levels of copper in solution. The

reports of acid rain in various parts of the world

are of serious concern. Due to the variety of

conditions which influence the metal's avail, the

total copper content of the soils is not an

accurate indication of deficiencies or excess of

copper in soil rooted plants. /Copper salts/

[Seiler, H.G., H. Sigel and A. Sigel (eds.).

Handbook on the Toxicity of Inorganic Compounds.

New York, NY: Marcel Dekker, Inc. 1988. 273].

Synonyms/Substance Identification:

1721 GOLD [609]

ALLBRI NATURAL COPPER [609]

ANAC 110 [609]

ARWOOD COPPER [609]

BRONZE POWDER [609]

CDA 101 [609]

CDA 102 [609]

CDA 110 [609]

CDA 122 [609]

CI 77400 [609]

CI PIGMENT METAL 2 [609]

COPPER BRONZE [609] 

COPPER M 1 [609]

COPPER POWDER [609]

COPPER SLAG-AIRBORNE [609]

COPPER SLAG-MILLED [609] 

COPPER-AIRBORNE [609]

COPPER-MILLED [609] 

CU M3 [609]

GOLD BRONZE [609]

KAFAR COPPER [609]

M 1 [609]

M 3 [609]

M 4 [609]

M1 (COPPER) [609]
M2 (COPPER) [609]

M3 (COPPER) [609]

M3R [609] 

M3S [609]

M4 (COPPER) [609]

OFHC CU [609] 

RANEY COPPER [609]

Caswell No 227 [609]

CE 1110 [609]

Copper, Metallic Powder [609]

E 115 (metal) [609]

EPA Pesticide Chemical Code 022501 [609]

Cuprum (Latin) [609].

 Molecular formula [609]:

Cu

Associated Chemicals or Topics (Includes Transformation Products):

See also individual metals entries which are important because

of interactions with copper:

Cadmium

Mercury

Zinc

Copper usually occurs as part of the oxidizing enzymes such as

ascorbic acid oxidase, tyrosinase, lactase, and monoamine

oxidase [280]. These enzymes, which are high-molecular-weight

proteins containing 0.05%-0.35% of Cu, play an important part

in living oxidation and reduction reactions, in which the

copper undergoes cyclic changes between Cu(I) and Cu(II)

oxidation states [280]. 

Toxic compounds in distilled water, frequently copper, may

result in low BOD [861].

Metabolism/Metabolites [940]:

Transition metals (such as copper) are known to catalyze

lipid peroxidation, possibly forming free radicals.

However, copper is usually incorporated into stable

complexes within cells or vascular fluids. [USEPA;

Drinking Water Criteria Document for Copper (Final Draft)

p.VII-1 (1985) EPA-600/X-84-190-1].

Copper is incorporated into >12 specific copper proteins,

such as cytochrome oxidase, tyrosinase, and erythrocyte

superoxide dismutase. Copper is essential for hemoglobin

formation, carbohydrate metabolism, catecholamine

biosynthesis, and cross-linking of collagen, elastin, and

hair keratin. Other metals such as zinc, iron, and

molybdenum interact with copper to affect copper
absorption, distribution, metabolism, and utilization.

[USEPA; Health Issue Assessment: Copper p.3 (1987)

EPA/600/8-87/001].

Impurities [609]:

In electrolytic copper, the highest level of impurities

other than oxygen are found only to the extent of 15-30

ppm. Up to 0.05% oxygen is present in the form of

copper(I) oxide. [Kirk-Othmer Encyclopedia of Chemical

Technology. 3rd ed., Volumes 1-26. New York, NY: John

Wiley and Sons, 1978-1984.,p. 6(79) 859].

Impurity with corresponding range: Antimony, 1-20 ppm;

arsenic, 1-10 ppm; bismuth, 0.1 to 5 ppm; lead, 3-50 ppm;

iron, 5-25 ppm; nickel, 4-40 ppm; tellurium, 1-15 ppm;

tin, 2-15 ppm [Kirk-Othmer Encyclopedia of Chemical

Technology. 3rd ed., Volumes 1-26. New York, NY: John

Wiley and Sons, 1978-1984.,p. 6(79) 862].

Water Data Interpretation, Concentrations and Toxicity (All Water

Data Subsections Start with "W."):

W.Low (Water Concentrations Considered Low):

Leland and Kuwabara, 1985: In non-polluted areas,

baseline concentrations as low as 0.0003 mg/l have been

recorded [177].

Very low concentrations are usually the result of pH and

other physical/chemical factors [190].

W.High (Water Concentrations Considered High):

In polluted areas, baseline concentrations as high as 100

ug/l have been recorded [190].

Leland and Kuwabara, 1985: In polluted areas,

concentrations as high as 9 mg/l have been recorded

[177].

While experiments show that copper does not leach

significantly from soil, levels of copper as high as 2.8

ppm have been found in some groundwater [979].

Copper concentrations in wastewater from a selected open

pit and underground copper mine were 1.05 ppm and 0.87

ppm, respectively [979]. Results of an EPA industrial

effluent survey show that mean and maximum levels of

copper in treated wastewater from six industries exceeded

1 and 10 ppm, respectively [979]. These industries and

their mean and maximum discharges in ppm are: inorganic

chemicals manufacturing (less than 1.6, 18); aluminum
forming (less than 160, 2200); porcelain enameling (1.3,

8.8); gum and wood chemicals (1.4, 3.0); nonferrous

metals manufacturing (1.4, 27.0); and paint and ink

formulation (less than 1.0, 60.0) [979]. 

W.Typical (Water Concentrations Considered Typical):

USGS 1985: Levels near 10 ug/L can be commonly expected

in river water [190]. Very low concentrations are

usually the result of pH and other physical/chemical

factors [190].

Median for Treated Drinking Water: 8.3 ug/L [190].

In southern Ontario, Canada, where the average

concentration of copper in rain was 1.57 ppb during 1982,

1.36 mg of copper was deposited annually per square meter

as a result of wet deposition [979]. For central and

northern Ontario, the mean concentrations of copper in

rain were 1.36 and 1.58 ppb, respectively [979].

The median concentration of copper in natural water is 4-

10 ppb [979]. It is predominantly in the Cu(II) state

[979]. Most of it is complexed or tightly bound to

organic matter; little is present in the free (hydrated)

or readily exchangeable form [979]. The combined

processes of complexation, adsorption, and precipitation

control the level of free Cu(II) [979]. The chemical

conditions in most natural water are such that, even at

relatively high copper concentrations, these processes

will reduce the free Cu(II) concentration to extremely

low values [979].

Copper in wastewater discharged into a river leading into

Chesapeake Bay, MD, contained 53 ppb of copper, of which

36 ppb were in the form of settleable solids [979]. The

concentration of copper rapidly decreased downstream of

the outfall; 2-3 km from the outfall, the copper

concentration had fallen to 7 ppb [979]. The

concentration of copper in sediment downstream from the

outfall was about a factor of 10 higher than in

uncontaminated 6 [979].

Geometric mean from Storet Database, surface waters: 4.2

ppb [979].

Median concentration from Storet Database, surface

waters: 4.0 ppb [979].

In the EPA-sponsored National Urban Runoff Program, in

which 86 samples of runoff from 19 cities throughout the

United States were analyzed, copper was found in 96% of

samples, at concentrations of 1-100 ug/L (ppb) [979]. Of

the 71 priority pollutants analyzed for, copper, along
with lead and zinc, was the most frequently detected

[979]. The geometric mean copper concentration in runoff

water was 18.7 ug/L [979].

Concentrations of copper in influents to 239 wastewater

treatment plants (12,351 observations) were 0.0001-36.5

ppb [979]. and the median value was ~0.4 ppb [979].

 

Typical Ocean Concentrations:

EPA 1981: 0.003 mg/l [83], sometimes lower or

higher [177]. 

Copper is present to the extent of 0.020-0.001

parts per million in seawater [280,366]. 

 Typical Freshwater Concentrations:

EPA 1981: 0.01 mg/l [83]. 

In an Arizona intermittent stream, copper was less

than 0.05 mg/l above an open-pit copper mine

outfall and 0.09 mg/l below the outfall [221].

California, 1986: Ambient background level for

water was 0.001 mg/l [222].

The average concentration of copper in tap water ranges

from 20 to 75 parts copper per billion parts water (ppb)

[979]. However, many households have copper

concentrations of over 1000 ppb [979]. That is more than

1 milligram per liter of water [979]. This is because

copper is picked up from copper pipes and brass faucets

when the water sits in the pipes overnight [979]. After

the water is allowed to run for a while, the

concentration of copper in the water decreases [979]. The

average concentration of copper in lakes and rivers is 4

ppb [979]. The average copper concentration in

groundwater is similar to that in lakes and rivers;

however, monitoring data indicate that some groundwater

contains higher levels of copper [979]. This copper is

generally strongly attached to particles in the water

[979]. 

Effluents from power plants that use copper alloys in the

heat exchangers of their cooling systems discharge copper

into the receiving waters [979]. The largest discharges

occur after start-up and decrease rapidly thereafter

[979]. At the Diablo Canyon Nuclear Power Station, a very

high start-up discharge containing 7700 ppb of copper

fell to 67 ppb after 24 hours [979]. During normal

operation at two nuclear power stations, copper levels

ranged between 0.6 and 3.3 ppb [979]. 
Information from HSDB [609]:

DRINKING WATER: Because the concentration of

copper in drinking water is highly variable, means

are of limited significance. Approx 55% of the 604

water samples analyzed by the USEPA (1975)

contained measurable levels of copper. The mean of

these samples was 60 ug/l. The mean of another

study was 150 ug/l. /Copper salts and copper (II)

oxides/ [National Research Council. Drinking Water

and Health. Volume 3. Washington, DC: National

Academy Press, 1980. 313] [609].

DRINKING WATER: Very large variations may occur

depending on type of water, eg, hardness & pH, &

types of pipes & taps. Concentrations from a few

micrograms to more than 1 mg/l have been reported

... . /Copper salts and copper (II) oxides/

[Friberg, L., Nordberg, G.F., Kessler, E. and Vouk,

V.B. (eds). Handbook of the Toxicology of Metals.

2nd ed. Vols I, II.: Amsterdam: Elsevier Science

Publishers B.V., 1986.,p. V2 236] [609].

A combination of low pH and soft water passing

through copper pipes and fittings may produce high

copper levels in drinking water; however, only a

little over 1% of USA drinking water exceeds the

drinking water standard of 1 mg/l, with the avg

copper concentration(s) in drinking water reported

as approx 0.13 mg/l. ... Background

concentration(s) of copper in USA surface waters is

< 20 ug/l. /Copper salts and Copper(II) oxides/

[USEPA; Health Issue Assessment: Copper p.22 (1987)

EPA/600/8-87/001] [609].

Water particularly water that is acidic, low in

hardness and alkalinity, and consequently corrosive

to piping, may leach copper from drinking water

pipes. /Soluble copper salts and copper(II) oxides/

[USEPA; Drinking Water Criteria Document for Copper

(Final Draft) p.II-12 (1985) EPA-600/X-84-190-1]

[609].

A study was conducted on the distribution of

manganese, iron, copper, lead, and zinc in the

water and sediment of Kelang esturary in 1981. The

mean total levels of manganese, iron, copper, lead,

and zinc in the estuarine water were 27.1 ug/l,

106.5 g/l, 10.0 ug/l, 4.1 ug/l and 17.9 ug/l

respectively. The results indicate that Kelang

estuary is polluted with lead, manganese, and iron.

However, levels of these heavy metals may still be

considered safe for aquaculture, if the farm is

located at least 10 km away from the river mouth.
[Law AT, Singh A; Pertanika 9 (2): 209-18 (1986)]

[609]

W.Concern Levels, Water Quality Criteria, LC50 Values, Water

Quality Standards, Screening Levels, Dose/Response Data, and

Other Water Benchmarks:

W.General (General Water Quality Standards, Criteria, and

Benchmarks Related to Protection of Aquatic Biota in

General; Includes Water Concentrations Versus Mixed or

General Aquatic Biota):

Notes on total vs. acid soluble vs. dissolved

metals:

Although most of the lab tests done to develop

water quality criteria and other benchmarks

were originally based on "total" values rather

than "dissolved" values, some regulatory

authorities nevertheless recommend comparing

criteria with dissolved or acid soluble metals

concentrations. EPA gave many reasons why

water quality criteria should be compared to

acid soluble values [25]. For detailed

discussion, see the Laboratory and/or Field

Analyses section (far below).

EPA 1996 IRIS database information [893]:

Clean Water Act (CWA) Ambient Water Quality

Criteria for Aquatic Organisms [893]:

Acute Freshwater Criterion: 9.2E+0 ug/L

hardness dependent [893]. 

The equation is acute = e to the

power of (0.9422[ln(hardness)]-

1.464) [649]. Further

clarification:

e is the base of natural

logarithms and numerically

equals 2.72 (rounded), and

In(hardness) equals the natural

logarithm of the measured

hardness (Gary Rosenlieb,

National Park Service, Personal

Communication, 1997).

Older published freshwater acute

criteria was 18 ug/L, hardness

dependent criterion rounded to two

integers (100 mg/L CaCO3 used)
[446,689]. 

 

Chronic Freshwater Criterion: 6.5E+0 ug/L

hardness dependent [893]. 

Older Freshwater Chronic Criteria

was 12 ug/L, a hardness dependent

criterion rounded to two integers

(100 mg/L CaCO3 used) [689]. The

equation is chronic = e to the

power of (0.8545[ln(hardness)]-

1.465) [649].

Further clarification:

e is the base of natural

logarithms and numerically

equals 2.72 (rounded), and

In(hardness) equals the natural

logarithm of the measured

hardness (Gary Rosenlieb,

National Park Service, Personal

Communication, 1997).

Marine Acute Criterion: 2.9E+0 ug/L

[446,893].

Marine Chronic Criterion: None Published

[893].

NOTE: Before citing a concentration

as EPA's water quality criteria, it

is prudent to make sure you have the

latest one. Work on the replacement

for the Gold Book [302] was underway

in March of 1996, and IRIS is

updated monthly [893].

Oak Ridge National Lab, 1994: Ecological Risk

Assessment Freshwater Screening Benchmarks for

concentrations of contaminants in water [649]. To

be considered unlikely to represent an ecological

risk, field concentrations should be below all of

the following benchmarks [649]:

For CAS 7440-50-8 (Copper, the benchmarks in

ug/L are [649]:

NATIONAL AMBIENT WATER QUALITY CRITERION

- ACUTE: 18

The above is a hardness dependent

criterion (100 mg/L CaCO3 was used

to calculate the above

concentration).
NATIONAL AMBIENT WATER QUALITY CRITERION

- CHRONIC: 12

The above is a hardness dependent

criterion (100 mg/L CaCO3 was used

to calculate the above

concentration).

 

 SECONDARY ACUTE VALUE: No information

found

SECONDARY CHRONIC VALUE: No information

found

LOWEST CHRONIC VALUE - FISH: 3.8

LOWEST CHRONIC VALUE - DAPHNIDS: 0.23 

 

LOWEST CHRONIC VALUE - NON-DAPHNID

INVERTEBRATES: 6.066 

LOWEST CHRONIC VALUE - AQUATIC PLANTS: 1

LOWEST TEST EC20 - FISH: 5

LOWEST TEST EC20 - DAPHNIDS: 0.205

SENSITIVE SPECIES TEST EC20: 0.26 

Other Concern Levels for Water Concentrations:

EPA's original 1980s permissible

concentration(s) of total recoverable copper

in water to protect freshwater aquatic life

was 5.6 ug/l as a 24 hr avg. The log of this

concentrtion should not exceed the numerical

value of log (0.94 In (sic) (hardness) -1.23).

The corresponding value to protect saltwater

aquatic life is 4.0 ug/l as a 24 hr avg, and

should not exceed 23 ug/l at any time

[25,609].

NOTE: Recent (1992) data suggests

hardness may not be as important for

toxicity of copper to aquatic life as is

implied in the gold book; using currently

available water chemistry data it is not

possible to accurately predict copper

toxicity in water, especially chronic

toxicity (Robert Winner, University of

Wyoming, personal communication).

Florida's water quality standard applied to

some wetland sites was 30 ug/l [220].
A State of California recommendation based on

direct toxicity was that 1.2 ug/L be the water

quality criteria (1.4 ug/l was one adverse

effects level) [222].

W.Plants (Water Concentrations vs. Plants):

LC50 for Enteromorpha sp. (green algae) is 9.9 ug/L

(ppb) for a 5-day exposure [998].

LC50s for Scenedesmus dimorphus (green algae) were

76.9 ug/L for a 24-hr exposure, 61.7 ug/L for a 6-

day exposure, and 91.8 ug/L for a 15-day exposure

[998].

Copper (copper sulfate) is used in aquatic

herbicides, and copper concentrations as low as 1

ug/L have been shown to inhibit growth of aquatic

plants [25]. Some of the highest bioconcentration

factors recorded for copper are for the freshwater

alga Chlorella regularais [25].

Shallow Groundwater Ecological Risk Assessment

Screening Benchmark for Terrestrial Plants Listed

by Oak Ridge National Lab, 1994 [651]:

To be considered unlikely to represent an

ecological risk, field concentrations in

shallow groundwater or porewater should be

below the following benchmark for any aqueous

solution in contact with terrestrial plants. 

Toxicity of groundwater to plants may be

affected by many variables (pH, Eh, cation

exchange capacity, moisture content, organic

content of soil, clay content of soil,

differing sensitivities of various plants, and

various other factors). Thus, the following

solution benchmark is a rough screening

benchmark only, and site specific tests would

be necessary to develop a more rigorous

benchmark for various combinations of specific

soils and plant species [651]:

For CAS 7440-50-8, COPPER, the Benchmark

is 0.03 mg/L (porewater or groundwater).

W.Invertebrates (Water Concentrations vs. Invertebrates):

LC50s for Acartia tonsa (Calanoid copepod) were 17,

17, 31, 55 and 64 ug/L (ppb) for 96-hr exposures

[998].

LC50s for Amnicola sp. (Spire snail) were 1.50 and
4.50 mg/L (ppm) for 24-hr exposures and 9.30 and

0.90 mg/L (ppm) for 96-hr exposures [998].

LC50s for Artemia salina (brine shrimp) were 0.80

mg/L for a 24-hr exposure and 0.44 mg/L for a 48-hr

exposure [998].

LC50s for Balanus improvisus (barnacle) were 0.14

mg/L for a 12-hr exposure, 0.11 mg/L for a 24-hr

exposure, and 0.10 mg/L for 48-, 72-, and 96-hr

exposures [998].

LC50s for Brachionus calyciflorus (rotifer) were

about 30 ug/L (ppb) for 24-hr exposures [998].

LC50s for Calanoida (copepod order) were about 52

ug/L (ppb) for 96-hr exposures [998].

LC50s for Ceriodaphnia dubia (water flea) were:

649 ug/L (ppb) for a 24-hr exposure; 17 to 406 ug/L

for a 48-hr exposure, with most between 20 and 80

ug/L; 302 ug/L for a 5-day exposure; and 192 ug/L

for a 10-day exposure [998].

24-hr LC50s were 3.16 to 23.6 mg/L (ppm) for

Chironomus plumosus (midge), 3.40 to 13.43 mg/L for

Chironomus riparius (midge), and 2.70 to 10.10 mg/L

for Chironomus tentans (midge) [998].

96-hr LC50s were 0.53 to 2.20 mg/L (ppm) for

Chironomus plumosus (midge), 0.64 to 1.27 mg/L for

Chironomus riparius (midge), and about 0.50 mg/L

for Chironomus tentans (midge) [998].

LC50s for Crangon crangon (common shrimp) were 10.0

to 33.0 mg/L for 48-hr exposures [998].

LC50s for Crassostrea rhizophorae (mangrove oyster)

were 40.0 mg/L for a 5-day exposure and 2.5 mg/L

for a 7-day exposure [998].

LC50s for Daphnia magna (water flea) ranged from 24

to 96 ug/L (ppb) for 48-hr exposures, with most

below 55 ug/L [998].

LC50s for Daphnia pulicaria (water flea) ranged

from 7.24 to 627 ug/L (ppb) for 48-hr exposures,

with most below 85 ug/L [998].

LC50 for Lamellidens marginalis (mussel) was 5.00

mg/L (ppm) for a 96-hr exposure [998].

LC50s for Tubifex tubifex (Tubificid worm) were 0.4

ug/L (ppb) for a 12-hr exposure, 0.21 ug/L for a
48-hr exposure, and 0.15 ug/L for a 5-day exposure

[998].

Acute values are as low as 6.5 ug/L for Daphnia

magna in hard waters [25].

Estuarine clams were exposed to copper or mercury

at 300 or 600 ug/l for 96 hr and the toxic effects

evaluated by determining tissue carotenoids, lactic

acid and glycogen contents; with carotenoids

increasing, lactic acid increasing, and glycogen

levels decreasing in the metal exposed claims

compared to the controls. During the 1st 48 hr of

exposure, the metabolic rates of the clams were

decreased by both metals; some adaptation of the

clams occurred during the next 48 hr (Sathyanathan

B et al; Bull Environ Contam Toxicol 40 (4): 510-

16, 1988) [609].

See also the below W.Misc section.

W.Fish (Water Concentrations vs. Fish):

Water copper levels of 4 ppb can severely alter

migratory and other behaviors of teleost fish

[488]. In view of the chronic bioaccumulation of

Cu and the many effects observed in Cu-exposed

fish, revision of existing water quality standards

for Cu seems prudent [488].

LC50s for Osteichthyes (bony fish class) were 14 to

3120 ug/L (ppb) for 48-hr exposures, and 8.7 to

1130 ug/L for 96-hr exposures [998].

LC50s for Pimephales promelas (fathead minnow)

ranged from 0.0885 to 21.0 mg/L (ppm) for 96-hr

exposures, and was 0.070 mg/L for a 7-day exposure

[998].

LC50s for Atherinops affinis (topsmelt) were about

0.235 mg/L (ppm) for 96-hr exposures, and ranged

from 0.134 to 0.365 mg/L for 7-day exposures [998].

The no-observed-effect-concentrations (NOEC) for

death of topsmelt were 90 to 160 ug/L (ppb) for 96-

hr exposures, and 100 and 180 ug/L for 7-day

exposures [998].

