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August 1996

Standards and Guidelines Branch Environmental Assessment Division Environmental Regulatory Service

The water quality guideline derived in this document protects freshwater aquatic life against copper toxicity. This guideline is based on up-to-date, high quality scientific information and is derived according to the Protocol to Develop Alberta Water Quality Guidelines for Protection of Freshwater Aquatic Life (Alberta Environmental Protection 1996). Using the Protocol document with this guideline document will place the copper guideline in context.

This document has been reviewed within Alberta Environmental Protection. However, we recognize that other information may exist that could have a bearing on this document. For this reason alone, this document is called "Draft". Comments from the public are invited until September 30, 1997. After this period, the comments will be addressed in a "Final" document.

Any comments, questions, or suggestions regarding the content of this document may be directed to: Standards and Guidelines Branch Alberta Environmental Protection 6th Floor, 9820-106 Street Edmonton, Alberta T5K 2J6 Phone: (403) 422-6102

Additional copies of the Alberta Water Quality Guideline for the Protection of Freshwater Aquatic Life - Copper may be obtained by contacting : Regulatory Approvals Centre Alberta Environmental Protection Main Floor, 9820-106 Street Edmonton, Alberta T5K 2J6 Phone: (403) 427-6311


This document contains the relevant toxicological information and other literature used to develop a water quality guideline that protects freshwater aquatic life against copper toxicity. Its derivation follows the Protocol to Develop Alberta Water Quality Guidelines for Protection of Freshwater Aquatic Life (Alberta Environmental Protection 1996).

Copper is an essential compound for plants and animals in small quantities. However, copper becomes toxic when biological requirements are exceeded. Copper is widely distributed in environmental media because it is a naturally occurring element. Compared to natural emissions, emissions of copper from human activities are substantial. Most copper released from human activities comes from disposal of coal ash residue and spreading of municipal and industrial wastes on land.

Cupric ion is the main toxic form of copper. Cupric ion in water is bound (complexed) with inorganic and organic compounds, which reduces cupric ion concentrations (and its toxicity) substantially. The effects of copper on freshwater organisms are numerous. This document describes physiological effects, behavioral effects, acute toxicity (lethal effects), chronic toxicity (long-term effects), microcosm and ecosystem effects, and genotoxic effects. This document also presents a water quality guideline based on the acute toxic effects, chronic toxic effects and genotoxic effects of copper.

High quality (primary) information on short-term effects (acute toxicity) of copper was available for 29 fish species (five different orders), 24 invertebrate species (11 different orders) and one amphibian species. According to the Protocol to Develop Alberta Water Quality Guidelines for Protection of Freshwater Aquatic Life (Alberta Environmental Protection 1996), the minimum requirements for developing an acute guideline were amply met. The acute toxicity information on three species and one invertebrate species clearly indicated that acute copper toxicity diminished in water with increasing hardness. This relationship was included in deriving an acute copper guideline equation.

Primary data on long-term effects (chronic toxicity) of copper were available for 11 fish species (from four different orders), eight invertebrate species (form five different orders), and five plant species. According to the Protocol to Develop Alberta Water Quality Guidelines for Protection of Freshwater Aquatic Life (Alberta Environmental Protection 1996), the minimum requirements for developing a chronic guideline were amply met. The chronic toxicity information did not indicate that chronic toxicity of copper was affected by water hardness.


The resulting Alberta water quality guideline that protects freshwater aquatic life against copper toxicity is: Copper Guideline (mg/L) Acute Chronic 1 e0. In surface water. ii . many substances are present that bind copper: the amount of copper that could be toxic is thereby greatly diminished. Specific guidance in this document should be used to accurately apply the copper guideline.64497 0.0071 The chronic toxicity of copper in soft water was inconclusive: the chronic guideline can therefore only be applied at water hardness equal to or greater than 50 mg/L CaCO3. Additional guidance is provided in the Protocol to Develop Alberta Water Quality Guidelines for Protection of Freshwater Aquatic Life (Alberta Environmental Protection 1996). Both acute and chronic copper guidelines apply to acid-extractable copper concentrations.979123*ln(hardness)-8.

. . . .3 Organic Complexation . . . . . . . . . 23 3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2 Alberta Chronic Guideline . . . . . . . . . . . 1 1. . . . . . . .1 Effects of Copper on Fish . . . . . . . . . . . . . . 4 1. . . . . . . . . . . . . . . 3 1. . . . . . . . . . . . . . . . . . . .1 Final Acute Value and Alberta Acute Guideline . . . . . . . . . . . . . 1 1. . . . . . . . . . . . . . . . . . . . . . . . . . . .5 Environmental Concentrations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28 DERIVATION OF ACUTE AND CHRONIC GUIDELINES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 2. . .8 Metal-binding Proteins (Biomarker) . . . . . . . . . . 8 2. . . . . . . . . . . . . . . . . . . . . . . . .7 Genotoxicity of Copper . . . . . . . . . . . . . iii 1 BACKGROUND INFORMATION ON COPPER . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4 Adsorption . . . . 1 1. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3 Production and Uses . . . . . . . . . . . . . . . . . . 29 4. . . 44 2 3 4 5 6 7 iii . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 3. . . . . . . . . . . . . . . . . .TABLE OF CONTENTS EXECUTIVE SUMMARY . . . . . . . . . . . . . . . . .2 Inorganic Complexation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3 Application of the Alberta Copper Guideline . . . . . . . . . . . . . . . . 12 3. . . . . . . . . . . 17 3. . . . . . . 33 4. .1 Physical and Chemical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 ENVIRONMENTAL EFFECTS OF COPPER . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 3. . . . . . i TABLE OF CONTENTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 2. . . . . . . . . . . . 29 4. . . . . . . . . . . . . . . . . . . . . . . . . . . 21 3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41 COPPER GUIDELINES FROM OTHER JURISDICTIONS . . . . . . . . . . . . . . . .4 Sources to the Environment . . . . . .2 Effects of Copper on Invertebrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6 Effects of Copper on Microcosms and Ecosystems . . . . . . . . . . . . . . . . . . . . . . . .5 Effects of Copper on Other Microorganisms . . . . . . . 42 REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1 Oxidation states . . . . . . . . . . . . . . . . . . . . . . . . . . .2 Method of Analysis & Current Detection Limits . . . . . . . . . . . . 38 DATA GAPS . . . . . . . . . . . 6 ENVIRONMENTAL FATE AND BEHAVIOUR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3 Effects of Copper on Amphibians . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4 Effects of Copper on Plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 2. . . . . . . . . . . . . . 27 3. . .

. . . . . . Figure 4. . . . . . . . . . . . . Table 8. . . Figure 3. APPENDIX 8. Table 6. . . 102 Chronic copper toxicity data on freshwater fish . . . . . . . . . . . . . . . . . . Table 4. . . . . . . . . . . . . . . . . . . . . 34 Primary copper toxicity studies: acute toxicity versus acute-to-chronic ratio (ACR) . . . . . . . 30 Statistical information on regression analyses for a chronic guideline . Table 5. . . . . . . . . Table 3. . . . . . . APPENDIX 5. . . . . . . . 78 Acute copper toxicity data on freshwater fish . . . . . . . . . . . 2 Analytical methods for determining copper in water and wastewater . . . . . . . . . . . . . . . . . . 3 Worldwide emissions of copper (103 t/yr) into the environment at the beginning of the 1980s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43 List of Figures Figure 1. . . . . . . . . . . . . . 42 Comparison of freshwater aquatic life guidelines for copper (in :g/L) from various jurisdictions. . . Figure 2. . . . . . . . . . . . . 122 List of Tables Table 1. . . . . . . . . . . . . . . . . . . . . . APPENDIX 2. . . . . . . . APPENDIX 4. . . . . . . . . APPENDIX 3. . . . . . . . . . . . . . . . . 84 Acute copper toxicity data on freshwater invertebrates . . . . . . . . . . . . 36 iv . . . . . 34 Copper guidelines for the protection of freshwater aquatic life in other jurisdictions. . . . . . . . . . . . Physical and chemical properties of metallic copper . . . . . . . . . . . . . . . . . . . . 5 Statistical information on regression and ancova analyses (Sokal and Rohlf 1981) for derivation of an acute copper guideline. . . . . 118 Computations for the chronic Alberta copper guideline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Table 7. . . . . . . Acute and chronic copper toxicity data on amphibians . . . . . . . . . . . . . . . . . . . . . . . . . Table 2. . . . . . . .APPENDIX 1. . . . . . . . . . . . . . . . . . . . . . . 35 Primary copper GMCVs (Genus Mean Chronic Values) . . . . . . . . . . . . . . APPENDIX 7. . . . . . . . . . . . . 114 Chronic copper toxicity data on freshwater invertebrates . . . . . . . . . 33 Primary acute-to-chronic ratios (ACR) from copper toxicity studies. . . . . . . . . 32 Correlation between chronic copper toxicity and water hardness for fathead minnow . . . . . . . Primary copper GMAVs (Genus Mean Acute Values) . . . . . . . . . . . 95 Computations for the acute Alberta copper guideline . . . . . . . . . . . 76 Copper toxicity data on freshwater algae and plants . . . . . . . . . . . . . . . APPENDIX 6. . . . . . . . . . . . . . . . . . . . . . . . .