LC50 for Channa striata (snake-head catfish) was

12.4 mg/L (ppm) for a 72-hr exposure [998].

LC50s for Oncorhynchus mykiss (rainbow trout,

donaldson trout) were 130 ug/L for a 24-hr exposure
and 250 ug/L for a 96-h exposure [998].

Information from HSDB [366]: 

Embryos of the fathead minnow, Pimephales

promelas Rafinesque, were exposed to total

copper concentrations of 0.6, 61, 113, 204,

338, and 621 ug/l from 5 to 10 hr post

fertilization through 2 days post hatch. A

decrease in hatching time was observed with

increasing total copper concentration but

there was no decrease in embryonic

developmental rate. Therefore, embryos hatched

at earlier stages of development. Significant

(p= 0.05) declines in percent survival and

percent total hatch were observed at 621 ug/l

total copper concentration(s) but not at 338

ug/l total copper concentration(s) or lower

concentrations. The percentage of embryos with

abnormalities was greater at 338 and 621 ug/l

total copper concentration(s) than at 204 ug/l

total copper concentration(s) and lower

concentrations. Individuals exposed to copper

during early development were then exposed to

the same test concentrations for 28 days post

hatch. Survivors at 113 through 338 ug/l total

copper concentration(s) were at earlier stages

of development than were control fish. The

percentage of fish surviving decreased with

increasing copper concentration over the range

61 through 204 ug/l total copper concn. The

percentage of fish surviving at 204 ug/l total

copper concentration(s) was not significantly

different from that at 338 ug/l total copper

concn. Surviving larvae at all copper

concentrations from 61 through 621 ug/l total

copper concentration(s) showed decreased

length, weight, and coefficient of condition

compared to controls. The percentage of larvae

with abnormalities increased significantly

with increasing copper concentration. The

calculated 96 hr LC50 (larval stage) was 250

ug/l total copper concentration(s) and the 28

day LC50 (larval stage) was approximately 123

ug/l total copper concn. [Scudder BC et al;

Aquat Toxicol (AMST) 12 (2): 107-24 (1988)]

W.Wildlife (Water Concentrations vs. Wildlife or Domestic

Animals):

To protect livestock/cattle use, general irrigation

water should not exceed 0.2 ppm copper in coarse

soils or 5 ppm in firm soils [671]. 
Oak Ridge National Lab, 1994: Risk Assessment

Screening Benchmarks for Wildlife derived from NoObserved-Adverse-Effect (NOAEL) levels (see

Tis.Wildlife, B) section below for these). To be

considered unlikely to represent an ecological

risk, water concentrations should be below the

following benchmarks for each species present at

the site [650]:

For CAS 7440-50-8, COPPER AS COPPER SULFATE,

the benchmarks are: 

 WATER CONCEN-

 SPECIES TRATION (ppm)

Mink (test species) 0.00000

Short-tailed Shrew 212.82600

Little Brown Bat 367.84600

White-footed Mouse 137.54200

Meadow Vole 240.72400

Cottontail Rabbit 114.06500

Mink 118.28300

Red Fox 84.41600

Whitetail Deer 47.23000

Comment: Actually, the number of

significant figures for a benchmark value

should never be more than one; even if

these values have been taken directly

from another report, they should be

rounded; otherwise the impression is

given of a level of accuracy that is

simply unwarranted. The uncertainties are

too large to justify such a fine

distinction (Owen Hoffman, SENES Oak

Ridge, Personal Communication, 1997).

Lifetime exposure to 42.5 mg Cu/kg/d as copper

gluconate in drinking water resulted in a 12.8%

reduction of the maximal lifespan (from 986 to 874

days) in mice [979].

W.Human (Drinking Water and Other Human Concern Levels):

EPA 1996 IRIS database information [893]:

Maximum Contaminant Level Goal: 1.3 mg/L

[893].

Status/Year: Final 1991 Reference: 53 FR

31516 (08/18/88); 56 FR 26460 (06/07/91);

56 FR 32112 (07/15/91) [893]. 

Contact: Health and Ecological Criteria
Division / (202)260-7571 Safe Drinking

Water Hotline / (800)426-4791 [893].

Discussion: The MCLG of 1.3 mg/L for

copper is based on potential adverse

effects (gastrointestinal) reported in

human studies [893].

Maximum Contaminant Level (MCL): None given in

IRIS [893].. 

Status/Year: Final 1991 Econ/Tech?: Yes,

does consider economic or technical

feasibility Reference: 53 FR 31516

(08/18/88); 56 FR (06/07/91); 56 FR 32112

(07/15/91) [893].

Contact: Drinking Water Standards

Division / OGWDW / (202)260-7575 Safe

Drinking Water Hotline / (800)426-4791 

[893].

Discussion: EPA concluded that setting

an MCL for copper is not feasible and

believes that the treatment approach

contained in the final rule (corrosion

control, source water reduction, public

education and copper service line

replacement) will achieve the public

health goals of the SDWA without the

problems associated with establishing

MCL's [893]. [893].

Note: The older proposed Drinking

Water MCL was 1300 ug/L [446].

Older Federal Drinking Water Standards [609]:

EPA 1300 ug/l (Action Level) [USEPA/Office of

Water; Federal-State Toxicology and Risk

Analysis Committee (FSTRAC). Summary of State

and Federal Drinking Water Standards and

Guidelines (11/93)].

Plain language summary: EPA says drinking

water should not contain more than 1.3

ppm copper [979].

Older Federal Drinking Water Guidelines [609]:

EPA 1000 ug/l [USEPA/Office of Water; FederalState Toxicology and Risk Analysis Committee

(FSTRAC). Summary of State and Federal

Drinking Water Standards and Guidelines
(11/93)].

Plain language summary: EPA says surface

waters should not contain more than 1.0

ppm copper to protect humans from copper

ingested in water and aquatic organisms

[979].

The national secondary drinking water

contaminant level for copper and

compounds for public water systems is 1

mg/l (40 CFR 143.3, 7/1/88) [609].

Older Water Quality Criteria in ug/L [446]:

Human Health Risk Level for Carcinogens (risk

of one additional case in 1 million, 1E-06):

Older Published Criteria for Water and

Organisms: 1000 ug/L [689]. The

Environmental Protection Agency (EPA) has

determined that the level of copper in

water (lakes, streams) should be limited

to 1 ppm to protect human health from the

toxic properties of copper ingested

through water and contaminated aquatic

organisms [979]. Older IRIS Recalculated

(9/90) Criteria for Water and Organisms:

1300 ug/L [446,689]. 

IRIS Recalculated (9/90) Criteria for

Organisms Only: None

Bureau of Land Management RMC Benchmarks, 1995:

Risk Management Criteria (RMC) developed for the

mostly dry BLM lands in the western U.S. These

risk management criteria should be used by the land

manager as a cautionary signal that potential

health hazards are present and that natural

resource management or remedial actions are

indicated [715]. Exceedances of the criteria

should be interpreted as follows [715]:

Less than criteria: low risk

1-10 times the criteria: moderate risk

10-100 times the criteria: high risk

>100 times the criteria: extremely high

risk

Human RMC (BLM) criteria for copper in surface

waters. These categories of humans not

exposed to surface waters with concentrations

of copper exceeding the below RMCs are not

expected to experience adverse toxic effects
[715]:

Camp host: 11,490 ug/L

Child Camper: 10,522 ug/L

Boater: 41,035 ug/L

Swimmer: 17,768 ug/L

Human RMC (BLM) criteria for copper in ground

water. These categories of humans not exposed

to ground waters with concentrations of copper

exceeding the below RMCs are not expected to

experience adverse toxic effects [715]:

Child resident (living on properties

adjacent to BLM lands): 18 ug/L

Camp host: 137 ug/L

Child Camper: 377 ug/L

Worker: 287 ug/L

Surveyor: 2872 ug/L

State drinking water standards: the lowest listed are

Kansas and Rhode Island (1000 ug/L) and Minnesota (1300

ug/L) [979].

Other Listing of State Drinking Water Standards [609]:

(AZ) ARIZONA 1000 ug/l [USEPA/Office of Water;

Federal-State Toxicology and Risk Analysis

Committee (FSTRAC). Summary of State and Federal

Drinking Water Standards and Guidelines (11/93)].

(IL) ILLINOIS 5000 ug/l /Standard applies only to

source water sample/ [USEPA/Office of Water;

Federal-State Toxicology and Risk Analysis

Committee (FSTRAC). Summary of State and Federal

Drinking Water Standards and Guidelines (11/93)].

State Drinking Water Guidelines [609]:

(AZ) ARIZONA 1300 ug/l [USEPA/Office of Water;

Federal-State Toxicology and Risk Analysis

Committee (FSTRAC). Summary of State and Federal

Drinking Water Standards and Guidelines (11/93)].

(MA) MASSACHUSETTS 1300 ug/l [USEPA/Office of

Water; Federal-State Toxicology and Risk Analysis

Committee (FSTRAC). Summary of State and Federal

Drinking Water Standards and Guidelines (11/93)].

(MN) MINNESOTA 1000 ug/l [USEPA/Office of Water;

Federal-State Toxicology and Risk Analysis

Committee (FSTRAC). Summary of State and Federal

Drinking Water Standards and Guidelines (11/93)].
W.Misc. (Other Non-concentration Water Information):

Domestic wastewater is the major anthropogenic source of

copper in waterways. Louis showed discharges of copper

into sewer systems from residential areas to be

significant, with an average loading of 42 mg/day/person

[979].

In some Colorado settings, net-spinning caddisflies were

shown to be more sensitive to predation when copper is

present (Will Clements, Colorado State University,

personal communication, 1994). Thus, direct toxicity is

only one of the many types of impact which copper can

have on aquatic life, and some of the indirect forms of

impact relate to tolerance mechanisms.

Lakes and reservoirs recently treated with copper

compounds to control algae or receive cooling water from

a power plant may have high concentrations of dissolved

copper [979]. Once in natural water, much of this copper

soon attaches to particles or converts to forms that

cannot easily enter the body [979].

As most adult fish are able to tolerate relatively high

concentration of copper for short periods of time, the

critical effect of copper is its greater toxicity to

younger fish [302].

Increased synthesis of metallothionein in response to

copper exposure may help animals (including fish) acquire

a somewhat increased tolerance of this metal [180].

Colloids can potentially play a role in copper toxicity,

at least from the standpoint of colloidal iron hydroxide

in the water column and on the bottom attracting toxic

compounds such as copper and zinc, then moving those

toxic compounds to bottom habitats or far downstream (in

either case this provides movement of toxics into

proximity of new biota and they can be mobilized later by

changes in pH, after exposure to air and chemical

changes. Perhaps the spring toxicity seen at Soda Butte

Creek in Yellowstone related partly to colloidal and

other changes going on the bioassay cups? In the field,

we might expect spring toxicity to relate to rapid

mobilization of metals from formerly dry stream banks and

other spring flushing aspects (Roy Irwin, National Park

Service, personal communication, 1997]. 

In metals avoidance experiments, fish can detect and

avoid metals even if the metals are attached to colloidal

particles. Colloidal transport into the food chain can

be very important. Bio-film: the slime layer on rock

increases in metals due to colloids and presence of
bacteria. Scraper and grazer invertebrates are eating the

whole thing; the periphyton, bio-film, and colloidal

metals. Metals are typically highest in sediments and

bio-film. Herbivores are high in metals after feeding

feed on slime layers. Small filter feeders get more

metals; so fish that feed on small invertebrates get more

metals too, and this is often the smallest (first 100 mm

of growth) immature fish which are at a vulnerable stage.

(Don Woodward, USGS, personal communication, 1996).

Algae filter out colloids and the colloids settle on

rocks. Iron fixing bacteria are important. The orange

bottom is the collection of colloidal material. Colloids

become part of the food chain, can serve as toxic metal

storage medium. Metals can coat benthic invertebrates

eaten by fish. Seasonal variation: high flows flush out

colloids first; zinc and copper can double in

concentration in a storm. New areas are inundated by

high water, colloids and metals in general (some now in

more bioactive form) are now mobilized and can cause

spikes in toxicity. There are good reasons to think that

the colloids can affect chronic toxicity. Annual and

seasonal flushes may relate to spring toxicity. Colloids

can interact with sewage discharges (Briant Kimball,

USGS, personal communication, 1996). 

Dissolved metals are critical to fish and invertebrates,

but the possibility of having colloidal material present

means there is a readily available supply of metals in a

state in which the metals can quickly be reduced and/or

mobilized. In river banks, reducing environments form

just under the surface quickly. Toxic metals of concern

would include zinc, lead, copper, and cadmium. Colloidal

metals may effect biota more than is widely recognized.

Brown trout are effected by colloids which travel kind of

like dissolved fractions, don't settle out. There may be

little understood colloidal pathways of metals to fish,

for example. Colloidal metals become part of the caddis

fly cast. Once the cast is in the acidic fish stomach or

gut, metals can be released. On the Arkansas River of

Colorado below Leadville, the dissolved metals have gone

down with treatment, but Will Clements of CSU has

discovered the toxicity has not been reduced to the same

extent as have the dissolved metals. Treatment has not

eliminated colloidal fractions loaded with cadmium and

copper, and this is possibly impacting the fish. In

rivers, there is often annual flushing of the colloids,

loads are much greater during runoff. Colloids do move

in surface water, 140 miles downstream of Leadville, CO

for example, but also in groundwater (Briant Kimball,

USGS, personal communication, 1996).

Copper is not entirely removed in POTWs, and releases

from these facilities contribute ~8% of all copper
released to water [979]. Inputs into the Narraganset Bay,

Rhode Island, in decreasing order of importance, are:

sewage effluent, rivers, urban runoff, and atmospheric

fallout [979]. Ninety percent of both dissolved and

particulate copper was from effluent of sewage treatment

plants that discharged into the Providence River [979].

While copper is removed from the waste stream by sewage

treatment facilities, considerable copper remains in the

effluent and is released into receiving waters [979]. The

range of removal efficiencies reported for pilot and full

scale plants suggests that removal depends strongly on

plant operation or influent characteristics [979]. The

best data on typical POTWs using secondary treatment are

that 55-90% of copper is removed in these plants with a

median and mean removal of 82% [979]. 1980) [979]. By

contrast, those plants using only primary treatment had

a 37% median removal efficiency [979]. A more recent

study focused on heavy metal removal in three POTWs that

received primarily municipal sewage and which used

activated sludge as a secondary treatment [979]. The

study looked at removals in both the primary and

secondary treatment stage [979]. The average removal of

soluble copper and total copper after secondary treatment

was 49- 82% and 83-90%, respectively [979]. The average

copper concentration in the final effluent was 17-102 ppb

[979]. Discharges to water from active mining and milling

are small, and most of the western operations do not

release any water; water is a scarce resource and is

recycled [979]. Discharges from electroplating operations

are either directly to water or indirectly via POTWs

[979]. Runoff from abandoned mines is estimated to

contribute 314 million tons annually [979]. These

discharges are primarily insoluble silicates and sulfides

and readily settle out [979]. Releases from coppercontaining products may be substantial but difficult to

predict [979]. Corrosion of copper in plumbing or

construction may result in direct discharges or runoff

into waterways [979]. Copper and brass production

releases relatively little copper to water [979].

Wastewater generated from mining operations comes from

seepage, runoff from tailing piles, or from utility water

used for mine operation [979].

Hazardous amounts of copper should not leach into

groundwater from sludge, even from sandy soils [979] (see

Soil.general section for details).

A potential complication in comparing contaminants data

is that different investigators have sometimes meant

different things when they put the words "dissolved" or

"total" in front of a reported measurement. In the case

of nutrients, the "dissolved" portion is usually simply

that portion which has passed through a 0.45-micrometer

membrane filter and the "total" measurements implies that
it was not filtered and includes both dissolved and other

forms of the nutrient [141]. However, usage of the words

dissolved and total has not been uniform in the past and

there is still considerable debate about which methods

should truly be considered "dissolved" or "total" (Merle

Schlockey, USGS, personal communication).

Water bodies are often marked by heterogeneity of the

distribution of undissolved materials [691]. The size of

any effects depends on the difference in density of the

undissolved materials and the water, the size of the

particles or bubbles of the materials, and various

hydrodynamic factors such as the degree of turbulence in

the water. Thus, undissolved inorganic materials in

rivers and other natural water-bodies tend to increase in

concentration with increasing depth because the particles

tend to settle [691]. On the other hand, certain

biological detritus may tend to rise towards the surface

of the water because its density is less than that of

water; oils also commonly demonstrate this effect

markedly [691]. The surface microlayer is usually higher

in concentration of many metallic and organic

contaminants than the water column further down. 

If the only change one makes is to use the prefix

"dissolved" rather than the prefix "total" in an

otherwise identical water quality standard, the effect

can be a weakening of the standard related to total

loading of a system. Many contaminants which are not

currently dissolved can become dissolved at a later time,

when encountering different conditions (perhaps

downstream), such as changes in pH, additions of

surfactants or humic substances, bioturbation,

methylating organisms, and various other physical,

chemical, or biological changes.

One problem with relying too heavily on dissolved

fractions of metals is that the dissolved fraction misses

the metals carried by colloids. Colloids were found to

carry toxic metals 140 miles downstream of mining sources

in Leadville, Colorado, to be repeatedly washed from

flood deposited lowlands back into the river year after

year in spring runoff (Briant Kimball, USGS Salt Lake

City, as quoted in U.S. Water News, April 5th, 1995).

See Laboratory section below for EPA generic

(guesstimate) conversion factors to convert total to

dissolved concentrations.

Some environmental toxicologists make the argument that

dissolved metals in surface water and porewaters

represent most of what is bioavailable and thus "total"

metals parameters are not good as a measure of potential

biological effects. This is mostly true in many
situations, but it should be kept in mind that fish and

other aquatic organisms do not typically live in filtered

water and that many fish and other aquatic organisms live

in the sediments and in other situations in which they

come in contact with toxic or otherwise harmful compounds

(as certain colloids, precipitates, oxides, adsorbed

metals), etc. Sometimes the effect of total metals is

partially related to physical or chemical aspects, such

as when ferric oxide coats or covers benthic organisms.

Another factor to consider: contaminants carried

downstream by erosion of bottom sediments or colloids can

be mobilized when they come in contact with different

physical/chemical environments downstream (for example,

a tributary bringing low pH into the system).

Sediment Data Interpretation, Concentrations and Toxicity (All

Sediment Data Subsections Start with "Sed."):

Sed.Low (Sediment Concentrations Considered Low):

Leland and Kuwabara, 1985: In non-polluted areas,

baseline concentrations as low as 5 mg/kg dry weight have

been recorded [177].

In relatively clean sediment, the copper concentration is

50 ppm [979].

Sed.High (Sediment Concentrations Considered High):

Texas: The statewide 90th percentile value was 40 mg/kg

dry weight [7].

Cu can reach several thousand ppm in polluted areas

[979].

Texas Playa Lake Study Sediment Concentrations: Two

feedlot playa lakes had copper concentrations which were

somewhat elevated (42.3 and 35.1 mg/kg dry weight) (Roy

Irwin, National Park Service, personal communication

1992). 

Great Lakes Harbors, EPA 1977: Sediments having

concentrations of copper higher than 50 mg/kg dry weight

were classified as "heavily polluted" [145,347]. Also,

25 to 50 mg/kg dry weight is considered "moderately

polluted" [347,386].

 

Illinois EPA, 1984: Sediments having concentrations

higher than 60.0 mg/kg dry weight were classified as

"elevated" [145]. 

Leland and Kuwabara, 1985: In polluted areas,

concentrations as high as 2000 mg/kg have been recorded
[177].

Highway runoff routed through a detention pond and then

a cypress wetland resulted in much higher sediment levels

of copper in the detention pond (49 ppm) than in the

wetland (3 ppm) [220].

Buffalo Lake National Wildlife Refuge, Texas, Sediment

Concentrations: Copper concentrations in three sediment

samples from the upstream Tierra Blanca Creek site (NRB)

and three sediment samples from the playa lake (PL) offstream site were quite low, all samples being at or below

10 mg/kg dry weight [401]. By contrast, three samples

from the Tierra Blanca Creek site (TRIS) suspected of

being polluted by a large feedlot had higher copper

concentrations (from 25-29 mg/kg dry weight) and the

waste water pond in the feedlot had highly elevated

copper concentrations (81-90 mg/kg). A Mann-Whitney

statistical test showed copper concentrations from the

six samples to be significantly lower than the six

samples known or suspected of being influenced by feedlot

wastes (significant at 0.0051). Copper compounds are

used as a feed additives at some feedlots [401].

Analyses of sewage sludges from 50 publicly owned

treatment works by the U.S. Environmental Protection

Agency (1985): The mean concentration of copper was

562.4 ppm (dry weight) [347].

Analyses of 74 Missouri sewage sludges (1985): The

median for copper was 390 ppm and the range was 45-5,200

[347].

Estuarine and Marine Information:

NOAA National Status and Trends Program (1984-1990)

[698]: High concentration for copper in finegrained sediment (n=233) = 84 ug/g dry weight at

4.6% TOC dry weight. The above concentration was

adjusted for sediment grain-size in the following

way: the raw concentrations were divided by the

fraction of particles less than or equal to 64 um.

"High" NOAA concentrations are equal to the

geometric mean plus one standard deviation on the

log normal distribution [696].

NOTE: Fine-grained sediment would typically

contain more copper than course-grained

sediment, and sediments higher in total

organic carbon (TOC) would typically have more

copper than sediments which are similar except

for being lower in TOC, which is why NOAA and

many others are now normalizing sediment

values for grain size, and reporting TOC.
Sed.Typical (Sediment Concentrations Considered Typical):

Great Lakes Harbors, EPA 1977: Sediments having sediment

concentrations lower than 26.0 mg/kg dry weight were

classified as "non polluted [145]." Guidelines for the

pollution classification of Great Lakes harbor sediments

(1977): A copper value of less than 25 ppm (dry weight)

indicates nonpolluted sediment [347].

International Joint Commission, 1988: The International

Joint Commission considered <21.1 mg/kg dry weight as a

background sediment level [145]. The control site in one

Great Lakes study had a sediment concentration of 10.4

mg/kg dry weight [145].

NOAA National Status and Trends Program (1984-1990)

[698]: Geometric mean for copper in fine-grained

sediment (n=233) = 35 ug/g dry weight at 1.4% TOC dry

weight. The above concentration was adjusted for

sediment grain-size in the following way: the raw

concentrations were divided by the fraction of particles

less than or equal to 64 um. 

NOTE: Fine-grained sediment would typically contain

more copper than course-grained sediment, and

sediments higher in total organic carbon (TOC)

would typically have more copper than sediments

which are similar except for being lower in TOC,

which is why NOAA and many others are now

normalizing sediment values for grain size, and

reporting TOC. 

The range of copper in sediments of eddy drop zones in

(metals-impacted) Soda Butte Creek, Montana, was 15-57

ppm (Andrew Marcus, Montana State University, personal

communication, 1995).

Playa Lake Study Sediment Concentrations: Dry weight

concentrations of copper in two of the four cattle

feedlot-impacted playa lakes (in the Texas Panhandle) Roy

Irwin has studied were not especially elevated (14.6 and

18.6 mg/kg). However, the other two feedlot playa lakes

had copper concentrations which were somewhat elevated

(42.3 and 35.1 mg/kg). By contrast, ephemeral row-crop

agriculture playas had sediment copper concentrations of

11.9, 15.9, 19.1 and 15.9 mg/kg [401].

Sed.Concern Levels, Sediment Quality Criteria, LC50 Values,

Sediment Quality Standards, Screening Levels, Dose/Response

Data and Other Sediment Benchmarks:

Sed.General (General Sediment Quality Standards,

Criteria, and Benchmarks Related to Protection of Aquatic
Biota in General; Includes Sediment Concentrations Versus

Mixed or General Aquatic Biota):

Oak Ridge National Lab, 1994: Risk Assessment

Screening Benchmarks for Sediment Concentrations.

To be considered unlikely to represent an

ecological risk, field concentrations should be

below all of the following benchmarks in mg/kg

(ppm) dry weight [652]:

For CAS 7440-50-8 (Copper, the benchmarks are:

 

EFFECTS RANGE - MEDIAN (NOAA): 270

EFFECTS RANGE - LOW (NOAA): 34 

Other Concern Levels for Sediment Concentrations

(Dry Weight): 

EPA Region 6, 1973: The concentration

proposed by EPA Region 6 as a guideline for

determining acceptability of dredged sediment

disposal was 50 mg/kg [143].

Ontario Ministry of the Environment Freshwater

Sediment Guidelines, 1993: Lowest effect

level: 16 mg/kg dry weight. Severe Effect

Level: 110 mg/kg dry weight [761].

 

Older benchmarks: Ontario, 1978,1986:

The concentration proposed by the Ontario

Ministry of the Environment as a

threshold for evaluations of dredging

projects was 25.0 mg/kg [145]. Ontario

Ministry of the Environment guidelines

for open lake disposal of sediments

(1986): The guideline for copper is 25

ppm [347].

International Joint Commission, 1988: The IJC

suggested sediment concentrations not exceed

background levels of 21.0 mg/kg [145].

AET 1988: The apparent effects threshold

concentrations for copper in sediments

proposed for Puget Sound ranged from 390 mg/kg

dry weight (microtox) to 1300 mg/kg dry weight

(amphipods) [416]. 

NOTE: Although the authors of the Puget

Sound AETs have cautioned that Puget

Sound AETs may not be appropriate for

comparison with data from other

geographic areas, so few concern levels

for this chemical have been published
that the proposed Puget Sound concern

level is included in this text as an item

of interest.

NOAA 1995 Concern Levels for Coastal and

Estuarine Environments: After studying its

own data from the National Status and Trends

Program as well as many literature references

concerning different approaches to determining

sediment criteria, NOAA suggested that the

potential for biological effects of this

contaminant sorbed to sediments was highest in

sediments where its concentration exceeded

the 270 ppm dry weight Effects Range-Median

(ERM) concentration and was lowest in

sediments where its concentration was less

than the 34 ppm dry weight Effects Range-Low

(ERL) concentration [664]. To improve the

original 1990 guidelines [233], the 1995

report included percent (ratios) incidence of

effects for ranges below, above, and between

the ERL and ERM values. These numbers

represent the number of data entries within

each concentration range in which biological

effects were observed divided by the total

number of entries within each range [664]:

<ERL 9.4

ERL-ERM 29.1

>ERM 83.7 

Wisconsin interim criteria for sediments from

Great Lakes harbors for disposal in water

(1985): Copper should not exceed 100 ppm (dry

weight) [347].

St. Lawrence River Interim Fresh Water

Sediment Criteria, 1992: No effect: 28 mg/kg

dry weight. Minimal effect: 28 mg/kg dry

weight. Toxic effect 86 mg/kg dry weight

[761].

Environment Canada Interim Sediment Quality

Assessment Values, 1994. Threshold effect

level: 35.7 mg/kg dry weight. Probable

effect level: 196.6 mg/kg dry weight [761]. 

Guidelines for the pollutional classification

of Great Lakes harbor sediments (1977): A

copper value of less than 25 ppm (dry weight)

indicates nonpolluted sediment, a copper value

between 25-50 ppm (dry weight) indicates

moderately polluted sediment, copper values

above 50 ppm (dry weight) indicate heavily
polluted sediment [347,761].

Guideance for New York Freshwater Dredging,

1994: A copper value of less than 16 ppm (dry

weight) indicates nonpolluted sediment, a

copper value between 16-110 ppm (dry weight)

indicates moderately contaminated sediment,

and copper values above 110 ppm (dry weight)

indicate heavily contaminatged sediment [761].

Sed.Plants (Sediment Concentrations vs. Plants):

No information found.

Sed.Invertebrates (Sediment Concentrations vs.

Invertebrates):

In a study of the Trinity River, crayfish, turtles,

and clams tended to be higher in copper than fish

at identical sites [201]. A nationwide study of

copper in bivalves showed less variation in levels

from various locations than from various species

[62]. The number of insect and macroinvertebrate

species is very sensitive to the degree of exposure

to elevated levels of copper [110,111]. Sediment

concentrations of copper from Trinity River sites 9

through 12 downstream of Dallas exceeded the

statewide 90th percentile level, 40.0 mg/kg, in at

least 50% of the historical records from 1974 to

1985 [7]. 

Sed.Fish (Sediment Concentrations vs. Fish):

Fish living or foraging in contaminated sediments

may accumulate it directly from the sediments [95].

In a study of the Trinity River, crayfish, turtles,

and clams tended to be higher in copper than fish

at identical sites [201].

Sed.Wildlife (Sediment Concentrations vs. Wildlife or

Domestic Animals):

Bureau of Land Management RMC Benchmarks, 1995:

Risk Management Criteria (RMC) were developed for

the mostly dry BLM lands in the western U.S. These

risk management criteria should be used by the land

manager as a cautionary signal that potential

health hazards are present and that natural

resource management or remedial actions are

indicated [715]. Exceedances of the criteria

should be interpreted as follows [715]:

Less than criteria: low risk
1-10 times the criteria: moderate risk

10-100 times the criteria: high risk

>100 times the criteria: extremely high

risk

Wildlife criteria for copper in soils and

sediments. Wildlife not exposed to

soils/sediments with concentrations of copper

exceeding the below RMCs are not expected to

experience adverse toxic effects [715]:

Rabbit: 77 mg/kg

 Bighorn Sheep: 16 mg/kg

 Whitetailed Deer: 38 mg/kg

 Mule Deer: 47 mg/kg

 Elk: 39 mg/kg

 Mallard: 119 mg/kg

 Canada Goose: 111 mg/kg

 Trumpeter Swan: 120 mg/kg

Sed.Human (Sediment Concentrations vs. Human):

No information found.

Sed.Misc. (Other Non-concentration Sediment Information):

Sediment is an important sink and reservoir for copper

[979]. The form of copper in the sediment will be sitespecific [979]. Organics (humic substances) and iron

oxides are the most important contributor to binding of

copper by aerobic sediments [979]. However, in some

cases, copper is predominantly associated with carbonates

[979]. In anaerobic sediment, Cu(II) will be reduced to

Cu(I) and insoluble cuprous salts will be formed [979].

In sediments of (metals-impacted) Soda Butte Creek,

Montana (NE corner of Yellowstone Park) copper

concentrations were highest in attached bars and lowest

in low gradient riffles. Copper concentrations were

found in the following habitats in order of highest

sediment concentrations to lowest sediment

concentrations: attached bars, backwater pools, high

gradient riffles, lateral scour pools, detached bars,

glides, and low gradient riffles. There was no

significant difference up and downstream within each

micro-habitat sub-unit (attached bars, glides, low

gradient riffles, etc.). There was no significant

difference in lateral variation (right side of stream,

middle, left side) within each micro-habitat sub-unit

(Andrew Marcus, Montana State University, personal

communication, 1995). 

In sediments of (metals-impacted) Soda Butte Creek,
Montana (NE corner of Yellowstone Park) copper

concentrations were higher in the fall than in the

spring; more metals seemed to be carried on the down-side

of flood events than during the event (Del Nimmo, NBS,

personal communication, 1995).

A cycle of bio-mobilization of sedimentary copper by

algae, followed by movement of the algae downstream and

return of the copper to the sediments when the algae

dies, may play a role in moving copper downstream [95].

Highway runoff routed through a detention pond and then

a cypress wetland resulted in much higher sediment levels

of copper in the detention pond than in the wetland

[220]. The same study indicated that copper deposits

near the outlet of a freshwater wetland were lower than

those in the middle [220].

General notes related to interpretation of copper

sediment data vs. AVS and SEM:

Copper sulfides have gotten quite a bit of

attention in environmental toxicology related to

their tendencies to bind copper in the sediments

and the relationship of sulfides to acid mine

drainage. The primary ores of copper are

chalcopyrite (CuFeS2) and chalcocite (Cu2S) [495].

For some metals, copper for example, acid volatile

sulfides are not consistently predictive of

bioavailability in freshwater sediments and may not

be as good for such predictions of toxicity as are

pore water concentrations (Bill Brumbaugh, Columbia

National Fisheries Contaminant Research Center,

Fish and Wildlife Service, personal communication,

1992). 

A 1993 paper confirmed that Acid Volatile Sulfides

alone is not an appropriate partitioning phase for

predicting copper bioavailability in freshwater

sediments [496]. A more recent paper suggests that

Simultaneously Extracted Metals (SEM) to AVS ratios

(SEM:AVS), and the spatial and temporal variability

of AVS, should be considered in sediment toxicology

and may be important in bioavailability dynamics

[981]. The AVS normalization hypothesis, which

predicts greater bioavailability of metals (such as

copper and zinc) at SEM:AVS ratios of greater than

1.0 seems generally useful in some cases but has

several important limitations [981].

In early 1995, proposals were circulating in EPA

suggesting that lower bound metals sediment

criteria be developed along the following line: if
sufficient AVS is present [that is, the total

simultaneously extracted metal (SEM) is equal or

less than the concentration of AVS, then no effects

are expected [700]. If SEM exceeds AVS, then other

binding phases become important; the next most

important phase is organic carbon (TOC) [700]. EPA

now suggests that AVS be conducted in combination

with interstitial water, particularly if effects

are seen when AVS criteria are not exceeded [700].

Some have argued that AVS is not necessary for

biological assessment work because significant AVS

presence reflects anoxic conditions and AVS tends

to go to zero when exposed to oxygen. Great care

must be taken when collecting sediment samples for

AVS not to expose them to air. Since most living

things require oxygen, if there is no oxygen there

are few if no living things so why use AVS to look

at toxicity aspects (Tom O'Connor, NOAA, personal

communication, 1995)?

Others would respond that it seems to work as a

toxicity normalization parameter anyway, and point

out that certain invertebrates, bacteria, etc. do

live in low oxygen conditions in sediments. For

mid to high range levels of AVS, exposure to air

while sampling does not seem to critical, though

head space in the jar should be minimized. As of

October, 1995, the EPA method for AVS (method

376.3, similar but different from older reactive

sulfide methods) was still a draft. AVS detection

limits should be down in the 3 ppm range (~0.1

micro mole); any lower than that and the problems

of lack of buffering and field contamination of

samples by air or redox changes become more

critical (Bill Brumbaugh, Columbia Lab, NBS,

personal communication, 1995).

When sulfide is present, as it is in estuarine

sediments rich in organic debris, it will combine

with metals such as copper, cadmium, zinc, and

lead. The metal sulfides that form are highly

insoluble and will tend to be sequestered in the

sediments (Bender M, 1989, Heavy metals in

Narragansett Bay sediments. MARITIMES, 33 (4): 5-7.

Off. Mar. Programs, Mar. Resour. Build., URI

Narragansett Bay Campus, Narragansett, RI 02882-

1197, USA) [940].

Soil Data Interpretation, Concentrations and Toxicity (All Soil

Data Subsections Start with "Soil."):

Soil.Low (Soil Concentrations Considered Low):
The low for copper in U.S. soils was 1 ppm [347].

Soil.High (Soil Concentrations Considered High):

Copper in German Gulch (highly polluted Upper Clark Fork

Superfund Site Area, Montana) samples ranged from 58.6 to

236.5 ppm and averaged 148.4 ppm [699].

Copper concentrations close to 7000 ppm have been found

near copper production facilities [979]. High

concentrations of copper may be found in soil because

dust from these industries settles out of the air, or

waste from mining and other copper industries are

disposed of on the soil [979]. Another common source of

copper in soil results from spreading sludge from sewage

treatment plants [979]. This copper generally stays

strongly attached to the surface layer of soil [979]

Analyses of sewage sludges from 50 publicly owned

treatment works by the U.S. Environmental Protection

Agency (1985): The mean concentration of copper was

562.4 ppm (dry weight) [347].

Analyses of 74 Missouri sewage sludges (1985): The

median for copper was 390 ppm and the range was 45-5,200

[347].

Soil.Typical (Soil Concentrations Considered Typical):

The national average concentration for copper in U.S.

soils is 30 mg/kg [98]. 

A 1984 survey: average copper concentrations in soil

[979]:

25 ppm agriculural land

50 ppm suburban/residential land

100 ppm industrial land mixed with residential

175 ppm inner city and industrial

Western U.S. Soil Median Concentrations [715]: 27 mg/kg.

Analyses of sewage sludges from 50 publicly owned

treatment works by the U.S. Environmental Protection

Agency (1985): The mean concentration of copper was

562.4 ppm (dry weight) [347].

Analyses of 74 Missouri sewage sludges (1985): The

median for copper was 390 ppm and the range was 45-5,200

[347].

Soil generally contains between 2 and 250 ppm copper

[979].
Based on recent compilations of estimates, the average

natural copper concentration in soil ranges from 20 to 30

ppm (Baker, 1990) [699]. Generally, copper

concentrations reported for various soil types (sandy

soil and podzols, silty soils, loamy and clay soils,

rendzinas, chernozems, histosols, and other organic

soils) range from 1 to 100 ppm (Kabata-Pendias and

Pendias, 1992) [699]. Copper concentrations typically

are lowest in soils formed by granitic, igneous, or

carbonate parent materials. Kabata-Pendias and Pendias

(1992) cite 13-24 ppm as the average copper concentration

in soils of the United States, and Adriano (1986) cites

25 ppm as an average value for naturally occurring copper

in the U.S. soils [699].

Typical Soil Concentrations according to EPA 1981: 20

mg/kg dry weight [83].

Averages and ranges of concentrations of elements in

soils and other surficial materials in the United States

(1971): The mean for copper was 25 ppm and the range was

between 1 and 300 ppm [347].

Typical Igneous Rocks (Earth's Crust) Concentrations:

Average concentration in the earth's crust is about

50 parts copper per million parts soil (ppm) [979].

55 mg/kg dry weight [83]. 

70 parts per million of the Earth's [280,366].

Copper is present in concentration(s) averaging

about 4 ppm in limestones, 55 ppm in igneous rocks,

50 ppm in sandstones, and 45 ppm in shales [366]. 

The copper content of ore deposits ranges from 0.5-5% by

weight, whereas igneous rock contains 0.010% (Duby 1980)

and crystalline rock, 0.0055% by weight (55 ppm) [979].

Soil.Concern Levels, Soil Quality Criteria, LC50 Values, Soil

Quality Standards, Screening Levels, Dose/Response Data and

Other Soil Benchmarks:

Soil.General (General Soil Quality Standards, Criteria,

and Benchmarks Related to Protection of Soil-dwelling

Biota in General; Includes Soil Concentrations Versus

Mixed or General Soil-dwelling Biota):

Other Maximum Acceptable Concentration (MAC) levels

in ppm dry weight: 100 (Stuttgart, Germany), 50

(London-value given for soluble pool of the

element), 140 (London-value given for soluble pool

of the element) [719].
Proposal of European Economic Commission for MAC in

soils treated with sewage sludge: 50 (100) ppm dry

weight (London). Value in parentheses are

mandatory concentration [719].

Proposal of Ontario Ministry of Agriculture and

Food for MAC in soils treated with sewage sludge:

100 ppm dry weight (published in Tokyo; work done

for Ontario) [719].

The 1987 soil (clean up) criteria given by the New

Jersey Department of Environmental Protection for

copper is 170 mg/kg (ppm) dry weight [347,386].

In 1981 the U.S. Environmental Protection Agency

proposed 1000 ppm as an upper limit for copper for

sewage sludges suitable for land application [391].

Soil criteria for evaluating the severity of copper

contamination under the Dutch Soil Cleanup

(Interim) Act (1982): The background concentration

of copper is 50 ppm, moderate soil contamination is

100 ppm, and threshold value is 500 ppm [347].

Soil cleanup criteria for decommissioning

industrial sites in Ontario (1987): For

agricultural land copper should not exceed 100 ppm,

for residential or parklands copper should not

exceed 300 ppm, for commercial or industrial land

copper should not exceed 300 ppm [347].

Suggested cleanup guidelines for inorganic

contaminants in acidic soils in Alberta (1987):

The acceptable level of copper for acidic soils (pH

<6.5) is 200 ppm [347].

Maximum cumulative addition of metals (kg/ha) from

sewage sludge to Maryland agricultural soil (1986):

For a soil with a cation exchange capacity of less

than 5 meq/100 g copper addition should not exceed

140, for a soil with a cation exchange capacity of

greater than 5 copper addition should not exceed

280 [347]. The numbers are the same for addition

of metals from sewage sludge to Massachusetts

agricultural soil (1983) [347]. 

Maximum cumulative addition of metals from sewage

sludge that may be added to Minnesota soils used

for growing food crops (1987): For a soil with a

soil cation exchange capacity (CEC) of less than 5

meq/100 g copper should not be added at greater

than 140 kg/ha, for a soil with a soil CEC between

5 and 15 meq/100 g copper should not be added at

greater than 280 kg/ha, and for a soil with a CEC
greater than 15 copper should not be added at

greater than 560 kg/ha [347]. These values are the

same for addition of metals to privately owned

Missouri farmland (1988).

Cumulative amounts of metals per hectare that may

be added to New York State soils with sewage sludge

(1988): For productive agricultural soils copper

should not be added at greater than 84 kg/ha, for

less productive agricultural soils copper should

not be added at greater than 125 kg/ha, and for

forests copper should not be added at greater than

280 ppm [347].

Maximum heavy metal loading (kg/ha) recommended for

sludge applications to privately owned Oregon

farmland (1984): For a soil with a cation exchange

capacity (CEC) of less than 5 meq/100 g copper

should not be added at greater than 125 kg/ha, for

a soil with a CEC between 5 and 15 copper should

not be added at greater than 250 kg/ha, for a soil

with a CEC greater than 15 copper should not be

added at greater than 500 kg/ha [347].

Maximum cumulative additions (kg/ha) of metals from

sewage sludge that may be added to Vermont soils,

by soil texture (1984): For loamy sand copper

should not be added at greater than 140 kg/ha, for

fine sandy loam copper should not be added at

greater than 280 kg/ha, and for clay loam copper

should not be added at greater than 560 kg/ha

[347].

Maximum cumulative applications (kg/ha) of copper

from sewage sludge that may be added to Wisconsin

soils (1985): For a soil with a cation exchange

capacity (CEC) of less than 5 meq/100 g copper

should not be added at more than 125 kg/ha, for a

soil with a CEC between 5 and 10 copper should not

be added at greater than 250 kg/ha, for a soil with

a CEC between 11 and 15 copper should not be added

at greater than 375 kg/ha, and for a soil with a

CEC greater than 15 copper should not be added at

greater than 500 kg/ha [347].

Soil limit values determined by the Council of

European Communities for the addition of heavy

metals from sewage sludge to soil with a pH of 6.0

to 7.0 (1986): The limit value for copper is 50-

140 ppm [347].

Concern or Regulatory Levels for Soil

Concentrations of Copper Extractable with Ammonium

Acetate Buffer (mg/kg dry weight):
Soviet Union Maximum Allowable Concentration

in Soils, 1984: 3.0 mg/kg [347].

In laboratory experiments, three sludges containing

51, 66, and 951 ppm (dry weight) of copper were

applied to soil columns containing four coastal

plain soils [979]. The columns were subsequently

leached with distilled water at a rate of 2.5

cm/day for a total column application of 25.4 cm of

water [979]. Only small amounts (less than 0.01-

0.87 ppm) of copper were found in the leachate

(Ritter and Eastburn 1978) [979]. This indicates

that hazardous amounts of copper should not leach

into groundwater from sludge, even from sandy soils

[979]. In another study, soil cores taken after

sewage sludge was applied to grassland for 4 years

showed that 74% and 80% of copper remained in the

top 5 cm of a sandy loam and calcareous loam soil

[979]. Similarly, copper remains in the surface

layer when it is applied to soil as a liquid [979].

Soil.Plants (Soil Concentrations vs. Plants):

Some grasses around copper polluted areas are

copper tolerant [366].

Levels of copper (ppm dry weight) considered

phytotoxic: 100 (Vienna), 100 (Warsaw), 125

(Tokyo), 100 (Warsaw), 60 (Missouri), 100 (Ontario)

[719] 

Minimum soil concentration causing phytotoxicity:

60-125 [699].

At 400 ppm copper in the soil, several crops have

symptoms; at 15-30 ppm, citrus crops had effects;

spinach and gladiolus affected at 98-130 ppm, and

clover and alfalfa most sensitive of crops tested

[670].