These properties make it one of the most important metals (U. the use of copper ion electrode potentiometry permits determination of the hydrated cupric Cu(II) ion. electrochemical techniques. Copper deficiency results in reduced synthesis of the copper-containing electron carriers plastocyanin and cytochrome oxidase. etc. flow injection technique. it is not accurate at concentrations < 5 :g/L. Both anodic stripping voltammetry (ASV) and differential pulse ASV determine copper complexes of relatively low stability (Spear and Pierce 1979). Long and Martin 1992). malleability. Copper also serves as the oxygen coupling site in haemocyanin. Among electrochemical techniques.1 BACKGROUND INFORMATION ON COPPER Copper is considered to be an essential trace element for plants and animals. alloying ability. it is a component of many metalloenzymes and respiratory pigments (Demayo and Taylor 1981).2 Method of Analysis & Current Detection Limits Metals may be determined satisfactorily by atomic absorption spectrometry (AAS). high performance liquid chromatography. and aesthetically pleasing appearance. 1 . low corrosion. by colorimetric methods (Standard Methods 1992. with somewhat less precision and sensitivity. 1. inductively coupled plasma atomic emission spectrometry (ICP-AES). the respiratory blood pigment in many molluscs and certain other invertebrates (Birge and Black 1979). 1995). inductively coupled plasma mass spectrometry (ICP-MS). however. The various methods are listed in Table 2 with information on typical instrumental detection limits and analytical ranges. However. copper becomes toxic to aquatic biota when biological requirements are exceeded. or. high electrical conductivity. Department of Health & Human Services 1990). The reduction of these electron carriers reduces photosynthesis and respiration (Barón et al. 1. Copper is important for maintaining optimum plant metabolism. unless they are combined with various separation techniques such as ion chromatography.1 Physical and Chemical Properties Copper (Chemical Abstracts Service CAS Registry Number 7440-50-8) is classified as a noble metal (as are silver and gold) and can be found in nature in the elemental form. gas chromatography. These methods do not permit distinction between different chemical forms or species of copper. The physical and chemical properties of copper are presented in Table 1.S. It is required in the synthesis of chlorophyll (a photosynthetic pigment in plants) and haemoglobin (a respiratory blood pigment). Its chemical and physical properties include high thermal conductivity.

dissolved.001 mg/L). 2 . copper in an unfiltered sample after treatment with a hot dilute mineral acid or after the addition of a dilute mineral acid. Department of Health & Human Services 1990). Physical and chemical properties of metallic copper (from U. total and acid-extractable copper is measured by graphite furnace AAS (detection limit of 0. copper in an unfiltered sample after vigorous digestion with a concentrated acid.00005 mg/L).S. In Alberta.92 None No data No data No data insoluble (CuSO4 14. total copper in an unacidified sample retained by a 0. and.4 2567 8. (d) suspended/residue copper. mm Hg Autoignition temperature Copper 63.Table 1. and by ICP-MS (detection limit 0.546 reddish solid 1083. slightly soluble in ethanol) 10 (1870 oC) No data Different copper fractions in water may be reported: (a) dissolved copper.45 :m membrane filter.001 mg/L with 5-fold preconcentration). or the sum of dissolved and suspended copper. Property Atomic/Molecular Weight Color Physical State Melting Point oC Boiling Point oC Density g/cm3 Odour Odour Threshhold: Water/Air Taste Taste Threshhold Solubility Water (g/100mL) Organic Solvents Vapour pressure.45 :m membrane filter. (b) total copper.3 @ 0oC) " (CuSO4 soluble in methanol. copper in an unacidified sample that passes through a 0. by ICP-AES (detection limit 0. (c) acid-extractable copper.

00006-0.01 0.8%) and Ontario (24. Ontario. Long and Martin 1992).001* 0. Total production in 1990 was similar to the production in 1975 (Wood 1976. Rated milling capacity of mines with copper as a main product varied from 330 tonnes of ore per day (tpd) to 140.0005-0. Operations of these non-ferrous companies concentrate on smelting and refining. plumbing. as quoted in Demayo and Taylor 1981).000 tpd in 1990. The electrical industry is the largest single user (>50% of total 3 . and are largely export oriented (Industry Canada 1994). The main uses today are in the electrical. ductility.020 0. construction.4%).006 0. The metal copper and its compounds have been used by man since prehistoric times because of its properties such as malleability. In 1990 and 1991. alloying qualities. Standard Methods 1992.5 0.1 Optimum Range/ Upper Limit (mg/L) * combined with flow injection 1.00003 upper limit 50 0. Manitoba. These data indicated that most of the production is in British Columbia (61.3 Production and Uses In Canada. 35 mines produced copper as the main product or one of the products and three additional mines produced copper as a by-product during 1990 (Environment Canada 1992). corrosion resistance.2-10 0. Analytical methods for determining copper in water and wastewater (from Mancy and Allen 1977. Quebec and New Brunswick.0006 0.006 0. and pleasing appearance. The copper mines are located in British Columbia. three of these mines closed and one suspended operations.Table 2. and automotive industries. Instrument Detection Limit (mg/L) Atomic absorption Flame AAS Electrothermal AAS Plasma emission ICP-AES ICP-MS Electrochemical Anodic stripping voltammetry Colorimetric Neocuproine Bathocuproine 0. conductivity.005-0.

Principal natural sources are wind-borne soil particles and volcanoes. Releases to Water Both natural and anthropogenic sources contribute copper to water: natural weathering of soil.4% of copper released to the environment with windblown dust as the primary natural source (U. Department of Health & Human Services 1990). 1995.4 Sources to the Environment Copper and its compounds are naturally present in the earth's crust. and discharges from industry and wastewater treatment plants. atmospheric deposition.4% of the identified copper releases to the environment enters waterways. However.production) and covers power transmission. The main anthropogenic source is emissions from the primary non-ferrous metal industry (Pacyna et al. Construction and plumbing is the second largest user of copper (piping and the manufacture of alloys [e. Copper sulfate use represented 13% of the releases to water. Releases to Air On a global scale. electronics and electrical equipment. In the United States.S.g. natural and anthropogenic copper emissions to air are similar in magnitude. Department of Health & Human Services 1990). the use of copper as a biocide has decreased considerably (Demayo and Taylor 1981. copper emissions to air are estimated to be only 0. bronze. A 1976 evaluation in the United States determined that 2. 1995). 4 . 1. Moore and Ramamoorthy 1984).. The latest worldwide emission figures for various metals (including copper) are for the beginning of the 1980s (summarized by Pacyna et al. brass]). Copper sulfate and cuprous oxude have been used as fungicides for many decades. Department of Health & Human Services 1990).S. U. Mine tailing and slags and wastes from smelters can also be a major source of copper to soils: 657-1577 103 t/year (Nriagu and Pacyna 1988). Releases to Soil On a global scale. Natural discharges to air and water may therefore be significant. 1980 as quoted in U.S. The major source is from land runoff through natural weathering (68%. the two principal sources of copper to soils are disposal of ash residues from coal combustion and municipal and industrial wastes on land. urban runoff contributed 2% (Perwack et al. Table 3). Most of the copper released to the environment is released to soil and least is released to air (Table 3).

9-18.6-23. Agricultural products constitute 2% of the copper released to soil (Perwack et al. an estimated 97% of copper released into the environment is to land.0-36.0-15.0 93.4 2.0 11.5-1402.5 21.2 14.0 0.2-239. 1995).0 0.8 34.0 2.1-7. 1980 as quoted in U.0-56.6 2. Department of Health & Human Services 1990).7-50.2-35.2-6.5-26.5 0.1-2.1 11.8 In the United States.2-53.1-0.0 3.0 39.refining manufacturing processes atmospheric deposition Soil Anthropogenic disposal municipal and industrial waste wastage of commercial products coal fly ash and bottom fly ash fertilizer peat atmospheric deposition 103 t/yr 0.9 1.6-70.2 395.4 0. Worldwide emissions of copper (103 t/yr) into the environment at the beginning of the 1980s (after Pacyna et al. Sources Air Natural windborn soil particles seasalt spray volcanoes wild forest fires biogenic processes Anthropogenic non-ferrous metal industry fuel combustion other industry and use waste incineration Water Anthropogenic waste disposal steam electric mining.9 0.1-6.8-11.6 0-0. Tailings and overburdens from copper mines and tailings from mills are the primary source.8 Subtotal Total 19.7-190.0-335.0790.0 541. smelting.5 6.S.9-104. 5 .6-1.9-15.Table 3.4 15.0 0.