Oak Ridge National Lab, 1994: Risk Assessment

Screening Benchmarks for Terrestrial Plants. To be

considered unlikely to represent an ecological risk

to terrestrial plants, field concentrations in soil

should be below the following dry weight benchmark

for soil [651]:

For CAS 007440-50-8 (COPPER), the benchmark is

100 mg/kg dry weight in soil.

 

Density and biomass of certain grasses in meadows

of Soda Butte Creek (NE Yellowstone Park) seemed to

be reduced at copper soil concentrations (dry
weight) above 250 ppm (Julie Stoughton, Montana

State University, personal communication, 1995). 

 Some plants accumulate copper at high levels, with

low growing grasses generally having the highest

concentrations and tree foliage the lowest. The

major route of uptake appears to be from soil

rather than direct atmospheric deposition, since

copper is unlikely to be transported across leaf

cuticles. Radishes grown in controlled environments

in soils taken from areas of atmospheric deposition

exhibited elevated copper levels. Plants grown on

soils from areas closest to smelters exhibited

decreased growth but growth was improved by

addition of lime, presumably because higher soil pH

decreased metal solubility and uptake [366].

See also Soil.Misc section.

Soil.Invertebrates (Soil Concentrations vs.

Invertebrates):

The concentration of copper in earthworms is

correlated with soil concentrations, which may be a

consideration relative to birds feeding on sewage

sludge amended soils [179]. However, although

earthworms can usually live in metals contaminated

soils, copper is somewhat more toxic to them than

most metals and earthworms have been eliminated

from soils due to copper contamination [347]. 

Soil.Wildlife (Soil Concentrations vs. Wildlife or

Domestic Animals):

See also the Bureau of Land Management (BLM) Risk

Management Criteria (RMC) Benchmarks from [715] in

the Sed.Wildlife section above. 

The concentration of copper in earthworms is

correlated with soil concentrations, which may be a

consideration relative to birds feeding on sewage

sludge amended soils [179]. 

Soil.Human (Soil Concentrations vs. Human):

Acceptable level of copper for production of

healthy food: 23 (value given for soluble pool of

the element) ppm dry weight (Moscow) [719]. 

Bureau of Land Management RMC Benchmarks, 1995:

Risk Management Criteria (RMC) were developed for

the mostly dry BLM lands in the western U.S. These

risk management criteria should be used by the land
manager as a cautionary signal that potential

health hazards are present and that natural

resource management or remedial actions are

indicated [715]. Exceedances of the criteria

should be interpreted as follows [715]:

Less than criteria: low risk

1-10 times the criteria: moderate risk

10-100 times the criteria: high risk

>100 times the criteria: extremely high

risk

Human RMC criteria for copper in soil. These

categories of humans not exposed to soil with

concentrations of copper exceeding the below

RMCs are not expected to experience adverse

toxic effects [715]:

 Child resident (living on properties

adjacent to BLM lands): 74 mg/kg

Camp host: 1915 mg/kg

Child Camper: 1319 mg/kg

ATV Driver: 26929 mg/kg

Worker: 2872 mg/kg

Surveyor: 28724 mg/kg

Soil.Misc. (Other Non-concentration Soil Information):

Hazardous amounts of copper should not leach into

groundwater from sludge, even from sandy soils [979] (see

Soil.general section for details). 

Secondary sewage effluent spiked with 0.83 ppm of copper

was applied weekly to four different soils [979]. After

1 year of treatment, the concentration of copper in the

surface horizons increased greatly; 50-76X of applied

copper was found in the upper 2.5 cm and 91-138X was

found in the upper 12.7 cm [979].

Soil fertilization with copper has been used in Australia

& New Zealand but was ineffective in a high molybdenum

area in Nevada in reducing molybdenum or increasing

copper content of feeds. Treatment of pasture or crops

with copper has not been extensively used in the USA

[366].

Editor's note: According to an article in the Bozeman

(Montana) Daily Chronicle Newspaper of December 30, 1996,

increasing soil pH by adding lime, a remediation

sometimes used to reduce soil acidity and reduce the

mobility of metals such as copper, can result in the

(unintended) consequence of increasing the mobility of

arsenic and its transport to groundwater. The article
stated that Bill Inskeep, soil scientist at Montana State

University had seen an increase of arsenic percolation of

10 to 100 times after lime was added to arsenic

contaminated soils (News Media Report, not yet

independently confirmed, but included since lime is such

a common treatment for acidic metals contaminated soils).

Tissue and Food Concentrations (All Tissue Data Interpretation

Subsections Start with "Tis."):

Tis.Plants:

A) As Food: Concentrations or Doses of Concern to Living

Things Which Eat Plants:

A level of copper in alfalfa possibly toxic to

cattle is 115 ppm dry weight [739]. Alfalfa grown

in contaminated water downstream of Summitville

Mine, Colorado was slightly elevated above the 10

ppm dry weight copper dietary requirement for

cattle, but was still far below the 115 ppm concern

level for cattle [739].

B) Body Burden Residues in Plants: Typical, Elevated, or

of Concern Related to the Well-being of the Organism

Itself:

Copper plant tissue concentrations at the (highly

polluted) Smelter Hill (Upper Clark Fork Superfund

Site Area, Montana) site averaged 91.87 (ranging as

high as 467 ppm in horsebrush). Levels in unimpacted plants generally range between 1.5 and 30

ppm (CH2M Hill, 1987b, as cited in PTI, 1991a)

[699].

The following ranges of concentrations of copper in

plants (dry weight) were found in samples collected

along metals-impacted Soda Butte Creek in

Yellowstone Park in 1992 (Daniel Norton, USGS,

personal communication, 1995):

Grasses: 2.9 to 10 ppm

Lichen: 26.9 ppm (one sample)

Moss: 21.1 to 62 ppm

Willow: 4 to 11 ppm 

The contents of copper, molybdenum, sulphur, zinc,

selenium, iron, manganese, and the

copper/molybdenum ratio were determined in

different native plant species from a mountain area

of central southern Norway. The overall mean

values and ranges (mg/kg DM) were copper: 6.0,

0.9-27.2; molybdenum: 0.25, 0.01-3.57; zinc: 77, 8-

320; selenium: 0.05, less than 0.01-0.32; iron:
208, 15-2245; manganese: 338, 31-3784; sulfur:

(g/100 g DM) 0.20, 0.03-0.56; copper/molybdenum:

79, 1-7955. Levels of the individual elements

showed considerable variability, both between and

within plant groups. Mineral contents were

compared with the established requirements for

sheep and cattle, the following conclusion being

drawn. The levels of zinc, sulphur, iron, and

manganese were found to be adequate for ruminants

(Garmo TH et al; Acta Agric Scand 36 (2): 147-161,

1986) [609].

Willows and grasses downstream of Montana mining

areas tended to uptake some heavy metals (copper,

lead) in polluted areas to a greater degree than

farther downstream: results for zinc were

inconclusive, and levels of various metals in moss

and lichens tended to be much higher than willow

and grass (Daniel Norton, USGS, personal

communication, 1995). 

Both tree lichens and mosses are capable of

absorbing large quantities of metals and have been

used to map zones of impact from air pollution, so

the USGS has been developing baseline levels for

these plants [739].

Tis.Invertebrates:

A) As Food: Concentrations or Doses of Concern to Living

Things Which Eat Invertebrates:

Note: In humans, some oral intake of copper is

necessary for good health, but massive doses

can cause problems, especially for children

[979].

Legal Limits for Concentrations in Fish and Fishery

Products (these levels relate mostly but not

totally to fish, since fishery products includes

some general seafood and/or invertebrates in some

countries): The lowest legal limit is 10 mg/kg

(Venezuela, India, Ecuador, Chile) [216,418]. Nine

countries have limits less than or equal to 70

mg/kg, but the U.S. apparently has no limit

[216,418]. The Australian National Health and

Medical Research Council recommends 30 mg/kg copper

as a maximum content for seafood products [84].

B) Concentrations or Doses of Concern in Food Items

Eaten by Invertebrates:

No information found.
C) Body Burden Residues in Invertebrates: Typical,

Elevated, or of Concern Related to the Well-being of the

Organism Itself:

Accumulation of copper in a population of the

grasshopper, Chorthippus brunneus, from grasslands

around a copper refinery complex (0.75 sq km

divided into four sites) was monitored, and

compared with a control site distant from sources

of metal contamination. A sub-control site in an

unpolluted stabilized sand dune system where the

soil copper concentration was deficient was also

studied. Each site contained similar mixed grass

swards of copper-tolerant Agrostis stolonifera and

Festuca rubra which were the major components of

fecal pellets of refinery site grasshoppers.

Monthly samples of grasses and the insects, adult

and nymphal specimens were obtained for analysis

from June to November (n= >100/species/site).

Monthly mean copper concentrations in A stolonifera

were; (a) refinery sites, 39.4 ug/g to 152 ug/g,

respectively); (b) 1 km site, 16.8 ug/g; and (c)

control respectively); (b) 1 km site, 16.8 ug/g;

and (c) control site, 8.2 ug/g. For F rubra, copper

concentrations were: (a) refinery sites, 26.4 ug/g

to 86.3 ug/g; (b) 1 km site, 20.1 ug/g, and (c)

control site, 7.4 ug/g. For C brunneus

concentrations were: (a) refinery sites, 300 to 380

ug/g respectively); (b) 1 km site, 66.4 ug/g; and

(c) control site 37.5 ug/g. Total body

concentration of Cu in grasshoppers increased with

mean dietary contamination levels; the relationship

was not linear and reached a peak at 50 ug/g of

dietary Cu. Accumulation of Cu in the insects

closely followed the seasonal increase in

contamination levels of the grasses. Copper

accumulated progressively through the instars of

the insects. Nymphs from the refinery sites had

significantly increased copper concentration above

control values for all instars, and the

accumulation seemed to begin soon after hatching.

Concentrations are reduced in newly emerged adults

which suggests some copper is excluded at the final

molt. Both body and integumental concentrations

were significantly elevated in refinery samples

compared to controls, and refinery insects had a

significant elevation of integument over body

copper (Hunter BA et al; Arch Environ Contam

Toxicol 16 (6): 711-6, 1987) [366].

Copper does not accumulate to the same extent in

both oysters and mussels. Therefore, the following

information summarizes data gathered on both

oysters and mussels from the NOAA National Status
and Trends (NS&T) Program for the year 1990 [697]:

For copper in oysters (n=107), the Geometric

Mean was 150 ug/g dry and the "high"

concentration was 360 ug/g dry weight [697].

For copper in mussels (n=107), the Geometric

Mean was 8.9 ug/g dry and the "high"

concentration was 11 ug/g dry weight [697].

NOAA "high" concentrations are equal to the

geometric mean plus one standard deviation on

the log normal distribution [696].

Tis.Fish:

A) As Food: Concentrations or Doses of Concern to Living

Things Which Eat Fish (Includes FDA Action Levels for

Fish and Similar Benchmark Levels From Other Countries):

Note: In humans, some oral intake of copper is

necessary for good health, but massive doses

can cause problems, especially for children

[979].

Legal Limits for Concentrations in Fish and Fishery

Products: The lowest legal limit is 10 mg/kg

(Venezuela, India, Ecuador, Chile) [216,418]. Nine

countries have limits less than or equal to 70

mg/kg, but the U.S. apparently has no limit

[216,418]. The Australian National Health and

Medical Research Council recommends 30 mg/kg copper

as a maximum content for seafood products [84].

The Australian National Health and Medical Research

Council recommends 30 mg/kg copper as a maximum

content for seafood products [84].

Bureau of Land Management RMC Benchmarks, 1995:

Risk Management Criteria (RMC) were developed for

the mostly dry BLM lands in the western U.S. These

risk management criteria should be used by the land

manager as a cautionary signal that potential

health hazards are present and that natural

resource management or remedial actions are

indicated [715]. Exceedances of the criteria

should be interpreted as follows [715]:

Less than criteria: low risk

1-10 times the criteria: moderate risk

10-100 times the criteria: high risk

>100 times the criteria: extremely high

risk

Human RMC criteria for copper in fish consumed
by humans: These categories of humans not

exposed to fish with concentrations of copper

exceeding the below RMCs are not expected to

experience adverse toxic effects [715]:

Child resident (living on properties

adjacent to BLM lands): 2907 ug/kg

Camp host: 5984 ug/kg

Child Camper: 16487 ug/kg

B) Concentrations or Doses of Concern in Food Items

Eaten by Fish:

No information found.

C) Body Burden Residues in Fish: Typical, Elevated, or of

Concern Related to the Well-being of the Organism Itself:

Mean NCBP Levels (Tissue Concentrations): Copper

whole-body levels above 0.9 mg/kg wet weight were

higher than the concentrations of 85% of all fish

samples in a (NCBP) national survey [23]. A more

recent (1976-1984) NCBP survey report gave the

nationwide geometric mean concentration of copper

in composite samples of whole fish as 0.65 mg/kg

wet weight [384].

Edible Tissues (Mostly Fillet) Concentrations for

Copper:

Copper concentrations (1.21 to 7.76 mg/kg) in

muscle samples from the Pecos River near Pecos

National Monument & Historical Park were

consistently higher than copper concentrations

(<0.13 to 0.60) reported for trout collected

upstream in the Fish and Wildlife Service 1991

study of the Terrero Mine waste study area.

For additional comparison, highest

concentrations of copper in 5 studies of

edible fish tissues in several states ranged

from 0.88 to 14.97 mg/kg wwt [57]. 

Copper whole-body levels above 0.9 mg/kg are higher

than 85% of all fish in a NCBP national survey

[23]. This level was exceeded in 9 of 14 Big Bend

National Park tissue samples 65]. Four of the 5

highest Big Bend NP (Rio Grande River) copper

concentrations were from mosquitofish [65]. The

highest fish concentrations in Big Bend collections

were 2.6, 1.6, 1.5 mg/kg, respectively [65]. The

highest concentration (2.6 mg/kg) of copper from

Rio Grande river mosquitofish was higher than was

found in any of 24 mosquitofish samples from the

urbanized upper Trinity River [201]. This finding
is of interest because copper is one of the most

common urban runoff contaminants and therefore

might be expected to be more elevated in the highly

urbanized parts of the upper Trinity than in rural

areas. Gut-contents were not separated from the

above samples [65,201].

The highest concentration of copper found in 32

fish samples from the heavily agricultural areas of

the lower Rio Grande river, far downstream of Big

Bend National Park, was 5.09 mg/kg [202].

In a study of the Trinity River, mosquitofish data

showed no uniform upstream/downstream distribution

trends for copper (unlike other contaminants)

[201]. If they had been more uniformly present,

clams might be a better choice for gradient

monitoring of copper since they have an affinity

for heavy metals and tend to be good indicators of

metal pollution in general [95]. A nationwide

study of copper in bivalves showed less variation

in levels from various locations than from various

species [62]. Crayfish, turtles, and clams tended

to be higher in copper than fish at identical sites

[201]. The seven highest Trinity River

concentrations were from crayfish, turtles, and

clams rather than fish [201]. Nevertheless, copper

concentrations in the lean tissues of mosquitofish,

bullhead minnows, and red-eared slider turtles were

at least slightly higher at the site impacted by

urban runoff and urban point sources than those

from our reference/control site [201]. 

Tis.Wildlife: Terrestrial and Aquatic Wildlife, Domestic

Animals and all Birds Whether Aquatic or not:

A) As Food: Concentrations or Doses of Concern to Living

Things Which Eat Wildlife, Domestic Animals, or Birds:

No information found.

B) Concentrations or Doses of Concern in Food Items

Eaten by Wildlife, Birds, or Domestic Animals (Includes

LD50 Values Which do not Fit Well into Other Categories,

Includes Oral Doses Administered in Laboratory

Experiments):

Oak Ridge National Lab, 1994: Risk Assessment

Screening Benchmarks for Wildlife derived from NoObserved-Adverse-Effect (NOAEL) levels (mg

contaminant per kg body weight per day). To be

considered unlikely to represent an ecological

risk, wet-weight field concentrations should be
below the following (right column) benchmarks for

each species present at the site [650]:

For CAS 7440-50-8, COPPER AS COPPER SULFATE,

the benchmarks are:

 NOAEL FOOD CONCENSPECIES (mg/kg/day) TRATION (ppm)

Mink 11.71000 0.00000

 (test species) 

Short-tailed Shrew 46.82200 78.03600

Little Brown Bat 58.85500 176.56600

White-footed Mouse 41.26300 266.99400

Meadow Vole 32.82600 288.86800

Cottontail Rabbit 11.02600 55.82900

Mink 11.71000 85.47400

Red Fox 7.12800 71.28500

Whitetail Deer 3.09300 100.43200

Comment: Actually, the number of

significant figures for a benchmark value

should never be more than one; even if

these values have been taken directly

from another report, they should be

rounded; otherwise the impression is

given of a level of accuracy that is

simply unwarranted. The uncertainties are

too large to justify such a fine

distinction (Owen Hoffman, SENES Oak

Ridge, Personal Communication, 1997).

A level of copper in alfalfa possibly toxic to

cattle is 115 ppm dry weight [739]. Alfalfa grown

in contaminated water downstream of Summitville

Mine, Colorado was slightly elevated above the 10

ppm dry weight copper dietary requirement for

cattle, but was still far below the 115 ppm concern

level for cattle [739].

There appear to be few predator protection levels

suggested in the literature. However the

concentration of copper in earthworms is correlated

with soil concentrations, which may be a

consideration relative to birds feeding on sewage

sludge amended soils [179]. However, although

earthworms can usually live in metals contaminated

soils, copper is somewhat more toxic to them than

most metals and earthworms have been eliminated

from soils due to copper contamination [347]. 

Increased mortality was observed in rats fed a diet

containing 4000 ppm of copper (133 mg Cu./kg/d)

for 1 week [979]. Anorexia, possibly the result of
taste aversion, contributed to the deaths [979].

Weanling rats exposed to 300 mg Cu/kg/d as Cu(II)

in the diet (6000 ppm) died after 2 weeks [979].

The deaths were attributed to extensive

centrilobular necrosis [979]. 

C) Body Burden Residues in Wildlife, Birds, or Domestic

Animals: Typical, Elevated, or of Concern Related to the

Well-being of the Organism Itself:

Upper Trinity River: (The following text is quoted

from the Trinity River Report [201] for reference

comparison with values from other areas): Copper

concentrations above the detection limit (0.01

mg/kg) were found in 74 of 77 Trinity River

samples. The three samples containing less than the

detection level were from red-eared turtle shells.

Maximum Levels: The highest copper concentrations

were in whole-body samples of spiny softshell

turtles from sites 18 (12.8 mg/kg) and 11 (18.5

mg/kg) and from crayfish from site 5 (25.4 mg/kg)

[201].

 The Japanese serow, a bovine ruminant, is longlived and free-ranging. The animals were killed

during the winter 1981-82 in the Gifu and Nagano

Prefectures, Japan. The Cu concentrations were

measured by flame absorption spectrometry. On a wet

wt basis, the mean Cu concentration in muscle,

liver, kidney, and whole body of fetuses (gestation

age 0.3-0.7 yr, N= 13) were 0.59, 66.4, 3.76, and

2.56 ug/g, respectively; in fawns (age 0.0-0.5 yr,

N= 12), 2.02, 12.0, 2.90, and 1.52 ug/g,

respectively; in yearlings (age 0.5-2.5 yr, N= 6),

1.96, 32.8, 2.80, and 1.75 ug/g, respectively; in

adults (age 2.5 to 10 yr, N= 42), 1.84, 34.1, 2.81,

and 2.15 ug/g, respectively; and in adults (age 10

to 17.5 yr, N= 17), 1.79, 40.5, 2.63, and 2.25

ug/g, respectively. Sex differences were observed

in liver, with significantly higher concentrations

(p< 0.05) in males than in females. The mean Cu

concentration in fleece of fawns, yearlings, and

adults (age 2.5 to 10 yr) was 13.3, 14.8, and 10.6

ug/g, respectively. Bone samples of two adult

serows contained 0.35 to 0.83 ug/g. The body burden

of fetuses was low (<1%) compared with that of

their mothers. The Cu levels were high during

gestation and decreased after birth until about 2.5

yr of age as a result of hepatic accumulation.

There was no significant difference in Cu

concentration between collection locations. The Cu

uptake agreed well with the concentration found in

food plants (Honda K et al; Arch Environ Contam

Toxicol 16: 551-61, 1987) [366].
Tis.Human:

A) Typical Concentrations in Human Food Survey Items:

Copper content in human food was summarized by

ATSDR; unless massive doses are ingested, copper by

this route is usually not a problem [979].

Humans eat and drink about 1 milligram (l/1000 of a

gram) of copper every day [979]. The 1980

Recommended Dietary Allowances estimate that a

daily dietary intake of 2-3 mg Cu/d (0.03-0.04

mg/kg/d) by adults is safe and adequate [979]. The

dietary requirements for copper in rats and pigs is

3-6 mg/kg diet (0.15- 0.30 mg/kg bw/day) and 3-5

mg/kg diet, respectively [979].

B) Concentrations or Doses of Concern in Food Items

Eaten by Humans (Includes Allowable Tolerances in Human

Food, FDA, State and Standards of Other Countries):

Note: In humans, some oral intake of copper is

necessary for good health, but massive doses

can cause problems, especially for children

[979].

See also Tis.Fish, A) section above.

 Legal Limits for Concentrations in Fish and Fishery

Products: The lowest legal limit is 10 mg/kg

(Venezuela, India, Ecuador, Chile) [216,418]. Nine

countries have limits less than or equal to 70

mg/kg, but the U.S. apparently has no limit

[216,418]. The Australian National Health and

Medical Research Council recommends 30 mg/kg copper

as a maximum content for seafood products [84].

Thirteen of 53 patients died after ingesting 6-637

mg/kg copper [979]. Patients provided information

on intakes; thus, the reported doses may be

inaccurate [979]. The deaths were attributed to

shock and hepatic and/or renal complications [979].

The normal diet of humans includes between 2 and 5

mg of copper per day, exceeding the body

maintenance requirements of about 2 mg per day

[280]. Many forms of copper are not very toxic to

humans, with most problems related to human health

reported from individuals who have copper

metabolism disorders or who distill alcohol with

copper tubing [173]. Except for inhalation of

copper dusts, in humans copper itself probably has

little or no toxicity, although there are
conflicting reports in literature [366].

There are numerous reports of acute

gastrointestinal effects in humans after ingestion

of large amounts of copper, in the form of Cu (II)

[979]. Exposure levels that produced these

gastrointestinal effects were 0.07-1421 mg Cu/kg as

Cu (II) [979].

Oral RfD: none given [893].

The average daily dietary intake of copper by an

individual in the United States may range from < 2

to approx 4 mg. For ingestion, the dietary intake

is, in general, an order of magnitude higher than

intake from drinking water, except in rare cases of

consumption of soft water which has been supplied

by copper pipes. In the latter case, intake from

drinking water may be as high as >2 mg/day. /Copper

cmpd/ (USEPA; Health Issue Assessment: Copper p.23,

1987) EPA/600/8-87/001) [609].

The eastern oyster can concentrate copper by a

factor of 28200 and can accumulate so much copper

that they turn bluish green, but even high amounts

consumed by man orally may not be harmful [25].

C) Body Burden Residues in Humans: Typical, Elevated, or

of Concern Related to the Well-being of Humans:

No information found.

Tis.Misc. (Other Tissue Information):

Copper occurs naturally in plants and animals [979].

A number of plants have been described as indicators of

higher-than-normal concentrations of this element in the

soil [951]. A typical ratio of copper concentration from

plants to rock is 0.13 [951]. Bryophytes and lichens

tend to have an especially high ability to absorb trace

elements from their substrates and to tolerate adverse

ecological conditions [951].

Bio.Detail: Detailed Information on Bioconcentration, 

Biomagnification, or Bioavailability:

For a discussion of SEM and AVS issues vs bioconcentration,

see the Sed.Misc. section above.

Some plants accumulate copper at high levels, with low growing

grasses generally having the highest concentrations and tree

foliage the lowest. The major route of uptake appears to be from

soil rather than direct atmospheric deposition, since copper is
unlikely to be transported across leaf cuticles. Radishes grown in

controlled environments in soils taken from areas of atmospheric

deposition exhibited elevated copper levels. Plants grown on soils

from areas closest to smelters exhibited decreased growth but

growth was improved by addition of lime, presumably because higher

soil pH decreased metal solubility and uptake [366].

Some of the highest bioconcentration factors recorded for

copper are for the marine invertebrate polychaete worm Neanthes

(BCF = 2550), the eastern oyster (BCF =28200), and the freshwater

alga Chlorella regularais (BCF =2000) [25]. The oysters contained

so much copper that they turned bluish green, but even high amounts

consumed by man orally may not be harmful [25].

Preliminary data suggests the potential for bioaccumulation or

bioconcentration of copper is high to very high for the following

biota: mammals, birds, fish, mosses, lichens, algae, mollusks,

crustacea, lower animals, and higher plants [83]. The best

potential mediums for biological monitoring (including gradient

monitoring) appear to include clams, lichens, mosses, algae, and

higher plants [83]. As mentioned above, continued ingestion of

copper by animals in excess of dietary requirements led to some

accumulation in tissues, particularly the liver and kidneys [180].

The concentration of this metallic element in earthworms is

correlated with soil concentrations, which is a consideration

relative to birds feeding on sewage sludge amended soils [179].

In a study of the Trinity River, mosquitofish data showed no

uniform upstream/downstream distribution trends for copper (unlike

other contaminants) [201]. If they had been more uniformly

present, clams might be a better choice for gradient monitoring of

copper since they have an affinity for heavy metals and tend to be

good indicators of metal pollution in general [95]. A nationwide

study of copper in bivalves showed less variation in levels from

various locations than from various species [62]. Crayfish,

turtles, and clams tended to be higher in copper than fish at

identical sites [201]. The seven highest Trinity River

concentrations were from crayfish, turtles, and clams rather than

fish [201]. Nevertheless, copper concentrations in the lean

tissues of mosquitofish, bullhead minnows, and red-eared slider

turtles were at least slightly higher at the site impacted by urban

runoff and urban point sources than those from our

reference/control site [201].

From Sorensen's book [488], quoted with written permission of

CRC Press Inc.: 

"Accumulation of Elements from Mixtures: Copper, Zinc,

Mercury, Iron, Manganese: A few environmental studies address

accumulation levels for mixtures of metals. Cross and workers

(1973) catch fish at 2500 m deep near Cape Hatteras for

analysis of levels of Hg in white muscle. Mercury levels

increase with body weight (p<0.001) for bluefish (Pomatomus

saltatrix) and morid (Antimora rostrata). Bluefish are

epipelagic (living in the part of the ocean into which light

penetrates) and morids are bathyl-demersal (living near the

sea bottom in a biogeographic realm about 180-1800 m deep).

Mercury accumulation is probably increased as a result of high
lipid solubility, high electronegativity, and/or high affinity

for sulfhydryl groups. Decreasing levels of all metals except

Hg are noted for moridsan effect possibly due to growth

dilution effects, compositional changes in muscle, and/or

dietary changes in metal levels. In contrast to Hg levels,

the concentrations of Mn, Fe, Cu, and Zn decrease or remain

unchanged. In white muscle, the concentration factors (CF) of

Hg, Mn, Cu, Zn, and Fe are 3700, 100, 200, 2100, and 2300,

respectively. Obviously, metal accumulation patterns vary as

a function of species, fish size, and metal analyzed."

Interactions:

When sulfide is present, as it is in estuarine sediments rich

in organic debris, it will combine with metals such as copper,

cadmium, zinc, and lead. The metal sulfides that form are highly

insoluble and will tend to be sequestered in the sediments (Bender

M, 1989, Heavy metals in Narragansett Bay sediments. MARITIMES, 33

(4): 5-7. Off. Mar. Programs, Mar. Resour. Build., URI Narragansett

Bay Campus, Narragansett, RI 02882-1197, USA) [940].

For a discussion of SEM and AVS issues vs copper hazards and

bioconcentration, see the Sed.Misc. section above.

Toxic compounds in distilled water, frequently copper, may

result in low BOD [861].

Although hardness is widely recognized to affect aquatic

toxicity of metals (for example, hardness seems somewhat protective

of rainbow trout related to copper and zinc toxicity), pH often has

the largest effect on metals toxicity [25,39] (Confirmed by David

Mount, National Biological Service, Columbia, MO, personal

communication, 1994).

NOTE: For pH data, see also: Schubauer-Berigan, M.K., J.R.

Dierkes, P.D. Monson, and G.T. Ankley, 1993. pH dependent

toxicity of Cd, Cu, Ni, Pb, and Zn to Ceriodaphnia dubia,

Pimephales promelas, Hyalella azteca, and Lumbriculus

variegatus. Environmental Toxicology and Chemistry 12:1261-

1267.

Mercury can attack copper and copper alloy materials

(Mackison, F. W., R. S. Stricoff, and L. J. Partridge, Jr., eds.,

NIOSH/OSHA - Occupational Health Guidelines for Chemical Hazards.

DHHS-NIOSH Publication No. 81-123, 3 VOLS,. Washington, DC: U.S.

Government Printing Office, Jan. 1981. 2) [940].

Copper and mercury are antagonistic at lower concentrations,

additive at intermediate concentrations, and synergistic at higher

concentrations [488]. Evaluation of hatchability of trout embryos

shows synergistic, additive, and antagonistic relationships between

Cu and Hg. As with Cu and zinc, synergistic interaction exists at

high Cu and Hg concentrations in the water [488]. Additive effects

are noted at an intermediate level of about 0.03 ppm of equal

proportions of either element. Antagonism is noted at low levels

(<or=0.01 ppm of equal proportions of each metal). Moreover, the

complexity of elemental interactions is confirmed in such
comparisons, although Cu-Hg interactions seem less complicated for

channel catfish Ictalurus punctatus) and goldfish (Carassius

auratus) than for largemouth bass (Micropterus salmoides) and

rainbow trout (Salmo gairdneri). The LC50 values show Hg to be

twenty-five times more toxic than Cu to bass, trout, catfish, and

goldfish under conditions of this series of studies [488].

Interactions between Cu and Hg at the epidermis of fish hint

of the role of mucus in metal poisoning of fish [488]. Epithelial

mucus from plaice (Pleuronectes platessa) binds Cu and zinc at

levels 100-fold and 20-fold greater respectively, than levels in

water during exposures of fish to low aqueous concentrations.

Dialysis of mucus against deionized water results in only a small

decrease in the concentrations of Cu and zinc bound to mucus.

Glycoproteins low in sialic acid, aromatic and sulfur-containing

amino acids, phosphate, and sulphate appear to be involved in

binding of the two divalent cations. Moreover, Cu+2, Zn+2, and

Hg+2 precipitate fresh plaice mucus in the order Cu > Zn > Hg.

Mucus serves a protective function by binding excess aqueous metals

as a precipitate [488].

Zinc in water acts synergistically with copper and ammonia to

produce an increased toxic effect on fish [26,47]. A study in an

Arkansas river system showed that macroinvertebrate concentrations

were negatively correlated with zinc concentrations but not with

concentrations of iron or copper [72].

In western watersheds affected by metals, fish kills are often

associated with runoff and rainstorm events. Metals responsible

for toxicity are often copper and zinc, whose toxicity and/or

mobility are enhanced by the depressions of pH,

hardness/alkalinity, and dissolved organic carbon that typically

accompany these events (David Mount, National Biological Survey,

Columbia, MO, personal communication, 1994).

Intermediate concentrations of copper (Cu) and zinc (0.07 ppm

Cu and 0.69 zinc) elicit greater responses in fish ventilation

amplitude, ventilation rate, and coughing frequency than higher

concentrations [488]. Higher Cu or zinc levels cause more

variation in ventilation pressure changes than lower zinc levels.

Singly or in combination, zinc causes increased coughing frequency;

whereas, Cu does not. Therefore, combined exposure to zinc-Cu

results in synergism at intermediate levels of the elements. In

fact, coughing frequency at 0.04 ppm Cu and 0.66 ppm zinc combined

is about one and one-half times greater than the sum of the

responses to the single toxicants. The marked individual

variability in ventilatory activity is noteworthy and is generally

considered a result of irritation of buccal (and possibly gill)

membranes. Amplitude may be low and ventilation rate may be high

for one subject (or for one concentration) but not for a second

subject (or concentration). Unfortunately, the authors do not

report total respiratory activity for individual fish using

ventilation rate and amplitude date (e.g., volume of water breathed

per unit time). Perhaps the individual variation would be reduced

in such comparisons [488].

See also "Accumulation of elements from mixtures" information

[488] in Bio.Detail section above.
 Interactions [609]:

The antineoplastic drug BCNU, a known and potent inhibitor of

erythrocyte glutathione reductase, may enhance the oxidant

stress of known oxidizing agents (including copper) commonly

found in the environment. A BCNU induced deficiency of

erythrocyte glutathione reductase produced no enhanced

formation of methemoglobin or decrease in glutathione, under

exposure to the stressors. [Bott M, Calabrese EJ; J Environ

Sci Health A23 (3): 219-30 (1988)].

Vanadium compounds (sodium trivanadium and vanadyl sulfate) in

different oxidation states influenced metabolism in rats. The

intoxication with sodium trivanadium and vanadyl sulfate

significantly reduced the intestinal absorption of copper. The

inhibitory effect was elicited both by acute (single oral

dose) and subchronic (12 wk) administration. Furthermore, the

levels of ceruloplasmin in serum and the concentration(s) of

copper in liver were decreased in the rats exposed to

continuous oral administration of vanadium cmpd. [Witkowska D

et al; Bull Environ Contam Toxicol 40 (2): 309-16 (1988)].

Cysteine, via chelation reactions, ameliorates biochemical

lesions caused by excessive ingestion of several trace

elements. Because oral cysteine per se is considerably more

protective than the in vivo metabolic cysteine precursors,

methionine or cystine, chelation of cysteine with trace

elements likely occurs primarily in the gut, thereby

decreasing absorption of both cysteine and the trace element

in question. Using copper as an example, orally administered

cysteine markedly improves growth and reduces liver copper

deposition in chicks or rats fed a high level of inorganic

copper. Likewise, excessive copper ingestion impairs sulfur

amino acid utilization and increases the dietary requirement

for sulfur amino acid. [Baker DH, Czarnecki-Maulden GL; J Nutr

117 (6): 1003-10 (1987)].

Intestinal copper absorption and blood measures of copper

status were studied in healthy young men receiving varying

intakes of ascorbic acid over 14 wk. Copper absorption and

retention were assessed during four ascorbic acid intake

periods: 2 wk x 65 mg ascorbic acid, 4 wk x 5 mg/day, 3 wk x

605 mg/day and 4 wk x 5 mg/day. Measures of copper status were

serum copper and serum ceruloplasmin. Copper absorption,

copper retention, total serum copper and the serum level of

ceruloplasmin protein were not affected significantly by the

changes in ascorbic acid intake; however, the oxidase activity

of serum ceruloplasmin was decreased an average of 21% during

the high (605 mg/day) ascorbic acid intake period. The results

suggest that in adult men moderate supplemental intakes of

ascorbic acid reduce ceruloplasmin oxidase activity

specifically but do not depress intestinal copper absorption

or overall body copper status. [Jacob RA et al; J Nutr 117

(2): 2109-15 (1987)].
The effects of elevated dietary ascorbic acid and iron on

copper utilization were examined. Male Sprague-Dawley rats

were fed one of two levels of copper (deficient, 0.42

microgram copper/g, or adequate, 5.74 micrograms copper/g),

iron (moderate, 38 micrograms iron/g or high, 191 micrograms

iron/g), and ascorbic acid (low, 0% or high, 1% of the diet)

for 20 days. High iron decreased copper absorption only in

copper deficient rats. High ascorbic acid significantly

decreased tissue copper levels in copper adequate rats. High

iron with ascorbic acid caused severe anemia in copper

deficient rats and decreased plasma ceruloplasmin by 44% in

copper adequate rats. Copper, zinc superoxide dismutase

activity in erythrocytes was decreased by 14% during copper

deficiency but was not affected by iron or ascorbic acid.

[Johnson MA, Murphy CL; Am J Clin Nutr 47 (1): 96-101 (1988)].

An experiment was conducted with female Cobb feather sexed

chicks to study the influence of methionine and selected

nutrient supplement on the performance of chicks fed high

copper levels. Day old chicks were alloted randomly to pens

for the 22 day experiment. Treatments included copper at 0,

400, and 800 mg/kg. Supplemental methionine reversed the

growth depression observed in birds fed 400 but not 800 mg/kg

copper. Additions of 400 and 800 mg/kg copper to the basal

diet depressed feed consumption by 8.6 and 19.4%,

respectively. Hepatic copper concentrations increased linearly

with increasing dietary copper and were not influenced by

supplemental methionine or selected nutrient. Serum glutamicoxaloacetic transaminase activity was not influenced by

dietary copper. [Ledoux DR et al; Poult Sci 66 (8): 1379-84

(1987)].

Sodium aurothiomalate was given to male Wistar rats (initial

body weights: 150 g) by subcutaneous injection at doses of up

to 7.5 mg/kg (corresponding to 4.27 mg gold/kg), twice a week,

for 4-5 weeks. The concentrations of calcium, magnesium, iron,

copper, and zinc were measured in serum, urine, feces and in

the liver, kidney, spleen, heart, lung, testis, bone, and

muscle. The concentration of copper was increased 5 fold in

kidney while smaller increases of zinc in kidney, copper in

muscle, iron in muscle and testis, and calcium in spleen were

found. There was a significant reduction in the concentration

of copper in serum. Kidney cytosol from gold treated but not

from control animals contained a low molecular weight protein

which was associated with copper, zinc, and gold. The rats

developed proteinuria and microscopic changes to renal tubular

cell structure were also observed. It is suggested that the

gold induced accumulation of copper may follow from an

increased rate of synthesis of metallothionein and could be

responsible for the renal dysfunction which develops in a

proportion of rheumatoid arthritis patients who are treated

with gold. [Taylor A et al; Toxicol 47 (3): 339-50 (1987)].

Sea scallops Placopecten magellanicus in early gametogenesis
from the southern shelf of Hudson Canyon, New Jersey, were

exposed to sublethal levels of copper and cadmium in a flowing

seawater system. Exposure was to copper (10 and 20 ug/l: low

copper and high copper groups) or to a combination of copper

and equimolar cadmium (10 ug copper + 17.7 ug cadmium/l: low

copper/cadmium group) for 8 wk, with sampling at 2 wk

intervals. Copper had a strongly inhibitory effect on gamete

production and maturation, which was partially moderated in

the presence of cadmium in the female gonad only. Total gamate

wt/scallop doubled in control individuals but dropped 60% in

both high metal exposure groups over the 8 wk exposure period,

with a smaller, temporary decrease in the low copper group.

Cadmium did not add to the inhibition by copper of gamate

development in the low copper/cadmium group, but there was no

partial recovery at 8 wk, as was seen in female scallops

exposed to low copper alone. Gonadal RNA, higher in the

females, decreased proportionately more in that sex than in

the males of the metal exposure groups. Conversely, DNA levels

were higher in the male than in the female gonad, and

decreased sharply in all metal exposed males. Gonadal protein

concentration(s) also dropped in all metal exposed scallops

with time and degree of metal exposure. Copper uptake in the

gonad increased with time and metal exposure concn, and

cadmium increased in the low copper/cadmium group with time.

[Gould E et al; Mar Biol (Berlin) 97 (2): 217-23 (1988)].

The therapy of copper poisoning and of Wilson's disease with

2,3-dimercaptopropane-1-sulfonate may increase the copper

induced hemolysis. Incubation of 2,3-dimercaptopropane-1-

sulfonate with copper ions (free or bound with erythrocyte

membranes) is accompanied with generation of oxygen radicals.

Activated oxygen species produced via oxygen gas are able to

increase the hemolytic effects of cupric salts. Hence 2,3-

dimercaptopropane-1-sulfonate treatment in cases of copper

poisonings or Wilson's disease may involve risk of side

effects on the basis of activated oxygen species generation.

[Aaseth J et al; Pharmacol Toxicol 61 (4): 250-3 (1987)].

Five Bedlington Terriers with inherited copper (Cu)

hepatotoxicosis and with hepatic Cu concentrations ranging

from 3,000 to 11,000 micrograms/g of dry weight (normal, less

than 350 micrograms/g of dry weight) were treated daily for up

to 200 days with 2,3,2-tetramine tetrahydrochloride. During

treatment, no change was made in the dietary Cu intake, which

ranged from 12 to 16 micrograms/g of dry diet. Concentrations

of hepatic and serum Cu, iron, and zinc were determined before

and at the conclusion of the treatment period. In one dog, 24

hour urinary Cu concentration was measured before and during

treatment. A liver biopsy specimen obtained after treatment

had significantly (p < 0.05) reduced hepatic Cu concentration

(3,282 micrograms/g of dry weight; a 54.9% reduction),

compared with the pretreatment value (7,281 micrograms/g of

dry weight). After treatment, there was an overall general

lessening of the extent of hepatic morphologic damage.
Cytochemical examination for Cu in rhodanine stained biopsy

specimens revealed decreased numbers of Cu laden hepatic

lysosomes. The mean daily urinary Cu concentration increased

as much as 25 fold during 2,3,2-tetramine treatment. Hepatic

iron and zinc concentrations and serum Cu concentrations

remained within normal ranges after treatment. Clinical or

laboratory evidence of 2,3,2-tetramine tetrahydrochloride

toxicosis was not detected during treatment. [Twedt DC et al;

J Am Vet Med Assoc 192 (1): 52-6 (1988)].

Other metals such as zinc, iron, and molybdenum interact with

copper to affect copper absorption, distribution, metabolism,

and utilization. [USEPA; Health Issue Assessment: Copper p.3

(1987) EPA/600/8-87/001].

Uses/Sources:

Elemental copper supplied from a mixed copper ethanolamine

complex (Cutrine-plus algicide liquid concentrate, made by Applied

Biochemists Inc.) is a registered herbicide/algicide for use in

controlling Chara, Nitella, and hydrilla [218]. Copper sulfate is

also used to control Chara and pondweeds [218].

Plants take up copper from soil, groundwater, sewage sludge,

biocides, fertilizers and air pollution [83]. A number of plants

have been described as indicators of higher-than-normal

concentrations of this element in the soil [951]. Animals take up

copper from industrial sources, contaminated water, and

contaminated food [83]. Copper is one of the most common

contaminants associated with urban runoff, and specific sources

include soil erosion, corrosion of pipes and tubes, industrial

discharges, and sewage treatment plant discharges [25]. Copper is

also present in the leachate of some municipal landfills [80] and

in sludges generated by sewage treatment plants [94]. Water

(particularly water that is acidic, low in hardness and alkalinity,

and consequently corrosive to piping) may leach copper from

drinking water pipes [366].

 Additional Information on Uses [280]:

Copper was the first metal used by humans and is second only

to iron in its utility through the ages. Copper mixes well

with many elements, and more than 1,000 different alloys have

been formed, several of which are technologically significant.

The presence of the other element or elements can modify the

hot or cold machining properties, tensile strength, corrosion

fatigue, and wear resistance of the copper; it is also

possible to create alloys of pleasing colors. 

The electrical industry is a major consumer of copper. The

metal is used for the windings of generators and for conveying

electrical power. Its resistance to chemical attack and its

high thermal conductivity make copper a useful metal for

condensers in chemical plants and for car radiators. Copper
tubing is widely employed in plumbing, and finely divided

copper is used as an industrial catalyst in the oxidation of

methanol to formaldehyde. Copper compounds, such as Fehling

solution, are used in analytical tests for sugars. Copper(II)

sulfate has many industrial applications, including the

preparation of Bordeaux mixture (a fungicide) and the

manufacture of other copper compounds. It is also used in

electroplating solutions, in textile dyeing, and as a timber

preservative. Probably the earliest use of copper as a

fungicide was in the form of copper sulfate solution employed

as a seed dressing to destroy cereal disease, such as bunt. 

New materials are increasingly replacing copper: plastic for

pipe and tubing, glass fiber for wire, lightweight aluminum

for automobile parts. 

 Major Uses [609]:

Heating, chemical, and pharmaceutical machinery; alloys (monel

metal, beryllium-copper); electroplated protective coatings

and undercoats for nickel, chromium, zinc, etc; cooking

utensils; corrosion-resistant piping; catalyst; flakes used as

insulation for liquid fuels; whiskers used in thermal and

electrical composites. [Sax, N.I. and R.J. Lewis, Sr. (eds.).