Copper ranks 25th in abundance among the elements present in the earth's crust. This inventory includes all facilities that manufacture. Alberta has no mines that produce copper as a main product or a by-product. For those facilities reporting to NPRI.4% to water and 31. process or otherwise use any of the NPRI substances in quantities of 10 tonnes or more per year.Canadian Copper Releases A 1993 summary of copper (and its compounds) releases in Canada is provided by NPRI (National Pollutant Release Inventory).4% to air (stack. 0. copper mines are subject to the Metal Mining Liquid Effluent Regulations or associated guidelines. 32 facilities released more than 1.1 tonnes. 7 occasionally exceeded the regulations or guidelines (Environment Canada 1992). and 0.6 mg/L maximum concentration in a grab sample. 6 .45 mg/L maximum concentration in a composite sample. Although facilities engaged in mining are not subject to reporting their releases to NPRI.998 tonnes of copper per year. these facilities released 13.890 tonnes per year). Copper concentrations in pristine environments are generally less than 50 mg/kg dry weigth. Only one of the 32 facilities is located in Alberta (Sherritt Inc. most (99%) of it was landfarmed. In total. Copper concentrations in soils range between 2 and 100 mg/kg dry weigth with a mean value of 20 mg/kg (Bowen 1966 as quoted in Demayo and Taylor 1981).3 mg/L maximum monthly arithmetic mean. Fort Saskatchewan): their total release of copper in 1993 was 30. employ 10 or more people or manufacture. and process or otherwise used the substance in greater than 1% weight. while concentrations in polluted environments can be several thousand mg/kg (Harrison and Bishop 1989). Of this total. One of the 35 copper mines was not subject to the regulations or guidelines.5 Soil Environmental Concentrations The crustal average concentration of copper has been estimated at 55 mg/kg but varies with the type of rock (10 mg/kg for granite and 100 mg/kg for basalt). Sediment Mean copper concentrations in freshwater sediments ranged from 12 to 57 mg/kg with individual values as high as 4000 mg/kg (Spear and Pierce 1979). 85% was released to water from a copper mine in British Columbia (11.. The authorized numerical levels for copper in the regulations and guidelines are 0.9% to land (landfarm and landfill).0 tonne per year in 1993. The copper releases were 38. 29. 1. storage and fugitive). Of the remaining 34 mines.

mean total concentrations increased from 0. Dissolved copper levels in Canadian surface waters rarely exceed 5 :g/L (Spear and Pierce 1979).013 mg/L before the Peace River enters Lake Athabasca.005 mg/L.020 mg/L (Golder Associates 1994). the highest observed value was 0.4). The highest copper concentrations in sediments were found in reservoirs and sites with high levels of organic matter (Anderson et al. Stormsewers and combined sewers did not seem to be a significant source of copper during storms: flowweighted concentrations of total copper were mostly at or below detection limit (Mitchell 1994).Copper concentrations in sediments of the Battle River (Alberta) varied from 1.010 and 0. with a median of 10 :g/L.5N HCl-extractable). High copper values were generally observed in spring. municipal and industrial effluents on water quality in the North Saskatchewan River (Alberta). In the Red Deer River.C.001 mg/L). Most total copper concentrations were around the detection limit (0.032 mg/L (Noton and Shaw 1989. 1990).002 mg/L at the B. median concentrations of total and extractable copper varied from 0. Similar median values for total copper are reported for Federal-Provincial monitoring sites in British Columbia (Singleton 1987). In the North Saskatchewan River. In the Bow River. High copper levels were largely a result of increased suspended solid concentrations (Shaw et al. no spatial trends in total copper were observed. In the Athabasca River. copper concentrations occasionally exceeded 0. Dissolved copper was on average 25% of total copper.003 mg/L.004 mg/L and 0.16 to 35. total copper concentrations varied from below detection to 85 :g/L. Copper levels in river waters range from 0. 7 . median concentrations in most effluents were less than 0.006 to 0.5 mg/kg (0. associated with high concentrations of suspended solids (Noton and Saffran 1995). At 11 interprovincial border sites in the prairies. In the Peace River. most median values were around 3 :g/L with some values as high as 8 :g/L (PPWB 1993). 1994). Noton and Saffran 1995).5 to 1. Median total copper concentrations in the industrial effluents ranged from 0. In Alberta rivers.001 to 0. The highest median concentration was in Sherritt Inc's effluent: the only company located in Alberta that reported copper releases to NPRI (Section 1. Freshwater Copper is widely distributed in water since it is a naturally occurring element. Comprehensive studies determined the effect of stormsewers. Median total copper concentrations of the two municipal wastewater treatment facilities were 0. copper concentrations were generally higher downstream of the City of Edmonton than upstream.0 :g/L. combined sewers. The increase was due to natural and anthropogenic copper loads (Shaw et al. 1994). copper concentrations are generally near detection limit.093 mg/L.003 mg/L (Bow River Water Quality Task Force 1991). respectively (Shaw and Anderson 1994).001 to 0. Dissolved copper levels in uncontaminated freshwaters usually range from 0. increasing to > 2 :g/L in urban areas (Moore and Ramamoorthy 1984).-Alberta border to 0.6 to 400 :g/L.

and Cu(III). Cu(II) reduction increases with an increase in chloride concentrations and is likely controlled by poorly characterized organic chelators (Moffett and Zika 1987). Cu(I) disappears in milliseconds in oxic environments (Glazewski and Morrison 1995). However. 2. Cu(III) is strongly oxidizing and only occurs in a few compounds.S.S. Cu(II) ions coordinate with six water molecules: the arrangement is distorted in that four molecules closely bound to copper in a planar array and the other more loosely bound in the polar position. Moffett and Zika 1987). Cu(I) is still less than 0. In seawater. U. Department of Health & Human Services 1990). Cu(II). Irradiation with UV or reaction with hydrogen peroxide leads to the formation of Cu(I) from Cu(II) (Balzani and Carassiti 1970. However. Department of Health & Human Services 1990).2 ENVIRONMENTAL FATE AND BEHAVIOUR 2. the solubility of Cu(II) is controlled by malachite (Cu2(OH)2CO3) below a pH of 7 and by tenorite (CuO) above a pH of 7 (Stumm and Morgan 1981). The main inorganic cupric ion 8 . Cupric ion (Cu(II) or Cu2+) is the most important oxidation state and is the oxidation state generally encountered in water. The proportion of Cu(I) relative to Cu(II) increases with an increase in bicarbonate concentration and an increase in pH.1 Oxidation states Copper is the first element of Group 1B of the periodic table and displays four oxidation states: Cu(0). in which L is a ligand: (Balzani and Carassiti 1970). Azurite (Cu3(OH)2(CO3)2) may form instead of malachite depending on the carbonate and copper concentrations (Mancy and Allen 1977). Cu(I). None of these compounds are industrially important and environmentally significant (U. Cuprous ion or Cu(I) is difficult to study in aquaeous solution because of low solubility (Leckie and Davis 1979) and strong tendency to disproportionate according to the following reaction.5% of Cu(II) (Stiff 1971). Addition of ligands will successively displace only the four planar water molecules (Spear and Pierce 1979.2 Inorganic Complexation In freshwater free of organic complexing agents.

EDTA. Substantial organic-copper complexation also may occur in water with relatively low organic content (Nelson et al. Borgmann and Ralph 1983). fulvic acid. and TRIS). Nelson et al. algal exudates. The complexation reaction with fulvic acids and dissolved organic matter is fast (Gardner and Ravenscroft 1991. 1986). humic acids. extracellular polypeptides. Their toxicity varied with alkalinity. and Cu(CO3)22make up 98% of dissolved inorganic copper. glycine. chloride. amino acids. 1986). 1990b. 1979). 1986). The effect on copper toxicity was tested on various organisms with several organic compounds (NTA. pH and hardness (Straus and Tucker 1993). However. In freshwater. Cu(OH)3. chelators in pulp mill effluent. 2. Spear and Pierce 1979). sewage. The inorganic species most toxic to cutthroat trout are Cu2+. 1979. nitrogen. indicating that this copper species is rare (Nelson et al. sulphate. CuCO3 is generally not considered to be toxic (Chakoumakis et al. Insoluble coppersulfide forms in the presence of sulfides (Spear and Pierce 1979. the dominant species change from Cu2+. copperhydroxy and carbonate complexes also depend on alkalinity and the magnitude of stability constants for the formation of complexes. the magnitude of the stability constant of Cu(OH)2 formation is very large. Cu(OH)+. and phosphates make up less than 2% of dissolved inorganic copper (Nelson et al. Other chemical species complexed with hydroxides. and various copper chelators (Nelson et al. copper species other than Cu2+ are toxic to the waterflea Daphnia (Borgmann and Charlton 1984). 1994). organic ligands are more important in binding copper than inorganic ligands containing sulfur. ammonium.3 Organic Complexation Many studies indicate that copper in water is held in solution mainly by complexation with naturally occurring organic ligands (Mancy and Allen 1977. Lin et al. The affinity of copper varies among organic compounds: the affinity of copper for humic acids is greater than for fulvic acids (Huang and Yang 1995). Dissolved organic-copper include complexes with amino acids. Cu(OH)+ and Cu(OH)2 (Chakoumakis et al. These latter complexes are more important in seawater because of higher concentrations of these ligands (Flemming and Trevors 1989). Chelation complexes are expected to be relatively non-toxic (Spear and Pierce 1979). Stumm and Morgan 1981). 1986). phosphorus.(Stumm and Morgan 1981). 9 . Cupric ion is the main toxic species. However. Cu(CO3)22-. chlorides. The relative proportion of Cu2+. 1986). Although pH and alkalinity vary substantially in freshwater systems. However. carboxylic acids. copper complexation capacity increased with decreasing pH and increasing salinity (Gardner and Ravenscroft 1991). Cu(OH) ultimately Cu(OH)42. carbonates. Cu2+. humic acid.species present in freshwater vary with pH: with increasing pH. CuCO3. some of the copper-organic complexes were still toxic (Daly et al. In addition.