Hawley's Condensed Chemical Dictionary. 11th ed. New York: Van

Nostrand Reinhold Co., 1987. 308].

In works of art. [The Merck Index. 10th ed. Rahway, New

Jersey: Merck Co., Inc., 1983. 359].

Metal for electrical & electronic products (eg, wire) building

construction (eg, plumbing pipes), industrial machinery &

equipment, transportation industry (eg, automobiles), consumer

& general products (eg, coins), & in inorganic pigments (eg,

pigment metal 2); chem intermediate for copper chems (eg,

cupric sulfate). [SRI].

Copper has a contraceptive effect when present in the uterus.

It is added to some intrauterine contraceptive devices

permitting reduction in their size with concomitant reduction

in the associated side effects such as pain and bleeding.

[Reynolds, J.E.F., Prasad, A.B. (eds.) Martindale-The Extra

Pharmacopoeia. 28th ed. London: The Pharmaceutical Press,

1982. 930].

In agricultural products (insecticides, fungicides,

herbicides), anti-fouling paints, catalysts, corrosion

inhibitors, electrolysis and electroplating processes,

electronics, fabric and textiles, flameproofing, fuel

additives, glass, and ceramics. ... Used in cement, food and

drugs, metallurgy, nylon, paper products, pigment and dyes,

pollution control catalyst, printing and photo copying,

pyrotechnics, and wood preservatives. /Copper and cmpd/

[USEPA; Health Issue Assessment: Copper p.15 (1987) EPA/600/8-
87/001].

 Natural Sources [609]:

Occurrence /all forms/ in earth's crust: 70 ppm ... In

seawater: 0.001-0.02 Ppm. ... Found in nature in its native

state; also in combined form in several minerals incl

chalcopyrite, chalcocite, bornite, tetrahedrite ... Enargite

... Antlerite. [The Merck Index. 10th ed. Rahway, New Jersey:

Merck Co., Inc., 1983. 358].

Copper is present in concentration(s) averaging about 4 ppm in

limestones, 55 ppm in igneous rocks, 50 ppm in sandstones, and

45 ppm in shales. The marked concentrations of copper in

shales & sandstones suggest that copper in the lithosphere

exists largely as adsorbed ions, fine grained particles or as

one of many discrete sedimentary copper minerals. Generally,

these minerals occur only as sparse tiny grains that are

widely disseminated throughout the sedimentary rocks.

[Callahan, M.A., M.W. Slimak, N.W. Gabel, et al. Water-Related

Environmental Fate of 129 Priority Pollutants. Volume I. EPA440/4 79-029a. Washington, DC: U.S.Environmental Protection

Agency, December 1979.,p. 11-1].

Copper is widely distributed in nature in the elemental state,

in sulfides, arsenites, chlorides, and carbonates. The element

is only superficially oxidized in air, sometimes giving a

green coating of hydroxy carbonate and hydroxy sulfate. The

concentration of copper in the continental crust, generally

estimated at 50 ppm, tends to be highest in the ferromagnesium

minerals, such as the basalts pyropene and biotite, where it

averages 140 ppm. Sandstones contain 10-40 ppm, shales 30-150

ppm, and marine black shales 20-300 ppm. Coal is relatively

low in copper. /Copper and compounds/ [Seiler, H.G., H. Sigel

and A. Sigel (eds.). Handbook on the Toxicity of Inorganic

Compounds. New York, NY: Marcel Dekker, Inc. 1988. 266].

In the sedimentary cycle copper is concentrated in the clay

mineral fractions with a slight enrichment in those clays rich

in organic carbon. /Copper and compounds/ [Seiler, H.G., H.

Sigel and A. Sigel (eds.). Handbook on the Toxicity of

Inorganic Compounds. New York, NY: Marcel Dekker, Inc. 1988.

266].

 Artificial Sources [609]:

In the vicinity of copper mines or smelting works, where the

water and pasture have been shown to be contaminated with

copper. [Clarke, M. L., D. G. Harvey and D. J. Humphreys.

Veterinary Toxicology. 2nd ed. London: Bailliere Tindall,

1981. 45].

Smelting operations may produce elemental copper ... /and/ it

is likely that municipal incineration will produce copper ...
. [USEPA; Health Issue Assessment: Copper p.1 (1987)

EPA/600/8-87/001].

The principal source of elevated copper levels in air is

copper dust generated by copper processing operations. ...

Other possible sources of copper in air may be tobacco smoke

and stack emissions of coal burning power plants. /Copper dust

and copper oxides/ [USEPA; Ambient Water Quality Criteria Doc:

Copper p.C-18 (1980) EPA 440/5-80-036].

The reaction of soft water with the copper pipes that are used

in some household plumbing systems contributes to the copper

levels in water at the tap. /Oxidized copper (Cu(II)) complex/

[National Research Council. Drinking Water and Health. Volume

3. Washington, DC: National Academy Press, 1980. 312].

On a global basis, the atmospheric copper flux from

anthropogenic sources are approximately three times higher

than its flux from natural sources. Non-ferrous metal

production is the largest contributor of atmospheric copper

flux in the United States. /Copper dust, mist, and fume/

[USEPA; Health Issue Assessment: Copper p.1 (1987) EPA/600/8-

87/001].

Windblown dust accounts for approximately 65% of the overall

nonanthropogenic sources of copper emission to the atmosphere.

Sources of copper emission are: iron and steel production,

7.4%; coal and oil combustion, 4.6%; zinc smelting, 3.3%;

copper sulfate production, 2.7%; municipal incineration, 1.9%;

others, 2.3%. /Copper dust, mist, and fume/ [USEPA; Health

Issue Assessment: Copper p.13-14 (1987) EPA/600/8-87/001].

Forms/Preparations/Formulations:

Radionuclides:

The symbol for Copper-64 is 64Cu, the atomic number is

29, the half-life is 12.7 hours, and beta emission,

positron emission, and X-ray emission are the major forms

of decay [674].

 Formulations/Preparations [609]:

Commercial copper (Cu) is available in six general types:

Electrolytic tough-pitch, 99.90% Cu; Deoxidized, 99.90%

Cu; Oxygen-free, 99.92% Cu; Silver-bearing, 99.90% Cu;

Arsenical, 99.68%; Free-cutting, 99.4-99.5% [Considine.

Chemical and Process Technol Encyc p.316 (1974)].

Forms available: ingots, sheet, rod, wire, tubing, shot,

powder; high purity (impurities less than 10 ppm) as

single crystals or whiskers. [Sax, N.I. and R.J. Lewis,

Sr. (eds.). Hawley's Condensed Chemical Dictionary. 11th
ed. New York: Van Nostrand Reinhold Co., 1987. 308].

See also: Laboratory Section below for discussion of

total vs. Acid Soluble Metals.

Chem.Detail: Detailed Information on Chemical/Physical Properties:

 Solubilities [609]:

Insol (sic: note from Roy Irwin, editor: it is mostly the

sulfides are "relatively insoluble" while some of the salts

are more soluble) in hot & cold water; sol in nitric acid, hot

sulfuric acid; very slightly sol in hydrochloric acid,

ammonium hydroxide [Weast, R.C. (ed.) Handbook of Chemistry

and Physics, 68th ed. Boca Raton, Florida: CRC Press Inc.,

1987-1988.,p. B-88].

 Vapor Pressure [609]:

1 MM HG AT 1628 DEG C [Sax, N.I. Dangerous Properties of

Industrial Materials. 6th ed. New York, NY: Van Nostrand

Reinhold, 1984. 804].

 Density/Specific Gravity [609]:

8.94 [The Merck Index. 10th ed. Rahway, New Jersey: Merck Co.,

Inc., 1983. 358].

 Molecular Weight [609]:

63.546 [Weast, R.C. (ed.) Handbook of Chemistry and Physics,

68th ed. Boca Raton, Florida: CRC Press Inc., 1987-1988.,p. B88].

 Heat of Vaporization [609]:

1150 CAL/G [The Merck Index. 10th ed. Rahway, New Jersey:

Merck Co., Inc., 1983. 358].

 Boiling Point [609]:

2595 DEG C [The Merck Index. 10th ed. Rahway, New Jersey:

Merck Co., Inc., 1983. 358].

 Melting Point [609]:

1083 DEG C [The Merck Index. 10th ed. Rahway, New Jersey:

Merck Co., Inc., 1983. 358].

 Color/Form [609]:

REDDISH METAL; FACE CENTERED CUBIC STRUCTURE [The Merck Index.

10th ed. Rahway, New Jersey: Merck Co., Inc., 1983. 358].
 Other Chemical/Physical Properties [609]:

Lustrous, ductile, malleable metal; mohs' hardness: 3.0;

Specific resistance: 1.673 Microohm/cm; heat of fusion: 48.9

Cal/g; heat capacity (solid): 0.092 Cal/g/deg c at 20 deg c,

(liq): 0.112 Cal/g/deg c; becomes dull when exposed to air;

very slowly attacked by cold hydrochloric acid, dil sulfuric

acid, readily by dil nitric acid, hot concentration(s)

sulfuric acid and hydrobromic acid, attacked by acetic & org

acids; two naturally occurring isotopes: 63 (69.09%), 65

(30.91%); 9 Artificial isotopes [The Merck Index. 10th ed.

Rahway, New Jersey: Merck Co., Inc., 1983. 358].

It conducts heat and electricity exceedingly well

[International Labour Office. Encyclopedia of Occupational

Health and Safety. Vols. I&II. Geneva, Switzerland:

International Labour Office, 1983. 546].

Copper forms two series of salts, cu(1+) and cu(2+) both

valence types form complex ions that are stable. [Sax, N.I.

and R.J. Lewis, Sr. (eds.). Hawley's Condensed Chemical

Dictionary. 11th ed. New York: Van Nostrand Reinhold Co.,

1987. 308].

Readily attacked by alkalies. [Sax, N.I. and R.J. Lewis, Sr.

(eds.). Hawley's Condensed Chemical Dictionary. 11th ed. New

York: Van Nostrand Reinhold Co., 1987. 308].

 Reactivities and Incompatibilities [609]:

Reacts violently with ... ammonium nitrate, bromates,

chlorates, iodates, chloride, ... ethylene oxide, ...

hydrazine mononitrate, hydrazoic acid, ... and potassium oxide

... . [Sax, N.I. Dangerous Properties of Industrial Materials.

6th ed. New York, NY: Van Nostrand Reinhold, 1984. 804].

In the presence of wet acetylene and ammonia, copper and

brasses down to 60% copper react readily to form explosive

acetylides. ... A combination of finely divided copper with

finely divided bromates (also chlorates or iodates) of barium,

calcium, magnesium, potassium, sodium, or zinc will explode

with heat, percussion and sometimes light friction. [National

Fire Protection Association. Fire Protection Guide on

Hazardous Materials. 9th ed. Boston, MA: National Fire

Protection Association, 1986.,p. 491M-68].

Unstable acetylides form when acetylene is passed over copper

that has been heated enough to form a tarnish of oxide

coating. [National Fire Protection Association. Fire

Protection Guide on Hazardous Materials. 9th ed. Boston, MA:

National Fire Protection Association, 1986.,p. 491M-68].

Sodium azide ... Reacts violently with ... Copper ... .

[National Research Council. Prudent Practices for Handling
Hazardous Chemicals in Laboratories. Washington, DC: National

Academy Press, 1981. 146].

Fate.Detail: Detailed Information on Fate, Transport, Persistence,

and/or Pathways:

For a discussion of SEM and AVS issues vs fate, see the

Sed.Misc. section above.

A cycle of biomobilization of sedimentary copper by algae,

followed by movement of the algae downstream and return of the

copper to the sediments when the algae dies, may play a role in

moving copper downstream [95]. 

It is not always possible to separate the environmental fate

processes related to transport and partitioning from those related

to transformation and degradation for a metal, its various

compounds and complexes [979]. Part of this problem is that the

form of copper is rarely identified [979]. It is also difficult to

determine when a process such as adsorption should be treated as

partitioning or transformation, since the formation of strong bonds

to an adsorbent may be construed as a transformation to new

molecular species [979]. Separating weak and strong adsorption is

awkward and not always possible [979].

Copper is released to the atmosphere in the form of

particulate matter or adsorbed to particulate matter [979]. It is

removed by gravitational settling (bulk deposition), dry deposition

(inertial impaction characterized by a deposition velocity),

washout by rain (attachment to droplets within clouds), and rainout

(scrubbing action below clouds) [979].

In a groudwater study, copper showed a pronounced solubility

only in the oxidizing environment; in the reducing environment,

solubility was low, possibly due to the formation of sulfides

[979]. The form of copper at polluted and unpolluted sites may

affect its leachability, particularly by acid rain [979]. The

leaching of heavy metals by simulated acid rain (pH 2.8-4.2) was

measured by applying rainwater to columns containing humus layers

from sites in a Swedish spruce forest both near to and far from a

brass mill [979]. Leaching of copper increased considerably when

water with a pH 3.4 was applied to soil from polluted sites

[979]. Since 25 to 75% of copper entering POTWs is removed in

sludge, much of which is disposed of by spreading on land, it is

important to ascertain whether copper in sludge is apt to leach

into soil [979]. This does not appear to be the case [979].

Hazardous amounts of copper should not leach into groundwater from

sludge, even from sandy soils [979].

 Environmental Fate [609]:

AQUATIC FATE: ... some copper complexes may be metabolized

/however/ there is no evidence that biotransformation

processes have a significant bearing on the aquatic fate of

copper. /Copper salts and complexes/ [Callahan, M.A., M.W.

Slimak, N.W. Gabel, et al. Water-Related Environmental Fate of
129 Priority Pollutants. Volume I. EPA-440/4 79-029a.

Washington, DC: U.S.Environmental Protection Agency, December

1979.,p. 11-16].

TERRESTRIAL FATE: Factors affecting the balance between copper

in the parent rock & in the derivative soil include the degree

of weathering, the nature & intensity of the soil formation,

drainage, pH, oxidation-reduction potential, & the amount of

organic matter in the soil. Since copper in rocks is likely

to be more mobile under acidic than alkaline conditions, the

relation of pH to copper in the environ has been of great

concern to agriculturalists & biologists. Alkaline conditions

in the soil & the surface water favor precipitation of copper.

... Acid conditions promote solubility of copper, increase the

concentration(s) of ionic copper, & thereby change the

microorganism & other aquatic animal populations, depending on

tolerance for various levels of copper in solution. ... The

reports of acid rain in various parts of the world are of

serious concern. Due to the variety of conditions which

influence the metal's avail, the total copper content of the

soils is not an accurate indication of deficiencies or excess

of copper in soil rooted plants. /Copper salts/ [Seiler, H.G.,

H. Sigel and A. Sigel (eds.). Handbook on the Toxicity of

Inorganic Compounds. New York, NY: Marcel Dekker, Inc. 1988.

273].

Terrestrial Fate: The fate of copper with respect to its

leachability in purely organic spruce forest soils was

studied. Appreciable mobilization of copper occurred only with

prolonged leaching at pH 2.8. Therefore, it does not appear

likely that acidic rainfall will result in significant

mobilization of copper from organic soils unless the pH of

rainfall decreases to < 3. ... Estimated that approx 50% of

copper in the top few centimeters of these soils was

organically bound, approx 18% was in the hydroxy carbonate

form, approx 7% was in the adsorbed state, approx 11% was

bound by other anions and 6% was irreversibly adsorbed. Only

3% of the copper was extractable with water at pH 4.5; hence

only 3% was mobile at this pH. ... In urbanized areas the

effects of land clearing, profile disruption and increased

acid rainfall may increase copper mobilization in these soils.

[Tyler G; Water, Air, Soil Pollut 9 (2): 137-48 (1978) as

cited in USEPA; Health Issue Assessment: Copper p.18 (1987)

EPA/600/8-87/001].

In soils exposed to atmospheric deposition, high levels of

copper and other metals may occur that can be directly toxic

to certain soil microorganisms and can disrupt important

microbial processes in soil, such as nutrient cycling. Studies

concerning heavy metal effects on microbial and fungal

activity in soils, found that copper and other metals

inhibited mineralization of nitrogen and phosphorus in

contaminated forest soils. Regression analysis indicated that

copper was more important than other metals in controlling
these processes. Studies reported lower fungal species

diversity in soils contaminated with heavy metals. Copper was

found to be more toxic to these species than other metals.

This evidence suggests that while other metals in contaminated

soils contributed to the observed effects, copper may be the

most important in terms of toxicity. /Copper(II) salts and

other heavy metal salts/ [Hutchinson TC; Copper Environ p.451-

502 (1979) as cited in USEPA; Health Issue Assessment: Copper

p.25 (1987) EPA/600/8-87/001].

 Absorption, Distribution and Excretion [940]:

1. Small fragments of copper ... in the anterior vitreous just

behind the lens in a number of cases have been observed for

years, gradually dissolving & disseminating copper to lens,

cornea & iris, where copper has a predilection for the

basement membranes. [Grant, W.M. Toxicology of the Eye. 3rd

ed. Springfield, IL: Charles C. Thomas Publisher, 1986. 261]..

2. Copper dissolved from the wire used in certain intrauterine

contraceptive devices has been shown to be absorbed

systemically. [International Labour Office. Encyclopedia of

Occupational Health and Safety. Vols. I&II. Geneva,

Switzerland: International Labour Office, 1983. 547].

3. Intrauterine devices containing metallic copper ... raise

the endometrial copper concentration 2 fold, & this copper

excess might be transferred to the fetus. [Friberg, L.,

Nordberg, G.F., Kessler, E. and Vouk, V.B. (eds). Handbook of

the Toxicology of Metals. 2nd ed. Vols I, II.: Amsterdam:

Elsevier Science Publishers B.V., 1986.,p. V2 247].

4. Nonradioactive and radioactive metal salts were

administered intravenously to Sprague-Dawley rats. The highest

amount of each metal approached the maximum tolerated dose.

Cobalt, silver, and manganese were eliminated rapidly. The

elimination of 20 to 50 percent of the dosage was observed for

copper (Cu), thallium, bismuth, lead, cesium, gold, zinc,

mercury, selenium, and chromium. Copper, thallium, lead, and

zinc were excreted at a slower rate, with 30.6 to 38.3 percent

excreted on the first day. The rest of the metals were

eliminated slowly by the intestinal route. Copper was removed

rapidly via urine, while lead, tin, methyl mercury, silver,

iron, manganese, and cadmium were eliminated slowly. Copper,

selenium, lead, bismuth, and cobalt were eliminated at an

intermediate rate via the biliary route. Silver, arsenic,

manganese, copper, selenium, cadmium, lead, bismuth, and

methyl mercury were highly concentrated in bile relative to

plasma. Liver and kidney contained the highest concentrations

of most metals. The intestinal route was the major path of

elimination for silver, manganese, copper, thallium, lead,

zinc, cadmium, iron, and methyl mercury. Copper, cesium, gold,

selenium, and chromium were removed predominantly by urine.

[Gregus Z, Klaassen CO; Toxicol Appl Pharm 85 (1): 24-38
(1986)].

5. Circadian rhythms in the urinary excretion of eleven heavy

metals and organic substances were examined under free, water

restrictive and water loading conditions for 6 days (2 days

for each of the three conditions) in twenty metal workers

exposed to lead, zinc, and copper. Circadian rhythms were

found for all heavy metals and organic substances as well as

for urinary flow rate, creatinine and total urinary solutes.

The rhythm in the copper excretion depends on the creatinine

rhythm, ie the rhythm of glomerular filtration. [Aono H, Araki

S; Int Arch Occup Environ Health 60 (1): 1-6 (1988)].

6. The relationship between tissue levels of metallothionein

and metal concentrations was assessed for zinc, copper, and

cadmium in ten different organs from human autopsies and rats.

Human autopsy specimens were obtained from ten males between

the ages of 20 and 50 years within 2 days of sudden death.

Tissues assayed included pancreas, liver, kidney, brain, small

intestine, stomach, muscle, heart, lung, and spleen. Human

metallothionein levels were higher than rat levels for all

tissues assayed except brain and small intestine. The highest

metallothionein levels were found in human liver and kidney

cortex and rat kidney and brain. Zinc levels were highest for

human liver, kidney, and muscle; and copper levels were

highest for human liver, brain, and heart and rat liver,

kidney, and heart. Elevated cadmium levels were found in human

liver and kidney. All cadmium levels were below detectable

limits in rats. Significant correlations were established

between metallothionein levels and zinc and copper in human

liver and between metallothionein and cadmium in human kidney

cortex. [Heilmauer HE et al; Toxicol Lett 38 (3): 205-11

(1987)].

7. Accumulation of copper in a population of the grasshopper,

Chorthippus brunneus, from grasslands around a copper refinery

complex (0.75 sq km divided into four sites) was monitored,

and compared with a control site distant from sources of metal

contamination. A sub-control site in an unpolluted stabilized

sand dune system where the soil copper concentration was

deficient was also studied. Each site contained similar mixed

grass swards of copper-tolerant Agrostis stolonifera and

Festuca rubra which were the major components of fecal pellets

of refinery site grasshoppers. Monthly samples of grasses and

the insects, adult and nymphal specimens were obtained for

analysis from June to November (n= >100/species/site). Monthly

mean copper concentrations in A stolonifera were; (a) refinery

sites, 39.4 ug/g to 152 ug/g, respectively); (b) 1 km site,

16.8 ug/g; and (c) control respectively); (b) 1 km site, 16.8

ug/g; and (c) control site, 8.2 ug/g. For F rubra, copper

concentrations were: (a) refinery sites, 26.4 ug/g to 86.3

ug/g; (b) 1 km site, 20.1 ug/g, and (c) control site, 7.4

ug/g. For C brunneus concentrations were: (a) refinery sites,

300 to 380 ug/g respectively); (b) 1 km site, 66.4 ug/g; and
(c) control site 37.5 ug/g. Total body concentration of Cu in

grasshoppers increased with mean dietary contamination levels;

the relationship was not linear and reached a peak at 50 ug/g

of dietary Cu. Accumulation of Cu in the insects closely

followed the seasonal increase in contamination levels of the

grasses. Copper accumulated progressively through the instars

of the insects. Nymphs from the refinery sites had

significantly increased copper concentration above control

values for all instars, and the accumulation seemed to begin

soon after hatching. Concentrations are reduced in newly

emerged adults which suggests some copper is excluded at the

final molt. Both body and integumental concentrations were

significantly elevated in refinery samples compared to

controls, and refinery insects had a significant elevation of

integument over body copper. The copper [Hunter BA et al; Arch

Environ Contam Toxicol 16 (6): 711-6 (1987)].

8. Cultured C6 rat glioma cells were exposed to lead acetate

(0, 1, 10, or 100 uM) for 3-4 days. Cells were analyzed for

changes in viability and intracellular lead, iron, and copper

concentrations after lead treatment was discontinued. Lead

uptake did not affect intracellular iron or copper

concentrations. Unlike C6 cells, however, astroglia showed

elevations of intracellular iron or copper after lead

treatment. C6 cells appear to be an adequate model for

selected events in glial toxicosis, such as lead stimulated

protein synthesis in oligodendroglia and lead uptake in

astroglia, but not lead induced alterations of intracellular

copper and iron in astroglia. [Bratton GR; J Toxicol Environ

Health 23 (2): 267-80 (1988)].

9. The Japanese serow, a bovine ruminant, is long-lived and

free-ranging. The animals were killed during the winter 1981-

82 in the Gifu and Nagano Prefectures, Japan. The Cu

concentrations were measured by flame absorption spectrometry.

On a wet wt basis, the mean Cu concentration in muscle, liver,

kidney, and whole body of fetuses (gestation age 0.3-0.7 yr,

N= 13) were 0.59, 66.4, 3.76, and 2.56 ug/g, respectively; in

fawns (age 0.0-0.5 yr, N= 12), 2.02, 12.0, 2.90, and 1.52

ug/g, respectively; in yearlings (age 0.5-2.5 yr, N= 6), 1.96,

32.8, 2.80, and 1.75 ug/g, respectively; in adults (age 2.5 to

10 yr, N= 42), 1.84, 34.1, 2.81, and 2.15 ug/g, respectively;

and in adults (age 10 to 17.5 yr, N= 17), 1.79, 40.5, 2.63,

and 2.25 ug/g, respectively. Sex differences were observed in

liver, with significantly higher concentrations (p< 0.05) in

males than in females. The mean Cu concentration in fleece of

fawns, yearlings, and adults (age 2.5 to 10 yr) was 13.3,

14.8, and 10.6 ug/g, respectively. Bone samples of two adult

serows contained 0.35 to 0.83 ug/g. The body burden of fetuses

was low (<1%) compared with that of their mothers. The Cu

levels were high during gestation and decreased after birth

until about 2.5 yr of age as a result of hepatic accumulation.

There was no significant difference in Cu concentration

between collection locations. The Cu uptake agreed well with
the concentration found in food plants. [Honda K et al; Arch

Environ Contam Toxicol 16: 551-61 (1987)].

10. Copper concentrations in tissues of 10 human males (mean

age 43 yr) who suffered sudden death and six male Wistar rats

were measured. Copper was detected in all 10 tissues (brain,

heart, kidney cortex, liver, lung, muscle, pancreas, small

intestine, spleen, and stomach) of both rat and man. Highest

levels were in the liver of man and in the kidney of the rat.

In most tissues the levels of copper were within a factor of

two for the two species. Results were presented graphically

and no values were given. In human liver there was a positive

relationship between the concentration of copper and the

amount of metallothionein in the tissue. [Heilmaier HE et al;

Toxicol Lett 38 (3): 205-11 (1987)].

Laboratory and/or Field Analyses:

Many methods have been used to monitor for copper [861,979,

1001,1003,1004,1005,1006]. EPA methods recommended depend on the

application: whether for drinking water [40 CFR Part 141 and

1005,1006,1008], NPDES discharge permits [40 CFR 136 and

1005,1006], CERCLA [861,1005,1006], RCRA [861,1005,1006], or lowdetection-limit water-quality based permitting [1001,1003,1004].

Other agencies (USGS, APHA, ASTM, NOAA, etc. also publish different

"standard methods." If one simply wants to know whether or not the

concentration exceeds EPA criteria or various low concentration

benchmarks for humans, fish, or wildlife, it is not always too

clear which "standard method" is optimum, although some might argue

that for water, the 1996 EPA methods 1640 and 1669 (see details

below) should apply.

Standard water methods used in the past have included EPA

220.1, 220.2, and ICP method 200.7 (40 CFR, Part 136.3, Table 1B,

page 381, 1994). Inductively-coupled plasma (ICP) methods often

have sufficiently low detection limits for considering risks to

fish and wildlife.

However, detection limits should be no higher than comparison

benchmarks or criteria for various media (water, sediments, soil,

tissues, etc, see sections above) being considered. In some

situations (as when background concentrations and benchmark

comparisons are low), water detection limits as low as 0.024 ug/L

may be necessary, using EPA method 1640, since EPA Water Quality

Criteria are as low as 2.5 ug/L [1001]. Detection limits can be as

low as 0.2 ug/g in tissues and other solids [979]. 

In the case of copper, natural background levels are often

higher and thus the following ICP detection limits (the default

concentrations often recommended by the Fish and Wildlife Service

and the National Park Service) are often sufficiently low: 0.50 ppm

dry weight in tissues, 1.0 ppm in sediments and soils; 0.005 ppm

(mg/L) in water (Roy Irwin, National Park Service, Personal

Communication, 1996). 

Acceptable containers (after proper cleaning per EPA

protocols) for Antimony, Arsenic, Cadmium, Copper, Lead, Nickel,
Selenium, Silver, Thallium, and Zinc: 500-mL or 1-L fluoropolymer,

conventional or linear polyethylene, polycarbonate, or

polypropylene containers with lid [1003]. 

Since most analytical methods for copper do not distinguish

the form of copper present; it is known how much total copper is

present, but not the nature of the copper compounds or complexes

present or how labile or available they are [979].

Notes on total vs. acid soluble vs. dissolved metals: 

Although most of the lab tests done to develop water

quality criteria and other benchmarks were originally

based on "total" values rather than "dissolved" values,

the lab settings were typically fairly clean and the

numbers generated by the lab tests are therefore often

even more comparable to field "dissolved" values than to

field "total" values (Glen Suter, Oak Ridge National Lab,

Personal Communication, 1995). As of January 1995, the

U.S. EPA was recommending that states use dissolved

measurements in water quality standards for metals, in

concert with recommendations EPA previously made for the

Great Lakes [672]. The conversion factors recommended by

EPA for converting total recoverable metals criteria to

dissolved metal criteria were given as follows [672]:

Cooper conversion for acute or chronic criteria:

0.958 (that is, total recoverable metals criteria x

0.958 = dissolved metals criteria).

The conversion factor recommended by EPA for converting

total recoverable copper (both continuous and maximum

concentrastions) to dissolved concentrations in the

January 1997 draft EPA Guidelines for 5 year 305(B)

assessments was 0.960.

Note: None of these "generic" conversion factors

work well for all areas. Both total and dissolved

concentrations should be checked at new locations

before relying on generic conversion factors (Pat

Davies, Colorado Division of Wildlife, personal

communication, 1997).

Filtration and Acidification of Water Samples:

For ICP water samples for metals, EPA recommends the

following (40 CFR Part 136, Appendix C, pertaining to ICP

analyses using method 200.7, 1994 edition of CFR Part

40):

1) For samples of "total or total recoverable

elements," samples should be acidified to a pH of

two or less at the time of collection or as soon as

possible thereafter.
Note: In more recent (1996) guidance related

to the more rigorous method 1669, EPA

clarified (some would say confused or added

data variability) the issue of when to acidify

by stating:

"Preservation recommendations for

Antimony, Arsenic, Cadmium, Copper, Lead,

Nickel, Selenium, Silver, Thallium, and

Zinc: Add 5 mL of 10% HN03 to 1-L sample;

preserve on-site or immediately upon

laboratory receipt" [1003]. 

Note: the nitric acid (triple

distilled or not?) and dilution

water (contaminated or not?) and

containers (proper type, cleaned

correctly or not?) used are all

potential sources of contamination

(see more detailed note below

related to data variation factors).

2) For determination of dissolved elements, the

samples must be filtered through a 0.45 micron

membrane filter as soon as soon as practical after

collection, using the first 50-100 ml to rinse the

filter flask. Acidify the filtrate with nitric

acid to a pH of 2 or less. Normally 3 mL of (1+1)

of nitric acid per liter should be sufficient to

preserve the sample.

3) For determination of suspended elements, the

samples must be filtered through a 0.45 micron

membrane filter as soon as soon as practical after

collection. The filter is then transferred to a

suitable container for storage and shipment, with

no preservation required.

Sources of potential variation in contaminants data:

Variation in concentrations of contaminants may

sometimes be due to differences in how individual

investigators treat samples in the field and lab

rather than true differences in environmental

concentrations. Contaminants data from different

labs, different states, and different agencies,

collected by different people, are often not very

comparable. In fact, as mentioned above in the

disclaimer, the interagency task force on water

methods concluded that [1014]:

It is the exception rather than the rule that

water-quality monitoring data from different

programs or time periods can be compared on a
scientifically sound basis, and that...

No nationally accepted standard definitions

exist for water quality parameters. The

different organizations may collect data using

identical or standard methods, but identify

them by different names, or use the same names

for data collected by different methods

[1014].

 

As of 1997, the problem of lack of data

comparability (not only for water methods but also

for soil, sediment, and tissue methods) between

different "standard methods" recommended by

different agencies seemed to be getting worse, if

anything, rather than better. The trend in quality

assurance seemed to be for various agencies,

including the EPA and others, to insist on quality

assurance plans for each project. In addition to

quality control steps (blanks, duplicates, spikes,

etc.), these quality assurance plans call for a

step of insuring data comparability [1015,1017].

However, the data comparability step is often not

given sufficient consideration. The tendency of

agency guidance (such as EPA SW-846 methods and

some other new EPA methods for bio-concentratable

substances) to allow more and more flexibility to

select options at various points along the way,

makes it harder in insure data comparability or

method validity. Even volunteer monitoring

programs are now strongly encouraged to develop and

use quality assurance project plans [1015,1017]. 

At minimum, before using contaminants data from

diverse sources, one should determine that field

collection methods, detection limits, and lab

quality control techniques were acceptable and

comparable. The goal is that the analysis in the

concentration range of the comparison benchmark

concentration should be very precise and accurate.

It should be kept in mind that quality control

field and lab blanks and duplicates will not help

in the data quality assurance goal as well as

intended if one is using a method prone to false

negatives. Methods may be prone to quality

assurance problems due to the use of detection

limits that are too high, the loss or addition of

contaminants through inappropriate handling, or the

use of inappropriate methods.

 

It was recognition that collectors and labs often

contaminate samples that led EPA to develop the
1600 series of water protocols for low detection

limit applications [1001,1002,1003,1004]. In

comparing contaminants data from different labs,

different states, and different agencies, one

should keep in mind that they are often not

comparable. They may be as different as apples and

oranges since:

1) Different Agencies (EPA, USGS, NOAA, and

various State Agencies) publish different lab

and field protocols. Each of these protocols

is different and has typically changed over

time.

Note: Even "Standard EPA Methods" which

are supposedly widely used by

consultants, industry, and academia, have

been variable over time and between

application category (Drinking Water vs.

NPDES, vs. RCRA, vs. CERCLA, vs. WaterQuality Based permits, etc.). 

Preservation and other details of various

EPA lab and field protocols have changed

over the years, just as they have at USGS

and various States and other agencies.

USGS data from 30 years ago may be

different than USGS data today due to

differences (drift) in lab and field

protocols rather than differences in

environmental concentrations.

2) Independent labs and field investigators

are not always using "the latest and greatest

methods," and it is difficult for them to

keep up with all the changes from various

agencies in the midst of their "real world"

busy lives. Updates are not always convenient

to obtain. For example, EPA changes are

scattered through various proposed Federal

Register Notices, various updates of CFRs, and

numerous publications originating in many

different parts of EPA and their contractors.

The wording is sometimes imprecise and is

often inconsistent between EPA methods for

different applications. 

3) The details of the way one person collects,

filters, and acidifies water samples in the

field may be different than the way another

does it. Sources of potential variation

include the following:

A) The protocol phrases "As soon as
practical or as soon as possible."

Different situations can change the

elapsed time considered by the field

collector to be "as soon as practical."

It may take different amounts of time to

get to a safe or otherwise optimum place

to filter and/or acidify and cool the

samples. In one case precipitation and

other changes could be going on in the

collection bottle while the bottle is on

the way to filtration and acidification.

In other cases, the field collector

filters and acidifies the samples within

minutes. Weather, safety concerns, and

many other factors could play a role.

Further insight related specifically

to copper:

In a study at Yellowstone Park,

Soda Butte Creek, filtering and

then acidifying of water

samples was done in two ways:

The first way was in the field,

per original standard EPA

suggestions in 40 CFR. The

second way was in the in the

lab after 6 to 8 days. On two

dates, lab filtered and

acidified water was always

higher in dissolved copper, a

somewhat counter-intuitive

result (Al, Fe, Mn, Zn, and Ni

showed the opposite trend,

tending to be higher in field

filtered and acidified

samples). On a third date 6

lab filtered and acidified

samples were higher in copper

and 3 field filtered and

acidified samples were higher

(Del Nimmo, USGS, personal

communication, 1997). 

In other Yellowstone

investigations, grab samples of

clear leachate water from mine

tailings started precipitating

all of sudden, fairly soon

after collection. The water

was toxic if tested fresh from

the seep--it began the test as

clear but turned red on

oxidation. If the sample was
held overnight, shaken or

aerated, or centrifuged, it

became non-toxic to fish and

daphnids. An attempt was made

to analyze both the water and

(reddish) sediment that forms

after the water emerges and is

oxidized. The sample was

brought (unfiltered and

non-acidified) back to Colorado

State University. It was split

into two portions. One water

portion was analyzed using

total analysis, the other as

dissolved. The sediments were

also analyzed. Upon shaking the

sample, the red sediment on the

bottom became re-suspended.

There were many metals in the

water but the sediment was made

up of mainly Fe and Mn, both

very difficult to dissolve.

Results of the analysis of

sediment that precipitated in

the sample using ICP: Fe at

90.5 mg/l (not kg because he

had to dissolve it with HNO3)

and Mn at 3.8 mg/l. Another

worker used the standard EPA

recommended practice of used

acidification with HNO3 then AA

and reported Fe at below

detection as dissolved but 86

mg/l as total. Mn was 2.7 mg/l

as dissolved and 4.2 as total

(Del Nimmo, USGS, personal

communication, 1997).

B) Differences in numerous other details

of the method used can drastically change

the results. Some cold, wet, hurried, or

fire ant-bitten collectors might decide

that it is not "practical" to filter and

acidify quite so immediately in the

field, and may decide the shore, a

vehicle, a motel room, or even a remote

lab are more "practical" locations.

Filtering and acidifying in the field

immediately has been thought of as a

better option for consistency (see silver

entry fo an example of what can happen if

there is a delay). However, in recent

methodology designed to prevent some the

contamination and variability listed
above, EPA has recently suggested that

waiting until the sample arrives at the

lab before acidifying is OK [1003]. 

C) What kind of .45 micron filter was

used? The flat plate filters that were

used for years tended to filter .45

micron sizes at first and then smaller

and smaller sizes as the filtering

proceeded and the filter loaded up with

particulate matter. As the filter

clogged, the openings grew smaller and

colloids and smaller diameter matter

began to be trapped on the filter. For

this reason, both the USGS and EPA 1600

series protocols have gone to tortuouspath capsule filters that tend to filter

.45 micron sizes more reliably over time.

Example of specifications from EPA method

1669:

Filter—0.45-um, 15-mm diameter or

larger, tortuous-path capsule

filters, Gelman Supor 12175, or

equivalent [1003].

D) "Normally 3 mL of (1+1) of nitric acid

per liter should be sufficient to

preserve the (water) sample" (40 CFR Part

136, Appendix C, pertaining to ICP

analyses using method 200.7, 1994 edition

of CFR Part 40). Sometimes it is not,

depending on alkalinity and other

factors. What field collectors sometimes

(often?) do is just use pop tabs of 3 mL

of nitric acid and hope for the best

rather than checking to see that the

acidity has been lowered to below a pH of

two. EPA CFR guidelines just call for a

pH of below two, whereas samples meant to

be "acid soluble" metals call for a pH of

1.5 to 2.0 [25]. See also, various USEPA

1984 to 1985 Ambient Water Quality

Criteria Documents for individual metals.

Note: Some shippers will not accept

samples with a pH of less than 1 for

standard shipping (John Benham,

National Parks Service Personal

Communication, 1997).

E) One person might use triple distilled

concentrated nitric acid rather than

reagent grades of acid to avoid possible
contamination in the acid, while another

may not. When using very low detection

limits, some types of acid may introduce

contamination and influence the results.

Using a 10% dilution of nitric acid as

called for by EPA [1003] is another

potential source of contamination, since

the dilution water and/or containers may

be contaminated. Sometimes people may be

incorrectly determining that background

concentrations are high due to

contamination sources such as these (Pat

Davies, Colorado Division of Wildlife,

personal communication, 1997).

Note: Just using triple distilled

nitric acid may not be the total

answer to potential contamination.

The key issue to be sure that the

acid used is free of the metals

being analyzed. In guidance for EPA

method 1669, the use of "ultrapure

nitric acid; or Nitric acid, dilute,

trace-metal grade" is specified

[1003]. In guidance for EPA method

1638, the use of "Nitric

acid—concentrated (sp gr 1.41),

Seastar or equivalent" is specified

[1003].

F) Holding times can strongly influence

the results and there can be quite a bit

of variation even within EPA recommended

6 month limits (see Silver entry for

details). Holding times recommended for

EPA for water samples of metals other

than mercury or chromium VI have usually

been listed as 6 months (Federal

Register, Volume 49, No. 209, Friday,

October 28, 1984, page 43260). In the

1994 version of the CFR, NPDES holding

times for mercury and Chromium VI are the

same ones listed in 1984, but no EPA

holding times are given for other metals

(40 CFR, Part 136.3, Table 2, page 397,

1994). EPA sources stated this was a

typo, that no one else brought it to

their attention in the last 3 years, that

6 months is still an operable holding

time for "other metals" including this

one, and that 6 months is actually an

artifact from the days when 6 month

composite samples were used for NPDES

permits rather than having been
originally scientifically derived. 

Counterpoint: Although some

information suggests that 6 months

is probably too long for some

contaminants in some scenarios (see

silver and copper entries), not all

of the information in the literature

casts the 6 month metals holding

time in such questionable light. In

one study, two EPA research chemists

found that preservation under

certain conditions of drinking water

(EPA Method 200.8) metals samples to

a pH of less than 2 effectively

stabilized the metal concentrations

for 6 months. They found that trace

metal standards in the 10 to 50 ug/L

concentration could be held in 1%

nitric acid if a 5% change of

concentration was acceptable [1009].

Some metal concentrations changed

more than 5% (Zinc up to 24%,

Selenium up to 23%) [1009].

Vanadium, Manganese and Arsenic

changed up to 5-7% [1009]. In some

of the trials, metals were higher

after 6 months due to leaching from

containers, while in some they were

lower [1009]. The changes were

nevertheless considered not of great

consequence related to drinking

water MCLs and EPA method 200.8

[1009]. However, it is not clear

that the careful measures utilized

(like rechecking to make sure the pH

was less than 2, the use of

particular kinds of water samples,

the use of particular acids, etc.)

in this one study replicates what

goes on in day to day ("real world")

contaminants lab work around the

country.

Some EPA sources state that 6 months

should be OK if the sample bottle is

vigorously shaken and re-acidified

in the lab prior to lab analyses, a

practice not universally or even

particularly commonly done in labs

today. The degree to which a water

sample is re-acidified, re-checked

for pH, shaken before analysis, and

the length of time it sits before
and after these steps, seems to vary

a lot between laboratories, and EPA

guidance for various methods is not

consistent. Some labs recheck pH,

some don't. Some shake, some don't,

etc. For drinking water,

preservation is considered complete

after the sample is held in pH of

less than 2 for at least 16 hours

[1007]. New EPA Method 1638

specifies: 

"Store the preserved sample for

a minimum of 48 h at 0–4(C to

allow the acid to completely

dissolve the metal(s) adsorbed

on the container walls. The

sample pH should be verified as

<2 immediately before

withdrawing an aliquot for

processing or direct analysis.

If, for some reason such as

high alkalinity, the sample pH

is verified to be >2, more acid

must be added and the sample

held for sixteen hours until

verified to be pH <2" [1003].

For many other methods, the minimum

holding time in acid is not stated

or is different (see various EPA and

other Agency methods). 

G) If present, air in head space can

cause changes in water sample

concentrations (Roy Irwin, National Park

Service, Personal Communication, based on

several discussions with EPA employees

and various lab managers in February

1997).

Note: air from the atmosphere or in

headspace can cause oxidation of

anaerobic groundwater or anaerobic

sediment samples. This oxidation

can cause changes in chemical

oxidation states of contaminants in

the sample, so that the results are

not typical of the anaerobic

conditions which were present in the

environment prior to sampling (John

Benham, National Park Service,

Personal Communication, 1997). 
H) When is the sample shaken in the lab

or the field? If the filter is acidified

in the field, it will be shaken on the

way back to the lab. If lab acidified,

how much and when is the sample shaken

and then allowed to sit again for various

times periods before analyses? Many

methods treat this differently, and what

many field collectors and labs actually

do before analyzing samples is different

as well. For EPA method 1638, the word

shake appears in the "Alternate total

recoverable digestion procedure": 

"..Tightly recap the container and

shake thoroughly" [1003].

I) If one field filters and acidifies,

one often changes metal concentrations

and colloidal content compared to samples

not treated in this manner. Acidifying

effects microbial changes. If one holds

the samples a while before filtering and

acidifying, the situation changes. In

collection bottles, there are potential

aging effects: temperature changes,

changes in basic water chemistry as

oxygen and other dissolved gasses move

from the water into the headspace of air

at the top, potential aggregation of

colloidal materials, precipitation of

greater sizes over time, development of

bigger and more colloids, and more

sorption (Roy Irwin, National Park

Service, personal communication, 1997). 