1993 Brown and Rattigan 1979 Giesy et al. 1973 Shuttleworth and Unz 1991 Ivorra 1995 Mishra et al. Winner 1984 Daly et al. 1980). and fulvic acid did not reduce copper toxicity to the green alga Chlamydomonas whereas humic acid did (Garvey et al. Erickson et al. Xue and Sigg 1990 Lee et al. 1993 Garvey et al. 1976 Grande 1967. 1987. 1991). 1974 fish 10 . 1990a Chynoweth et al. 1991. 1973 Straus and Tucker 1993 Nelson et al. At copper concentrations greater than the pH-dependent solubility limit. A more recent study on the clawed toad (Xenopus laevis) indicated that fulvic acid only reduced toxicity if copper concentrations were less than its pH-dependent solubility limit. Only two studies indicated that organic chelators did not ameliorate toxicity: NTA did not affect copper toxicity to algae likely because chelators were present in the growth medium (Laube et al. Zitko et al. Oikari et al. 1996). 1995 Fogg and Westlake 1953 Steeman-Nielsen and Bruun-Laursen 1976 Morrison and Florence 1989. Azenha et al. Gächter et al. 1983 Porta and Ronco 1993 Borgmann and Ralph 1984 Rao 1985 Winner 1985 Khangarot et al. copper toxicity increased with greater fulvic acid concentrations (Buchwalter et al. Wilson 1972. McCrady and Chapman (1979) suggested that EDTA reduced the activity (concentration) of the toxic Cu2+ species.The presence of organic chelators generally decreased the toxicity of copper to aquatic organisms. 1986. 1996 Brown et al. Copper toxicity was reduced by organic chelators for: bacteria algae Pseudomonas Anabaena photosynthesis Chlorella filamentous algae desmids Nostoc Chlamydomonas Anacystis plants Elodea invertebrates Simocephalus Brachionus copepods Daphnia Daphnia pulex Daphnia magna Paratya guppies Atlantic salmon channel catfish fathead minnow rainbow trout Menkissoglu and Lindow 1991. 1992. Carson and Carson 1972.

the adsorptive surface becomes negatively charged. Adsorption of copper to suspended clays and oxides increased with increasing pH (Al-Sabri et al. Davis and Leckie 1978). Nelson et al. 11 . 1986). Increases in organic content however increased adsorption of copper onto clays and oxides (Nelson et al. At pH below 6. usually pH>6). and copper may be adsorbed (Spear and Pierce 1979. the pH at which the surface area has a zero charge.. particulates such as clays on organic materials may adsorb copper efficiently (Spear and Pierce 1979). Adsorbed copper is considered to be of low potency (Spear and Pierce 1979). Most copper in water was adsorbed and the amount adsorbed increased with an increase in suspended matter (Mouvet and Bourg 1983). At pH levels above the isoelectric point (i. organic compounds of high molecular weight. Ironoxyhydroxides adsorb copper and reduce uptake of copper by molluscs (Tessier et al. 1986). desorption of copper can occur (O'Connor and Kester 1975 referenced by Spear and Pierce 1979) possibly due to protons competing with copper for adsorption on the binding sites (Huang and Yang 1995). The addition of soil decreased copper toxicity to Eurasian milfoil (Myriophyllum spicatum) (Stanley 1974). 1984).e. Huang and Yang 1995).4 Adsorption Adsorption of copper to colloids and particulates occurs and can constitute a major proportion of copper. 1993. 1986. The presence of organic ligands may increase or decrease adsorption of copper according to Davis and Leckie (1978). Compounds such as hydrous metal oxides. The addition of clay reduced copper toxicity (increased the concentration lethal to 50% of the test organisms or LC50) to fathead minnow expressed as total copper (Nelson et al.2.

similar haematocrit levels.3 ENVIRONMENTAL EFFECTS OF COPPER 3. Brook trout exposed to copper had more PGOT enzyme and total protein content. 1975).1 Effects of Copper on Fish Physiological Effects Copper affected blood characteristics in fish. and carp (McKim et al. 1994). 1994). but had less plasma chloride and osmolarity decreased. Oxygen consumption in bluegills increased initially when exposed to copper. 1988). packed cell volume and a gradual decline in oxygen carrying capacity resulted from a sublethal copper exposure of Asian catfish. fell below base rate and recovered to the base rate after 7 days (O'Hara 1971). Rainbow trout exposed to 2 mg/L copper had higher blood sugar and plasma enzymes (Nemcsok and Hughes 1988). 1994). Mozabique tilapia exposed to copper however showed signs of haemodilution: lower haemoglobin levels.4 12 . Hemorrhaging in cardiac region and base of fins. arterial blood pressure and lactate concentrations increased. Copper exposure of rainbow trout resulted in respiratory toxicity: heart rate. Copper exposure of 0. Critical dissolved oxygen levels for the common carp increased from 1. and liver blood vessels were prominent in the body cavity (Svobodova et al. Sublethal copper exposure of bluegills however did not change whole body oxygen consumption after a 9-day exposure. Copper exposure of carp resulted in: production of skin and gill mucus. The plasma volume in striped bass exposed to copper increased (Courtois and Meyerhoff 1975). rainbow trout. and erythrocytes were swollen compared to unexposed fish (Cyriac et al. Copper affected short-term oxygen consumption in common carp and decreased ammonia excretion. and oxygen tension decreased (Wilson and Taylor 1993). and darkening of body coloration was observed in zebrafish exposed to copper (Weinstein 1978). white blood cells. 1970. but decreased oxygen consumption after a 32-day exposure (Felts and Heath 1984). a partial recovery of oxygen consumption in control fish did not occur in copper-exposed fish (Felts and Heath 1984). 1970). Lower red blood counts.05 mg/L significantly decreased haemoglobin and haemocrit values in Asian catfish (Saccobranchus fossilis) (Khangarot et al. Dick and Dixon 1985. When bluegills were exposed to increased temperature. Erythrocyte counts and haemoglobin generally increased whereas leucocytes and lymphocytes decreased in brook trout. Acute copper exposure of carp resulted in an increase in plasma glucose (Svobodova et al. Svobodova et al. whole body oxygen consumption increased. However. copper exposure of rainbow trout did not result in excess mucus or colour loss (Sellers et al. gills turned grey-red with heavy bleeding. Copper exposure damaged the surface of erythrocytes (Ahmad and Munshi 1992). After 9 month exposure. only PGOT was decreased (McKim et al. extruding scales. 1989). This may culminate in respiratory failure (Khangarot and Tripathi 1991).

Some restoration occurred after fish were removed from the copper solution (Saucier et al. Fathead minnows exposed to higher copper concentrations were less tolerant of low dissolved oxygen levels. However. but inhibited sodium influx and stimulated sodium efflux (Lauren and McDonald 1986. reduced number of splenic and kidney plaqueforming cells. respectively (Schreck and Lorz 1978. No significant change in oxidative capacity in the gills of rainbow trout was observed (Bilinski and Jones 1973). the effect on low dissolved oxygen tolerance was not persistent over longer exposure periods (Bennett et al. lesions in sensory and non-sensory epithelia compared to unexposed fish. more mucous cells. Cortisol and corticosteroid levels were higher in copper-exposed coho salmon and sockeye salmon.053 mg/L copper (De Boeck et al. High alkalinity reduced the effects of copper on sodium fluxes and on the permeability of gill membranes. sodium and potassium uptake by brown trout (Sayer et to 3. phagocytic acitivity in kidney and spleen cells and delayed eye-allograft rejection compared to control fish (Khangarot and Tripathi 1991). 13 . 1995). 1995). Copper reduced calcium. 1989). vacuoles in sensory epithelium. Reid and McDonald 1988). 1995). 1975). but inhibited whole body sodium influx (Pelgrom et al. Also copper did not appreciably alter arterial oxygen tension in rainbow trout (Sellers et al. Copper exposure of rainbow trout changed the histology of the olfactory organ: increase in goblet cells.022 mg/L copper. copper did not affect the immune response of rainbow trout to human red blood cell antigen (Viale and Calamari 1984). Copper exposure of rainbow trout resulted in ionoregulation interference (Wilson and Taylor 1993). Exposure of tilapia to copper had little effect on whole body sodium efflux and calcium transport across gill membranes. no recovery occurred at 0. Donaldson and Dye 1975).9 mg/L in the presence of 0. Copper affected the immune response of blue gourami to viral and bacterial antigens (Roales and Perlmutter 1977). The antibody levels against Vibrio were lower in copper-exposed coho salmon than in controls (Stevens 1977). However. The immune response of rainbow trout to fetal calf serum (measured as number of antibody producing cells) was inversely correlated with copper concentrations (Anderson et al. Asian catfish immunized with sheep red blood cells and exposed to copper had lower antibody titers. 1989). 1991). Copper had little effect on calcium transport across the gills of rainbow trout. High hardness however did not reduce sodium fluxes or the permeability of gill membranes (Lauren and McDonald 1986).

Liver and gills were the organs accumulating the most copper in rainbow trout (Handy 1993). gulping behaviour.Behaviour Copper reduced feeding in several fish species: rainbow trout (Lett et al. 1994). and increased swimming activity (Anderson and Weber 1975). Copper also increased prey handling time of bluegills (Sandheinrich and Atchison 1989) and reduced swimming performance of brown trout (Beamont et al. Preference or avoidance was influenced by temperature. Guppies exposed to copper showed increased rate and depth of opercular movement. Copper exposure also resulted in respiratory stress. Rainbow trout exposed to copper did not appreciably increase coughing (Sellers et al. the attraction was greatest in test with highest copper concentrations.0001 to 0. 1973) and carp (Svobodova et al. Copper exposure resulted in signs of restlessness and erratic swimming of the Indian warmwater fish Mystus vittatus and Colisa fasciatus (Pande and Shukla 1992). Bioconcentration Uptake of copper from water by fish is rapid. 1976.07 mg/L. In rainbow trout. Rapid and erratic ventilation was observed in zebrafish exposed to copper. 1995). equal and greater than those present in the Clark Fork River (Woodward et al. but surfaced frequently to gulp air (Singh and Reddy 1990). Despite avoidance of copper contamination after the initial attraction. Brown trout avoided simulated Clark Fork River water with a mixture of copper. Avoidance behaviour of copper by fish was summarized by Giattina and Garton (1983). 1995). Indian catfish were also lethargic. brown bullhead (Brungs et al. and bluegills (Sandheinrich and Atchison 1989). cramps and ataxia (Liepolt and Weber 1958). and lost equilibrium (Weinstein 1978). copper was quickly transferred to blood plasma (Zia and McDonald 1994). Rainbow trout were initially attracted to copper contaminated water. 1975). and/or (2) changes in sensitivity of the chemoreceptors at different concentrations may cause initial avoidance with subsequent attraction (Giattina and Garton 1983). rainbow trout experienced significant mortality (Pedder and Maly 1985). Atlantic salmon fingerlings (Grande 1967). with slow or no response to visual or tactile stimuli. zebrafish were generally sluggish. Increased copper was also observed in muscles of rainbow trout (Handy 1993). signs of stress however were deeper (but not faster) breathing. Two hypotheses were proposed to explain this ambivalent behaviour: (1) the attraction to high concentrations is a pseudo-attraction response caused by chemically induced narcosis. steepness of the copper gradient. Fish avoided copper concentrations varying from 0. This lack of feeding could have resulted in poor growth. Waiwood and Beamish 1978). which affected behaviour of several fish species. lead and zinc at concentrations half. Fish appeared to avoid low concentrations but preferred higher concentrations. In contrast to guppies. 14 . cadmium.

Uptake of copper by pumpkinseed sunfish and rainbow trout varied with fish size: copper uptake was less in bigger fish than in smaller fish (Anderson and Spear 1980a. Intermittent exposure of copper was more toxic to steelhead trout than continuous exposure (Seim et al. Anderson and Weber 1975). Fish size also seemed to affect copper toxicity. this copper tolerance was lost within 7 days (Dixon and Sprague 1981). Copper acted faster on rainbow trout exposed to higher temperature (Liepolt and Weber 1958). Copper toxicity decreased with an increase in suspended solids (rainbow trout. 15 . Increased calcium levels had the same effect in reducing copper toxicity to steelhead trout (Cusimano et al. Smith and Heath 1979) and a decrease in dissolved oxygen (rainbow trout. 1986. A similar trend was observed in stone loaches: copper loss from gills was fast whereas the liver appeared to retain copper (Solbe and Cooper 1976). channel catfish (Straus and Tucker 1993). Pre-exposure to copper reduced toxicity of copper to rainbow trout. and was faster in bigger fish (Anderson and Spear 1980a). 1984). Depuration Clearance of copper from pumpkinseed sunfish was fast: halftime was 1. 1986) and fathead minnows (Nelson et al. Copper was cleared from gills to less than 50% within 10 hour. However. Pickering and Lazorchak 1995. Smaller fish were more sensitive to copper than larger fish for the following species: cutthroat trout (Chakoumakis et al. fathead minnow (Nelson et al. 1979). Copper was more toxic to fathead minnow at 12 and 22 oC than at 5 and 32 oC (Richards and Beitinger 1995). Acute Toxicity Early lifestages of brook trout and chinook salmon were more susceptible to copper than older lifestages (McKim and Benoit 1971. rainbow trout (Howarth and Sprague 1978). pumpkinseeds (Anderson and Spear 1980b). Erickson et al. and guppies (Spear and Anderson 1975. and chinook salmon (Chapman and McCrady 1977). Lloyd 1961b). However. channel catfish and trout. the order of death in young Atlantic salmon was not related to size (Sprague 1964b) nor did size influence copper toxicity to rainbow trout (Anderson and Spear 1980b).6 to 4. 1996). Elimination of copper from carp was fast after fish were removed from copper solution to a water/EDTA mixture (Muramoto 1983). Lloyd 1961a). Hardness reduced copper toxicity to rainbow trout (Liepolt and Weber 1958. Brown et al.b). Copper in water with higher hardness was generally less toxic to fish than water with lower hardness. 1974) and H2S levels (Oseid and Smith 1972).8 hour. carp (Peres and Pihan 1991a). Copper toxicity also increased with an increase in temperature (goldfish. clearance of copper from liver took longer than 16 hours (Handy 1992). Chapman 1978).

Migration of salmon was also reduced when coho salmon exposed to copper in freshwater in the laboratory was released in a nearby creek (Lorz and McPherson 1976). However.018 mg/L (Stevens 1977). 1986. If a test species is sensitive to pH. the difference in body length became insignificant when yolk was absorbed (Servizi and Martens 1978). Asian catfish (Khangarot and Tripathi 1991). 1986. the speciation of copper changes at different pH (see Section 2. 1991). Hutchinson and Sprague 1989).1986).006 mg/L copper compared to controls. Copper delayed hatching of pink salmon but not of sockeye salmon. Initially. 1976). Copper is more toxic to fathead minnows at lower pH (Nelson et al.2). The toxicity of chelated copper to channel catfish increased at lower pH (Straus and Tucker 1993). and the Indian warmwater fish species Mystus vittatus and Colisa fasciatus (Pande and Shukla 1992). However. However. Welsh et al. which could affect the resulting toxicity.0 mg/L copper (Kaur and Virk 1980). 1996). respectively. Survival of coho salmon in seawater was reduced (Lorz and McPherson 1976. Exposure to copper reduced growth of rainbow trout (Lett et al. Survival of common carp hatchlings of common carp was affected at copper concentrations greater than 1. Chronic Toxicity The chronic toxicity of copper varied among fish species. 16 . Copper also acted faster in rainbow trout exposed to lower pH (Liepolt and Weber 1958). If species is not sensitive to pH. However. Hatchability of bluntnose minnow eggs was not affected by copper (Horning and Neiheisel 1979). Copper exposure in freshwater adversely affected seawater survival. hardness did not significantly affect survival of juvenile catfish (Wurts and Perschbacher 1994). higher toxicity at low pH would result. toxicity may be greater at higher pH due to diminished competition of Cu2+ and H+ ions at receptor sites compared to competition at lower pH (Cusimano et al. mucus secretion increased at low pH which may change copper species to less toxic forms. Schreck and Lorz 1978). Increased alkalinity also reduced copper toxicity to channel catfish (Straus and Tucker 1993) and chinook salmon (Chapman and McCrady 1977). In addition.018 and 0. Erickson et al. 1993. Coho salmon adaptation to seawater was affected at 0. 1996). 1986. increases in alkalinity did not significantly affect copper toxicity to fathead minnows (Nelson et al. The effect of pH on copper toxicity is not simple. the length of sockeye salmon and pink salmon alevins was less at 0. Copper retarded growth and development of early life stages of brown trout (Sayer et al. Erickson et al.

. was more than additive to young Atlantic salmon (Sprague 1964a. each chemical in the mixture contributes its proportional toxicity. When joint action of two toxicants is additive. Proportional toxicity is the concentration present in a mixture divided by its toxicity as a single toxicant (e.-Rozsa and Salanki 1990). Mixtures of copper and zinc had different effects on different fish. disruption of membrane permeability.g. Acute toxicity of copper and zinc was additive to rainbow trout (Brown and Dalton 1970) and bluegill sunfish (Thompson et al. 3. Exposure of the snail Biomphalaria glabrata to copper likely affected the osmoregulatory physiology: either by secretion of mucus resulting in suffocation. The osmotic and ionic regulation in the crayfish Orconectes rusticus was also affected: the antennal glands degenerated to varying degrees when exposed to low concentrations of copper. 1994).2 Effects of Copper on Invertebrates Physiological Effects Copper modified the effect of neurotransmittors and ionic current in the simple nerve systems of the pond snail Lymnaea stagnalis (S. Sprague and Ramsay 1965). Acute toxicity in mixtures of copper and cadmium was additive to juvenile chinook salmon (Finlayson and Verrue 1982). Toxicity in a mixture is more than additive if the toxicity in the mixture is greater than the sum of the proportional toxicity of the individual chemicals.Mixtures The joint action in mixtures of two toxicants can be described as: similar or dissimilar depending on whether the sites of primary action of the two toxicants are the same or different. Respiratory enzymes were inhibited at 17 . 1980). or disruption of normal cytoplasm function (Sullivan and Cheng 1975). Chronic toxicity of copper-cadmium-zinc mixtures was not additive to fathead minnow. and interactive or non-interactive depending on whether one toxicant does or does not influence the biological action of the other toxicant (Alabaster et al. Toxicity in a mixture is less than additive if the toxicity in the mixture is less than the sum of the proportional toxicity of the individual chemicals. however. acute toxicity indicated some interaction (Eaton 1973). Joint action is generally descibed in terms of additive. and copper with zinc and phenol mixtures was additive to rainbow trout (Brown and Dalton 1970). more than additive (supra-addition or synergistic) and less than additive. and was less than additive to juvenile chinook salmon (Finlayson and Verrue 1982). concentration lethal to 50% of the test organisms or LC50 ): [Cu]/LC50. copper with zinc and nickel. Acute toxicity of copper and phenol.