4) The guidance of exactly where to take

water samples varies between various state and

federal protocols. Taking water samples at

the surface microlayer tends to increase

concentrations of various contaminants

including metals. Other areas of the water

column tend to produce different

concentrations. Large quantities of

anthropogenic substances frequently occur in

the surface microlayer at concentrations

ranging from 100 to 10,000 times greater than

those in the water column [593]. These

anthropogenic substances can include plastics,

tar lumps, PAHs, chlorinated hydrocarbons, as

well as lead, copper, zinc, and nickel [593].

Sometimes a perceived trend can be more the

result of the details of the sample microlocation rather than real changes in
environmental concentrations (Roy Irwin,

National Park Service, personal communication,

1997). The new EPA method 1669 mentions the

microlayer, and states that one can use a

fluoropolymer closing mechanism, threaded onto

the bottle, to open and close a certain type

of bottle under water, thereby avoiding

surface microlayer contamination [1003].

However, even this relatively new EPA method

1669 also gives recommendations for ways to

sample directly at the surface, and does not

discourage the use of surface samples.

5) Although the above examples are mostly

related to water samples, variability in field

and lab methods can also greatly impact

contaminant concentrations in tissues, soil,

and sediments. Sediment samples from

different microhabitats in a river (backwater

eddy pools vs. attached bars, vs. detached

bars, vs. high gradient riffles vs. low

gradient riffles, vs. glides, etc.) tend to

have drastically different concentrations of

metals as well as very different data

variances (Andrew Marcus, Montana State

University, personal communication, 1995).

Thus, data is only optimally comparable if

both data collectors were studying the same

mix of microhabitats, a stratified sampling

approach which would be unusual when comparing

random data from different investigators. 

6) Just as there are numerous ways to

contaminate, store, ship, and handle water

samples, so are there different agency

protocols and many different ways to handle

samples from other media. One investigator

may use dry ice in the field, another may bury

the samples in a large amount of regular ice

immediately after collection in the field,

while a third might place samples on top of a

small amount of ice in a large ice chest. The

speed with which samples are chilled can

result in different results not only for

concentrations of organics, but also for the

different chemical species (forms) of metals

(Roy Irwin, National Park Service, personal

communication, 1997). 

7) In comparing contaminants metals data, soil

and sediment contaminant concentrations should

usually be (but seldom has been) normalized

for grain size, total organic carbon, and/or

acid volatile sulfides before biologically-
meaningful or trend-meaningful comparisons are

possible (Roy Irwin, National Park Service,

Personal Communication, 1997).

8) There has been tremendous variability in

the precautions various investigators have

utilized to avoid sample contamination.

Contamination from collecting gear, clothes,

collecting vehicles, skin, hair, collector's

breath, improper or inadequately cleaned

sample containers, and countless other sources

must carefully be avoided when using methods

with very low detection limits [1003]. 

Highlights from EPA Method 1669 for Sampling Ambient Water for

Trace Metals at EPA Water Quality Criteria Levels [1003]:

As of March 1997, the 1600 series methods had not yet

been officially approved in 40 CFR for use in NPDES

permits, but the improvements in these methods were

suggested by EPA staff to be wise practice when

attempting low detection limit analyses for metals.

This "field method details" protocol is for the

collection and filtration of ambient water samples for

subsequent determination of total and dissolved Antimony,

Arsenic, Cadmium, Copper, Chromium III, Chromium VI,

Lead, Mercury, Nickel, Selenium, Silver, Thallium, and

Zinc, at low (Water Quality Criteria Range)

concentrations [1003]. It is designed to support the

implementation of water quality monitoring and permitting

programs administered under the Clean Water Act [1003].

This method is not intended for determination of metals

at concentrations normally found in treated and untreated

discharges from industrial facilities [1003]. Existing

regulations (40 CFR Parts 400–500) typically limit

concentrations in industrial discharges to the mid to

high part-per-billion (ppb) range, whereas ambient metals

concentrations are normally in the low part-per-trillion

(ppt) to low ppb range [1003]. This guidance is

therefore directed at the collection of samples to be

measured at or near the water quality criteria levels

[1003]. Often these methods will be necessary in a water

quality criteria-based approach to EPA permitting [1001].

Actual concentration ranges to which this guidance is

applicable will be dependent on the sample matrix,

dilution levels, and other laboratory operating

conditions [1003].

The ease of contaminating ambient water samples with the

metal(s) of interest and interfering substances cannot be

overemphasized [1003]. This method includes sampling

techniques that should maximize the ability of the
sampling team to collect samples reliably and eliminate

sample contamination [1003].

Clean and ultraclean—The terms "clean" and "ultraclean"

have been used in other Agency guidance [1004] to

describe the techniques needed to reduce or eliminate

contamination in trace metals determinations [1003].

These terms are not used in this sampling method due to

a lack of exact definitions [1003]. However, the

information provided in this method is consistent with

summary guidance on clean and ultraclean techniques

[1004].

Preventing ambient water samples from becoming

contaminated during the sampling and analytical process

is the greatest challenge faced in trace metals

determinations [1003]. In recent years, it has been

shown that much of the historical trace metals data

collected in ambient water are erroneously high because

the concentrations reflect contamination from sampling

and analysis rather than ambient levels [1003].

Therefore, it is imperative that extreme care be taken to

avoid contamination when collecting and analyzing ambient

water samples for trace metals [1003].

There are numerous routes by which samples may become

contaminated [1003]. Potential sources of trace metals

contamination during sampling include metallic or metalcontaining sampling equipment, containers, labware (e.g.

talc gloves that contain high levels of zinc), reagents,

and deionized water; improperly cleaned and stored

equipment, labware, and reagents; and atmospheric inputs

such as dirt and dust from automobile exhaust, cigarette

smoke, nearby roads, bridges, wires, and poles [1003].

Even human contact can be a source of trace metals

contamination [1003]. For example, it has been

demonstrated that dental work (e.g., mercury amalgam

fillings) in the mouths of laboratory personnel can

contaminate samples that are directly exposed to

exhalation [1003].

For dissolved metal determinations, samples must be

filtered through a 0.45-um capsule filter at the field

site [1003]. The filtering procedures are described in

this method [1003]. The filtered samples may be

preserved in the field or transported to the laboratory

for preservation [1003]. 

This document is intended as guidance only [1003].

Use of the terms "must," "may," and "should" are

included to mean that EPA believes that these

procedures must, may, or should be followed in

order to produce the desired results when using

this guidance [1003]. In addition, the guidance is
intended to be performance-based, in that the

use of less stringent procedures may be used

so long as neither samples nor blanks are

contaminated when following those modified

procedures [1003]. Because the only way to

measure the performance of the modified

procedures is through the collection and

analysis of uncontaminated blank samples in

accordance with this guidance and the

referenced methods, it is highly recommended

that any modifications be thoroughly evaluated

and demonstrated to be effective before field

samples are collected [1003].

The method includes a great many details regarding

prevention of field contamination of samples, including

clothing needed, clean hands vs. dirty hands operations,

and numerous other details [1003]. 

Surface sampling devices—Surface samples are collected

using a grab sampling technique [1003]. Samples may be

collected manually by direct submersion of the bottle

into the water or by using a grab sampling device [1003].

Grab samplers may be used at sites where depth profiling

is neither practical nor necessary [1003].

An alternate grab sampler design is available [1003].

This grab sampler is used for discrete water samples and

is constructed so that a capped clean bottle can be

submerged, the cap removed, sample collected, and bottle

recapped at a selected depth [1003]. This device

eliminates sample contact with conventional samplers

(e.g., Niskin bottles), thereby reducing the risk of

extraneous contamination [1003]. Because a fresh bottle

is used for each sample, carryover from previous samples

is eliminated [1003].

Subsurface sampling devices—Subsurface sample collection

may be appropriate in lakes and sluggish deep river

environments or where depth profiling is determined to be

necessary [1003]. Subsurface samples are collected by

pumping the sample into a sample bottle [1003]. Examples

of subsurface collection systems include the jar system

device or the continuous-flow apparatus [1003]. 

Advantages of the jar sampler for depth sampling are (1)

all wetted surfaces are fluoropolymer and can be

rigorously cleaned; (2) the sample is collected into a

sample jar from which the sample is readily recovered,

and the jar can be easily recleaned; (3) the suction

device (a peristaltic or rotary vacuum pump, is located

in the boat, isolated from the sampling jar; (4) the

sampling jar can be continuously flushed with sample, at

sampling depth, to equilibrate the system; and (5) the
sample does not travel through long lengths of tubing

that are more difficult to clean and keep clean [1003].

In addition, the device is designed to eliminate

atmospheric contact with the sample during collection

[1003].

Selection of a representative site for surface water

sampling is based on many factors including: study

objectives, water use, point source discharges, non-point

source discharges, tributaries, changes in stream

characteristics, types of stream bed, stream depth,

turbulence, and the presence of structures (bridges,

dams, etc.) [1003]. When collecting samples to determine

ambient levels of trace metals, the presence of potential

sources of metal contamination are of extreme importance

in site selection [1003].

Ideally, the selected sampling site will exhibit a high

degree of cross-sectional homogeneity [1003]. It may be

possible to use previously collected data to identify

locations for samples that are well mixed or are

vertically or horizontally stratified [1003]. Since

mixing is principally governed by turbulence and water

velocity, the selection of a site immediately downstream

of a riffle area will ensure good vertical mixing [1003].

Horizontal mixing occurs in constrictions in the channel

[1003]. In the absence of turbulent areas, the selection

of a site that is clear of immediate point sources, such

as industrial effluents, is preferred for the collection

of ambient water samples) [1003].

To minimize contamination from trace metals in the

atmosphere, ambient water samples should be collected

from sites that are as far as possible (e.g., at least

several hundred feet) from any metal supports, bridges,

wires or poles [1003]. Similarly, samples should be

collected as far as possible from regularly or heavily

traveled roads [1003]. If it is not possible to avoid

collection near roadways, it is advisable to study

traffic patterns and plan sampling events during lowest

traffic flow [1003].

The sampling activity should be planned to collect

samples known or suspected to contain the lowest

concentrations of trace metals first, finishing with the

samples known or suspected to contain the highest

concentrations [1003]. For example, if samples are

collected from a flowing river or stream near an

industrial or municipal discharge, the upstream sample

should be collected first, the downstream sample

collected second, and the sample nearest the discharge

collected last [1003]. If the concentrations of

pollutants is not known and cannot be estimated, it is

necessary to use precleaned sampling equipment at each
sampling location [1003].

One grab sampler consists of a heavy fluoropolymer collar

fastened to the end of a 2-m-long polyethylene pole,

which serves to remove the sampling personnel from the

immediate vicinity of the sampling point [1003]. The

collar holds the sample bottle [1003]. A fluoropolymer

closing mechanism, threaded onto the bottle, enables the

sampler to open and close the bottle under water, thereby

avoiding surface microlayer contamination [1003].

Polyethylene, polycarbonate, and polypropylene are also

acceptable construction materials unless mercury is a

target analyte [1003]. Assembly of the cleaned sampling

device is as follows:

Sample collection procedure—Before collecting ambient

water samples, consideration should be given to the type

of sample to be collected, the amount of sample needed,

and the devices to be used (grab, surface, or subsurface

samplers) [1003]. Sufficient sample volume should be

collected to allow for necessary quality control

analyses, such as matrix spike/ matrix spike duplicate

analyses [1003].

Highlights from EPA Lab Method 1640: Determination of trace

elements in ambient waters by on-line chelation

preconcentration and inductively coupled plasma-mass

spectrometry:

This method is for the determination of dissolved

elements in ambient waters at EPA water quality criteria

(WQC) levels using on-line chelation preconcentration and

inductively coupled plasma-mass spectrometry (ICP-MS)

[1003]. It may also be used for determination of total

recoverable element concentrations in these waters

[1003]. This method was developed by integrating the

analytical procedures contained in EPA Method 200.10 with

the quality control (QC) and sample handling procedures

necessary to avoid contamination and ensure the validity

of analytical results during sampling and analysis for

metals at EPA WQC levels [1003]. This method contains QC

procedures that will assure that contamination will be

detected when blanks accompanying samples are analyzed

[1003]. This method is accompanied by Method 1669:

Sampling Ambient Water for Determination of Trace Metals

at EPA Water Quality Criteria Levels (the "Sampling

Method") [1003]. The Sampling Method is necessary to

ensure that contamination will not compromise trace

metals determinations during the sampling process [1003].

This method is applicable to the following elements:

Cadmium (Cd), Copper (Cu), Lead (Pb), and Nickel

(Ni) [1003].
Many of the requirements for this method are similar to

those for other EPA 1600 series methods [1003].

As of March 1997, the EPA 1600 series methods had not yet

been officially approved in 40 CFR for use in NPDES

permits, but the improvements in these methods were

suggested by EPA staff to be wise practice when

attempting low detection limit analyses for metals

[1003].

For dissolved metal determinations, samples must be

filtered through a 0.45-um capsule filter at the field

site [1003]. The Sampling Method describes the filtering

procedures [1003]. The filtered samples may be preserved

in the field or transported to the laboratory for

preservation [1003]. Procedures for field preservation

are detailed in the Sampling Method; provides procedures

for laboratory preservation are provided in this method

[1003].

Acid solubilization is required before the determination

of total recoverable elements to aid breakdown of

complexes or colloids that might influence trace element

recoveries [1003].

This method should be used by analysts experienced in the

use of inductively coupled plasma mass spectrometry (ICPMS), including the interpretation of spectral and matrix

interferences and procedures for their correction; and

should be used only by personnel thoroughly trained in

the handling and analysis of samples for determination of

metals at EPA WQC levels [1003]. A minimum of six

months' experience with commercial instrumentation is

recommended [1003].

Sample preservation—Preservation of samples and field

blanks for both dissolved and total recoverable elements

may be performed in the field when the samples are

collected or in the laboratory [1003]. However, to avoid

the hazards of strong acids in the field and transport

restrictions, to minimize the potential for sample

contamination, and to expedite field operations, the

sampling team may prefer to ship the samples to the

laboratory within 2 weeks of collection [1003]. Samples

and field blanks should be preserved at the laboratory

immediately when they are received [1003]. For all

metals, preservation involves the addition of 10% HNO3 to

bring the sample to pH <2 [1003]. For samples received

at neutral pH, approx 5 mL of 10% HNO3 per liter will be

required [1003].

Store the preserved sample for a minimum of 48 h at 0–4(C

to allow the acid to completely dissolve the metal(s)

adsorbed on the container walls [1003]. The sample pH
should be verified as <2 immediately before an aliquot is

withdrawn for processing or direct analysis [1003]. If,

for some reason such as high alkalinity, the sample pH is

verified to be >2, more acid must be added and the sample

held for 16 h until verified to be pH <2 [1003].

Highlights from EPA Method 1638: Determination of Trace

Elements in Ambient Waters by Inductively Coupled Plasma —

Mass Spectrometry:

This 1996 proposed EPA method is for the determination of

dissolved elements in ambient waters at EPA water quality

criteria (WQC) levels using inductively coupled plasmamass spectrometry (ICP-MS) [1003]. It may also be used

for determination of total recoverable element

concentrations in these waters [1003]. This method was

developed by integrating the analytical procedures in EPA

Method 200.8 with the quality control (QC) and sample

handling procedures necessary to avoid contamination and

ensure the validity of analytical results during sampling

and analysis for metals at EPA WQC levels [1003]. This

method contains QC procedures that will assure that

contamination will be detected when blanks accompanying

samples are analyzed [1003]. This method is accompanied

by Method 1669: Sampling Ambient Water for Determination

of Trace Metals at EPA Water Quality Criteria Levels

("Sampling Method") [1003]. The Sampling Method is

necessary to assure that trace metals determinations will

not be compromised by contamination during the sampling

process [1003].

This method may be used with the following metals:

Antimony (Sb), CAS 7440-36-0

Cadmium (Cd), CAS 7440-43-9

Copper (Cu), CAS 7440-50-8

Lead (Pb), CAS 7439-92-1

Nickel (Ni), CAS 7440-02-0

Selenium (Se), CAS 7782-49-2

Silver (Ag), CAS 7440-22-4

Thallium (Tl), CAS 7440-28-0

Zinc (Zn), CAS 7440-66-6

Lower detection levels for copper are available with EPA

method 1640 (see description above).

As of March 1997, the EPA 1600 series methods had not yet

been officially approved in 40 CFR for use in NPDES

permits, but the improvements in these methods were

suggested by EPA staff to be wise practice when

attempting low detection limit analyses for metals

[1003].

This method is not intended for determination of metals
at concentrations normally found in treated and untreated

discharges from industrial facilities [1003]. Existing

regulations (40 CFR Parts 400–500) typically limit

concentrations in industrial discharges to the mid to

high part-per-billion (ppb) range, whereas ambient metals

concentrations are normally in the low part-per-trillion

(ppt) to low ppb range [1003].

The ease of contaminating ambient water samples with the

metal(s) of interest and interfering substances cannot be

overemphasized [1003]. This method includes suggestions

for improvements in facilities and analytical techniques

that should maximize the ability of the laboratory to

make reliable trace metals determinations and minimize

contamination [1003]. These suggestions are ...based on

findings of researchers performing trace metals analyses

[1003]. Additional suggestions for improvement of

existing facilities may be found in EPA's Guidance for

Establishing Trace Metals Clean Rooms in Existing

Facilities, which is available from the National Center

for Environmental Publications and Information (NCEPI) at

the address listed in the introduction to this document

[1003].

Clean and ultraclean—The terms "clean" and "ultraclean"

have been applied to the techniques needed to reduce or

eliminate contamination in trace metals determinations

[1003]. These terms are not used in this method because

of their lack of an exact definition [1003]. However,

the information provided in this method is consistent

with the summary guidance on clean and ultraclean

techniques [1003].

The procedure given in this method for digestion of total

recoverable metals is suitable for the determination of

silver in aqueous samples containing concentrations up to

0.1 mg/L [1003]. For the analysis of samples containing

higher concentrations of silver, succeedingly smaller

volume, well-mixed sample aliquots must be prepared until

the analysis solution contains <0.1 mg/L silver [1003].

Sample preservation—Preservation of samples and field

blanks for both dissolved and total recoverable elements

may be performed in the field at time of collection or in

the laboratory [1003]. However, to avoid the hazards of

strong acids in the field and transport restrictions, to

minimize the potential for sample contamination, and to

expedite field operations, the sampling team may prefer

to ship the samples to the laboratory within two weeks of

collection [1003]. Samples and field blanks should be

preserved at the laboratory immediately upon receipt

[1003]. For all metals, preservation involves the

addition of 10% HNO3 to bring the sample to pH <2 [1003].

For samples received at neutral pH, approx 5 mL of 10%
HNO3 per liter will be required [1003].

Do not dip pH paper or a pH meter into the sample; remove

a small aliquot with a clean pipet and test the aliquot

[1003]. When the nature of the sample is either unknown

or known to be hazardous, acidification should be done in

a fume hood [1003]. 

Store the preserved sample for a minimum of 48 h at 0–4(C

to allow the acid to completely dissolve the metal(s)

adsorbed on the container walls [1003]. The sample pH

should be verified as <2 immediately before withdrawing

an aliquot for processing or direct analysis [1003]. If,

for some reason such as high alkalinity, the sample pH is

verified to be >2, more acid must be added and the sample

held for sixteen hours until verified to be pH <2 [1003].

For drinking water methods, EPA lists the following older

methods [893]:

Monitoring Requirements: Ground water systems monitored

annually; surface water systems monitored quarterly;

repeat monitoring dependent upon detection and compliance

history with a minimum of 5 years between sampling;

community and non-transient non-community water systems

to have different monitoring requirements for determining

compliance with corrosion control treatment techniques.

Analytical Methods: Atomic absorption/furnace technique

(EPA 220.2;ASTM D1688-90C; SM 3113); atomic

absorption/direct aspiration (EPA 220.1;ASTM D1688-90A;

SM 3111-B); inductively-coupled plasma (EPA 200.7; SM

3120);inductively-coupled plasma/mass spectrometry (EPA

200.8); atomic absorption/platform furnace (EPA 200.9).

See also: note on colloids in W.Misc. section above.

Detailed Information from ATSDR [979]:

BIOLOGICAL MATERIALS: 

Copper in other biological materials such as hair

and nails can be determined by using suitable

procedures for dissolving the sample matrix and

employing the same analytical techniques as with

blood and tissue [979]. These methods determine the

total amount of copper in the sample [979]. The

methodology for analyzing biological material is

similar to that used for environmental samples

[979]. The most commonly employed methods use

atomic adsorption spectroscopy or inductively

coupled plasma-atomic emission spectroscopy [979].

ENVIRONMENTAL SAMPLES: 
Analytical methods determine the total copper

content of the samples; determining specific copper

compounds and complexes in samples is difficult

[979]. The most common methods used for

environmental samples are atomic absorption

spectrometry, either flame or graphite furnace, and

inductively coupled plasma-atomic emission

spectroscopy [979]. Water and wastewater samples

can be analyzed for copper by EPA Test Method 220.1

(atomic absorption, direct aspiration) or 220.2

(atomic absorption, furnace technique) [979]. These

methods are suitable for groundwater and surface

water and domestic and industrial effluents [979].

Both freshwater and saline water samples can be

analyzed by these methods [979]. If the

determination of dissolved and suspended copper is

required, samples should be filtered using a 0.45

um membrane filter [979]. Suspended solids, as well

as sludge and sediment, may be analyzed by EPA

Methods 220.l and 220.2 after an initial acid

digestion with HNO3 [979]. Interference by other

elements is not a problem in the analysis; however,

background correction may be required in using

atomic absorption to correct for nonspecific

absorption and scattering which may be significant

at the analytical wavelength 324.7 nm [979]. In the

determination of trace metals, major concerns are

contamination and loss [979]. Contamination can be

introduced from impurities in reagents and

containers as well as from laboratory dust [979].

Losses may also occur due to adsorption onto

containers [979].

AAS = atomic absorption spectrometry; ASV = anodic

stripping voltammetry; ICP-AES = inductively

coupled plasma-atomic emission spectroscopy [979].

Other analytical methods used for copper analysis

include x-ray fluorescence, anodic stripping

voltammetry, neutron activation analysis, photoninduced x-ray emission, as well as chemical

derivation, followed by gas chromatographic or

liquid chromatographic analysis [979].