Copper concentrations were independent of the size of the amphipod Hyalella azteca. Survival of oligochaete worm Lumbriculus was not affected by copper in sediments (West et al. Uptake of copper by the isopod Asellus aquaticus increased at greater temperatures. Copper concentrations in the Pacific oyster (Crassostrea gigas) increased with size (Ayling 1974). 1990). Bioconcentration of copper by daphnids was reduced in water of greater hardness and higher concentration of humic acids. Conversely. but pH over a range from 5 to 8 did not significantly affect copper concentrations in the isopod. 1990. 1984). Copper concentrations in the freshwater mollusc E. 1990).copper concentrations greater than 1 mg/L (Hubschman 1967a). 1993). copper was bound in a stable body compartment (Van Hattum et al. 1993). acutus acutus) were unrelated to sediment copper concentrations (Finerty et al. complanata were less when more amorphous iron oxyhydroxides were present (Tessier et al.25-1 mg/L) resulted in increased respiration rates in the freshwater mussel Lamellidens marginalis compared to controls (Raj and Hameed 1991). The effect of animal size on the copper concentration in an animal is not clear. copper concentrations in crayfish (P. Trichoptera larvae (Plectrocnema conspersa) from a contaminated site (copper concentration in water 0.05 mg/L copper (Mersch et al. 1993).-Balogh 1989). acutus acutus: Finerty et al. Uptake of copper by the clam Anadonta cygnea was linear: depuration of copper from gills did not occur whereas copper concentrations in foot and mantle decreased in a linear fashion (Salanki and V. copper concentrations were highest in the hepatopancreas and gills (Cambarus bartoni: Zia and Alikhan 1989. Metal concentrations (including copper) in four species of mayfly larvae decreased with an increase in size (Jop 1991). Bioconcentration In crayfish. clarkii and P. Procambarus clarkii and P. Elimination of copper from the isopod was not generally observed. Copper concentrations in chironomids were positively related to easily reducible copper sediment concentrations and negatively with easily reducible iron sediment concentration (Young and Harvey 1991). the latter only in older daphnids (Winner 1985). Filtration by the zebra mussel Dreissenia polymorpha was inhibited at 0.84 mg/L) had high concentrations of copper in granules in malpighian tubule cells and 18 . Sublethal levels of copper (0. Highest copper concentrations were in gills and mantle of the freshwater mollusc Elliptio complanata (Tessier et al. Uptake of copper was rapid but these amphipods were able to control body burdens gradually and after long exposure periods (Borgmann and Norwood 1995). and Alikhan et al. 1984).

Copper concentration of 0. Size of the freshwater shrimp Gammarus pulex did not affect toxicity to copper (Stephenson 1983). freshwater shrimp Gammarus pulex (Stephenson 1983). oxygen consumption was severely reduced (Mule and Lomte 1994).subcuticular regions.01 and 0. Darlington and Gower (1990) suggested that these pigment granules prevent toxic effects. 1989. A number of environmental factors affected copper sensitivity of invertebrates: water hardness. Exposure of A. Belanger and Cherry 1990). Copper was more toxic to 19 . higher exposures caused the worms to break up in relatively large pieces (Baily and Liu 1980). The freshwater snail Thiara tuberculata reduced locomotion when exposed to 5 mg/L copper by withdrawing inside its shell. cygnea to 0. the opercululum closed at high copper concentrations (Arthur and Leonard 1970).125 to 0. Toxicity of copper to the amphipod Hyalella azteca was consistent across all age classes (Collyard et al. 1974). alkalinity. 1994). and pH. Hatekayama 1988). the rotifer Philodina acutiformis (Buikema et al. 1964). 1984b. Eggs of the snail Amnicola were less sensitive than adults (Rehwoldt et al. Feeding of the snail Campeloma decisum on clam meat ceased at copper concentration of 0.5 mg/L resulted in clumping of the oligochaete worm Lumbriculus variegatus. Exposure to 1 mg/L copper resulted in normal movement for the first 10 days and a gradual reduction up to 20 days. Exposure of tubificid worms (Tubifex tubifex) to copper resulted in sharp twisting motions. whereas crayfish eggs (Orconectes rusticus) were most sensitive (Hubschman 1967b). 1973). snails Stagnicola and Physa sp. The first instars of the midge larvae Chironomus tentans and Polypedilum nubifer were the life stage most sensitive to copper (Nebeker et al.015 and 0. (Howard et al. Behaviour Copper reduced the activity of many mollusks.028 mg/L. An increase in water hardness also reduced the acute toxicity to the cladoceran Ceriodaphnia dubia (Belanger et al. An increase in hardness or alkalinity decreased the toxicity of copper to tubificid worms (Brkovic-Popovic and Popovic 1977).-Balogh 1989). At high copper doses the snail Biomphalaria glabrata retreated in its shell (Sullivan and Cheng 1975).1 mg/L copper resulted in less active clams (Salanki and V. ionic strength. segmentation and disintegration (Brkovic-Popovic and Popovic 1977). Acute Toxicity No single life stage was consistently most sensitive to copper.

zinc and cadmium mixtures on filtration rates was no longer additive (Kraak et al. 1994). At 0.017 mg/L copper. Mixtures The waterflea Daphnia was exposed to an equitoxic mixture of As. An increase in pH reduced acute toxicity of copper to the cladoceran Ceriodaphnia dubia. The toxic effect on feeding (filtration rate) of copper and zinc were less than additive. 1984a). incompletely inflated or flattened. but did not affect chronic toxicity (Belanger and Cherry 1990). Copper concentrations equal to or greater than 0. 20 .5) decreased toxicity of copper to the snail Goniobasis livescens (Paulson et al. Cu. polymorpha) were exposed to metal mixtures. An increase in pH reduced copper toxicity to the waterflea Moina irrasa. Sublethal levels of copper (0. Hg. wings were either crumpled. legs were malformed. Cr. Pb. and the effect of the copper-cadmium-zinc mixture additive (Kraak et al. Zebra mussels (D. Zn: chronic effects were nearly additive (Enserink et al. 1991). Cd. Survival of the waterflea Daphnia magna was greater when food was added to the copper test solutions (Biesinger and Christensen 1972). Alkaline stress (pH 10. Ni. Copper also affected growth. the effect of copper and cadmium more than additive.017 mg/L prevented completion of the lifecycle of the caddisfly Clistoronia magnifica. During prolonged exposure of zebra mussels. An increase in water temperature resulted in faster death of the fleas when exposed to copper (Zou and Bu 1994). 1990b). Glochidia could not reopen and were therefore unable to attach to fish and continue their development (Huebner and Pynnonen 1992).the Australian freshwater shrimp Paratya australiensis at lower ionic strength either due to increased uptake (gill/respiration) or due to combined copper and ionic stress (Daly et al. Chronic toxicity Copper interrupted the lifecycle of a caddisfly and a clam.25-1 mg/L) resulted in greater weight loss of the freshwater mussel Lamellidens marginalis compared to controls (Raj and Hameed 1991). the effect of copper. 1983). 1993). detachment of pupal skin was incomplete and mating did not occur (Nebeker et al. The early life stage of the clam Anadonta cygnea was more sensitive to copper than adults.

At higher copper concentration. In frogs (Rana pipiens) exposed to copper above 0. Copper exposure delayed growth of the green alga Scenedesmus. and loss of equilibrium (Khangarot and Ray 1987a). and resulted in severe membrane decomposition. and general activity was lower (Kaplan and Yoh 1961). The cell size of Scenedesmus quadricauda was also enlarged after copper exposure (Khobot'yev et al. respiration. 1980). 1974. Similar effects were observed with clawed toad (Xenopis laevis) larvae (Fingal and Kaplan 1963).4 Effects of Copper on Plants Exposure to copper reduced growth of plants. reduced oxygen devolution. Deflagellation of the green alga Chlamydomonas was a more sensitive indicator of copper toxicity than population growth or encystment (Garvey et al. Behaviour was also affected by copper.1 mg/L copper but were attracted to 0. However. peroxidation of lipids (Sandmann and Boger 1980). Copper reduced growth of frog (Rana pipiens) tadpoles (Lande and Guttman 1973). In a study of several amphibian species. neuromuscular coordination was disturbed. However. Metamorphosis of boreal toad (Bufo boreas) larvae was not affected by copper (Porter and Hakanson 1976). 1975). larvae of marbled salamanders (Ambystoma opacum) were more sensitive to copper than embryos: the LC50 was lower when the toxicity study was extended beyond hatching. Copper exposure resulted in a reduction in the green alga Chlorella vulgaris growth and an increase in cell size (Rosko and Rachlin 1977). American toad (Bufo americanus) tadpoles avoided concentrations of 0. followed by loss of equilibrium and death (Rao and Madhyastha 1987).93 mg/L (Birge et al. Rosko and Rachlin 1977. mucus output increased. Larval LC50s for 2 toad (Fowler's toad Bufo fowleri and narrow-mouthed toad Gastrophryne carolinensis) and two frog (northern leopard frog Rana pipiens and southern gray treefrog Hyla chrysoscelis) species were not significantly changed from LC50s for egg hatching (Birge and Black 1979). photosynthesis. 21 .3 Effects of Copper on Amphibians The toxic effects of copper on amphibians are summarized in Appendix 1. and resulted in physiological damage and deflagellation. had erratic body movements. heart rate initially increased than decreased. 3.3. embryos were generally more sensitive to copper than larvae (Birge and Black 1979). destroyed chlorophyll-a. Frog tadpoles (Microhyla ornata) also showed signs of irritability when exposed to copper. Foster 1977.0015%. 1993). toad tadpoles (Bufo melanostictus) surfaced more. and nitrogen fixation. copper had little effect on average cell volume of the green algae Selenastrum capricornutum or Chlorella stigmatophora (Christensen and Sherfig 1979). Laube et al. up to 20 times the normal volume (Foster 1977). 1991). Growth of blue-green and green algae was delayed when algae were exposed to copper (Bartlett et al.

Lee et al.The blue-green alga Anabaena took up more copper than the green alga Scenedesmus and was more sensitive to copper.025 mg/L. 22 .25 mg/L. 1995). Bluegreen algae were most affected (Elder and Horne 1978). Dark respiration increased of the waterweed Elodea increased with copper exposure compared to controls. Cell division by Chlorella during dark periods was inhibited at lower copper concentrations than cell division during light periods (Kanazawa and Kanazawa 1969). indicating that copper decreased the tolerance to photoinhibition (Vavilin et al. toxicity was reduced as pH increased (Khare and Bisen 1991). 1975. Copper exposure significantly reduced chlorophyll-a concentrations. Stauber and Florence 1989. copper effected the light harvesting complex (Gupta and Singhal 1995). Copper complexes were less toxic than CuCl2 (Khobot'yev et al. Morrison and Florence 1989. Anabaena did not recover after re-inoculation at copper concentrations of 0. Copper also reduced PSII activity of the green alga Chlorella pyrenoidosa. 1993). The PSII inhibition was more pronounced at higher light levels. These growth media generally contain buffers and organic compounds (like EDTA). The copper concentration inhibiting growth of the bluegreen alga Cylindrospermum by 50% (IC50) was 0. chelators could overcome this effect (Brown and Rattigan 1979). 1978) and inhibited electron transport from watersplitting system to primary acceptor (Samson and Popovic 1988). 1969). Exclusion of copper was indicated as a mechanism to explain the difference in copper tolerance between the two strains of Chlorella vulgaris (Foster 1977). copper reduced PSII activity by causing structural alterations in the chlorophyll-proteins of the PSII complex. the speciation of copper was altered more by binding to algal exudates than by binding to algal surfaces (Xue and Sigg 1990). Copper reduced photoreduction of NADP+ (photosystem I . these organic compounds may change the speciation of copper and result in less toxic forms. Copper sulphate caused a reduction of nitrogen fixation and physiological damage (with a concomitant release of dissolved organic carbon and geosmin) of Aphanizomenon flos-aquae (Peterson et al. In addition. In the bluegreen alga Anacystis nidulans. Growth rate was inversely proportional to copper levels taken up by two strains of the green alga Chlorella vulgaris. 1995). As explained in Chapter 2. However.PSI) and DCIP (Photosystem II . whereas Scenedesmus recovered at concentrations less than 0. photosynthesis and nitrogen fixation.PSII) in the green alga Ankistrodesmus falcatus (Shioi et al. Copper may also bind to algal surfaces or to algal exudates resulting in lower toxicity.8 mg/L (Gibson 1972). Copper was more toxic at higher light intensity (Steemann Nielsen et al. Toxicity Toxicity tests with plants are performed in special growth media. Effects of copper on photosynthesis of the green alga Chlorella were fast (<24 hr). In a test with the green alga Chlamydomonas.

More than additive effects were observed with copper and manganese (Christensen and Sherfig 1979). The ciliate protozoan Spirostomum ambiguum was very sensitive to copper.004 mg/L copper at low hardness (2.006 mg/L (lowest observed effect concentration affecting photosynthesisGächter et al. Copper exposure of 13 different protozoan species resulted in lethal levels from 0.03 mg/L (Menkissoglu and Lindow 1991).11 mg/L for the protozoan Entosiphon sulcatum (Bringmann and Kuhn 1980).1 mg/L inhibited respiration 40% by Escherichia coli bacteria (Dorward and Barisas 1984). 1995). Respiration by E. Addition of copper greater than 1 mg/L to indoor ponds reduced E. 23 . coli numbers (Jana and Bhattacharya 1988). and 1. Threshold toxicity of the planarian Polycelis nigra was 0.6 mg/L after 24 hours. the LC50 was 0. whereas less than additive effects were observed with copper and lead (Christensen and Sherfig 1979). Toxicity effects of copper on the protozoan Paramecium tetraurelia were temperature dependent.1 to greater than 100 mg/L with a median toxicity limit of 1. However. copper and zinc (French and Evans 1988). Mixtures Several mixtures of metals including copper were tested on plants.2 mg/L copper (Dutka and Kwan 1981.005 at high hardness (250 mg/L CaCO3) (Nalecz-Jawecki et al. Microtox test results were variable between different laboratories: EC50 values varied from 8 to 20 mg/L copper (Dutka and Kwan 1981).47 mg/L copper (Jones 1940).5 mg/L (Bauer et al. Results from several microbial bioassays were compared: Microtox assay was the most sensitive test with EC50s (effect concentration that causes an effect in 50% of the test organisms) of 3. 1990. copper and iron (Jain et al.2 mg/L.03 mg/L for the bacterium Pseudomonas putida and 0.The toxic effects of copper on plants are summarized in Appendix 2. 3. Rachlin and Grosso 1993).1-0.8 mg/L copper (Ruthven and Cairns 1973). Codina et al. 0. 1989. The toxic threshold level for cell multiplication was 0. Maximum tolerated copper concentration by 17 strains of this species were 0.8 mg/L. 1973) to over 25 mg/L copper (growth Brady et al. Reteuna et al. coli was reduced at 5 mg/L (Jardim et al. Oxygen depletion by a bacterial community was reduced at a copper concentration of 0. 1993). The LC50 value for the protozoan Vorticella after a 3-hour exposure was 1.8 mg/L CaCO3) and 0. copper and cadmium (Lasheen et al. Toxicity endpoint for plants ranged from 0. 1994).5 Effects of Copper on Other Microorganisms Copper concentration of 1. respectively).12 to 0. toxicity increased at higher temperature (Szeto and Nyberg 1979). 1992). cadmium and cobalt (Rachlin and Grosso 1993). 1990). Treatment of 6 mg/L copper resulted in high mortality of Pseudomonas syringae bacteria (Azenha et al. 1993. 1981).

avoidance of high copper concentrations and restricted spawning. However. periphyton biomass did not decline due to an increase in the diatom Achnanthes (Leland and Carter 1984). 1988). Rapid recolonization by ciliates and rotifers occurred after the copper additions were halted (Leland and Kent 1981). Benthic commmunities upstream of the plant discharge were established on trays and transported to experimental streams supplied continuously with New River water. Ephemeroptera were most affected: they did not recover at sites further downstream. The number of species of ciliates and rotifers were affected at 0.05 mg/L copper and zinc).012 mg/L copper and zinc.01 mg/L during 1979/80 almost totally inhibited the filamentous green alga Spirogyra.12 mg/L copper during 75% of the study period (February 1970 to October 1972). Benthic invertebrate communities in the Clinch River. The resulting benthic invertebrate community was very similar to the community observed in the Clinch River below the plant discharge (Clements et al. Exposure of microbial communities to 0. However. 0. Copper additions of 0.02 mg/L copper reduced species richness and biomass (Pratt et al.005 to 0.0025 mg/L for both years.01 to 0. were dosed continuously with different CuSO4 concentrations during two 1-year experiments (starting in 1978 and 1979).6 Effects of Copper on Microcosms and Ecosystems Field experiments/studies Separate sections of Convict Creek.007 mg/L (LOEC) and 0. 3.42 mg/L copper (Cairns et al.005 mg/L during 1978 and 1979. 24 . were affected by the effluent of a coal-fired generating plant. and 0. Benthic invertebrate abundance and number of taxa decreased significantly in the experimental streams exposed to copper and zinc. the bluegreen alga Lyngbia. an oligotrophic Sierra Nevada creek in California. reduced the green algae Cladophora and Mougeotia (at 0. respectively. Copper and zinc was added (control. Partial recovery was observed after 144 hours when 14 species were present (Cairns and Dickson 1970). Shayler Run (Ohio) was dosed continuously with 0. Colonization of artificial "islands" around an epicenter by protozoans was affected by 0. CuSO4 additions affected fish species except for orange throat darter.Exposure to 24 mg/L copper reduced the number of protozoan species from an initial 46 species to 7 species after 24 hour exposure. No observed effect was observed at 0. and the diatom Amplipleura. Tanytarsini chironomids were also highly sensitive. Orthocladiini and Hydropsychidae were more tolerant: abundance was greater at downstream recovery stations than at upstream control sites. Virginia. 1980). The effects were death. Information from December 1967 to 1970 was used as background information. 1993). Concentrations of copper and zinc were elevated in water below the plant discharge.01 mg/L). Fewer taxa and individuals were observed below the plant discharge.

The periphyton community also changed: the dominant diatom (Cocconeis placentula) and filamentous alga (Cladophore glomerata) were replaced by three other species of diatoms (Nitzschia palea. However. A smaller dose of 1 mg/L copper completely controlled the filamentous green alga Spirogyra. green and bluegreen mats and scum developed by day 14 to 17. Coppersulfate addition to ponds resulting in 3 mg/L copper partially controlled waterweed Elodia nutallii and completely controlled the pondweed Potamogeton crispus. A copper-lead-zinc mine used to discharge metal mining waste into Butte Lake. McIntosh 1974). British Columbia. Decomposition of these plants decreased dissolved oxygen levels and increased hydrogensulfide (H2S) concentrations (McIntosh and Kevern 1974.17 to 0. A blue-green alga and two desmid species were more abundant in the coppertreated reach than in the control reach (Weber and McFarland 1981). and muscle metallothionein levels in rainbow trout returned to background levels. Removal of these species was only temporary. Navicula nigrii and N.Bluntnose minnows and stonerollers moved out of the copper-dosed area. The fifth abundant macroinvertebrate group (chironomids) flourished in the copper-dosed area (Geckler et al.04 mg/L. The macroinvertebrate community changed with distance downstream. short-term EC50 values were 25 . sowbugs. whereas number of cladocera and rotifers were depressed but later recovered. Phytoplankton in the enclosures with copper were affected by copper: 14C dioxide fixation was lower in those enclosures with higher copper concentrations. the phytoplankton communities exposed to copper developed tolerance over time. metallothionein levels in cutthroat trout and Dolly Varden did not change after discharge was stopped (Deniseger et al. Four of the five abundant macroinvertebrate groups were essentially eliminated (scuds. The result was a minor temporary decrease in chlorophyll-a levels. 1990). subtle changes in algal composition. 1975). 1980). Copper was added to Cazenovia Lake in New York for algacidal purposes. Copper concentrations were constant after this initial dose. seminulum). and bacteria were affected but recovered fast. CuSO4 was added three times. The phytoplankton species composition changed. which would have resulted in a completely mixed copper concentration of 0. Hepatic metallothionein levels were reduced in rainbow trout after discharge to the lake was eliminated. After termination of this discharge. After 12 days. green alga Oedogonium sp and stonewort (Chara). Plants and zooplankton were not affected by the copper addition (Effler et al. Copper was added once to several enclosures in Lake Bure. However. 1976). but none of the other species. Ostracods and copepods were not affected. The number of individuals and number of species were were lower at sites with higher copper concentrations (Winner et al.051 mg/L. Denmark (Gustavson and Wängberg 1995). lakewater copper concentrations dropped from 0. zooplankton community was more diverse. mayflies and riffle beetles).

the green alga Scenedesmus and blue-green algae.03 and 0. The equilibrium density of the prey P. 1987). oligochaetes disappeared (Sugiura et al. taxonomic richness was not affected at 0. At 0. After 21 days. This resulted in a destabilization of the predator-prey interaction.2 mg/L copper did not cause severe elimination in a continuous flow system. whereas the equilibrium concentration of the predator D.5 mg/L copper. At 0. At 0. Addition up to 1. The algal dominance changed from the bluegreen algae Nitzschia and Lyngbia to the green algae Ankistrodesmus and Scenedesmus (Harass and Taub 1985). however these measures may not be sensitive to other toxicants and are also subject to natural changes to individual species (Pratt et al.0127 mg/L (LOEC). 0. rotifers.5 and 2 mg/L copper. bacteria and the green alga Chlorella increased and blue-green algae. but was affected at 0. Laboratory Microcosms Continuous CuSO4 additions of 0. annelids.7 mg/L to a static version of the microcosm eliminated the rotifers. bacteria. insects and crustaceans was exposed to CuSO4 in a flow-through experiment. Predator-prey interaction were evaluated with copper concentrations up to 0. protozoa. An addition of 0.3 mg/L copper. In addition.0066 mg/L (NOEC). nasutum became negative.3 mg/L.3 mg/L copper. rotifers. The intrinsic rate of growth of both predator and prey species was greater when copper concentrations were between 0.18 mg/L compared to controls. A naturally colonized microcosm with protozoans. Copper was more acutely toxic to the protozoan predator Didinium nasutum than to its protozoan prey Paramecium caudatum. the intrinsic rate of increase of the predator D. caudatum tended to decrease as copper concentrations increased. the grazer Daphnia was unable to survive. this allowed accumulation of algal biomass and a rotifer bloom. nasutum did not change. oligochaetes and bacteria. An aquatic microcosm was set up with primary producers. Other measurements EC5 for chlorophyll-a and ATP were more sensitive than taxonomic richness. algae and grazers were severely affected. fungi. At the 2 mg/L copper. the equilibrium density of both predator and prey increased: predator efficiency decreased allowing the prey 26 . oligochaetes. diatoms.0093 mg/L copper to a flow-through microcosm changed the structure of the microcosm from an autotrophic to a heterotrophic system after 32 weeks (Hedtke 1984).higher for the copper exposed phytoplankton communities than for the control and lake communities. Aquatic microcosms with 10 algal species and 5 invertebrate species were subjected to 0. algae. algal biomass recovered in the copper-exposed enclosures after an initial decrease. 1982). rotifers.

Organisms containing haemocyanin (crustaceans. There was no evidence of biomagnification: the CF for predators was lower than the CF for plankton (zooplankton 3444. Concentrations of copper in biota decreased with increasing trophic level (Prahalad and Seenayya 1986. 1976). Concentration factors (CF) ranged from 149 and 156 for bullhead and pickerel (omnivorous and carniverous fish. respectively) up to 17667 for periphyton. Some data on fish suggest that copper is a a chemical that causes structural defects that affect the development of an organism (teratogen). 1995). Human data suggest that copper does not produce teratogenic effects (MacLaren Plansearch and FDC Consultants 1985). Copper levels in predators were low and equal to those in filter feeders. Biomagnification was also not evident in the several lakes. 1989). indicating the lack of biomagnification (Roch et al. Birge and Black (1979) indicated that the sensitive developmental stages of rainbow trout may be 27 . Copper was studied in the various compartments of the Wanapitei River. Department of Health and Human Services 1990).7 Genotoxicity of Copper Copper is not known to cause cancer (U. Deposit feeders contained higher copper levels. copper content decreased from zooplankton to stickleback and to cutthroat trout. and various aquatic biota at several sites in the Sacramento River basin indicated no sign of magnification of copper along the foodchain (Saiki et al. sediment. but higher than in sediments. However. protozoa and metazoa was not observed: algae contained 10 to 100 times more copper than the waterflea Daphnia (Jin et al.equilibrium density to increase (Doucet and Maly 1990). Hutchinson et al. southwest of Sudbury (Ontario). Radwan et al. 1990). 1985). There was no evidence of biomagnification as predators contained less copper than their prey (Timmermans et al. 1991).S. Larval survival of species with a high copper tolerance (bass. goldfish and catfish) was not affected by gross teratogenic impairment. gastropods and bivalves contained higher amount of copper. Biomagnification in a microcosm containing algae. No data are available to suggest that copper is a reproductive or teratogenic toxin (MacLaren Plansearch and FDC Consultants 1985). Treatment of fish eggs with copper however resulted in significant numbers of teratic larvae. Biomagnification Trace metal levels in the littoral foodweb of the Maarsseveen Lakes were studied. Copper concentrations in water. 3. In the Butte Lake (British Columbia) system.

Their characteristic amino acid composition (high cysteine content and poor in aromatic amino acids). Carpene 1993). 3.019 mg/L at pH 6. Fifty percent of the hatchlings were abnormal after exposing eggs to copper concentrations of 3. MT can be induced by a large number of diverse agents. The first compound with all these features was first detected in equine kidney cortex.affected as much by teratogenic effects as by egg mortality. Deformed vertebral column. upper jaw. The high cysteine content gives MT a very high binding capacity for metals. Not only should the identity and role of other metal binding proteins be understood (Hodson 1988). 1990). In a different study.8 Metal-binding Proteins (Biomarker) Metallothioneins (MTs) are low molecular weight proteins with a high content of certain trace metals. Skeletal defects (spinal column and jaw) were the most sensitive indicators of teratogenic effects (Birge and Black 1979). 1990). 28 . Teratogenic effects on rainbow trout increased at copper concentrations greater than 0. In addition to heavy metal exposure. The effects included a deformed head. the latter may not provide information on the stressor. sequence and spectroscopic properties make these proteins unique. Seasonal variations of MT levels also occur.5 mg/L. also the consequence of biochemical changes at the organism level to higher levels of organization (population and ecosystem level) need to be understood (Thomas 1990). 1996). Since this original discovery. Potential roles include: protection against toxicity (through chelation of reaction with MTthioles) or normal cellular function (regulation of zinc metabolism and a role in copper metabolism). spinal column. MT measurements include protein with and without bound metal. Petering et al. The role of MTs in aquatic species is unknown (Hodson 1988. several metalloproteins with similar biochemical proteins have been identified (Hodson 1988.3. Freshwater fish contain a large basal level of MT-like zinc and copper binding proteins.01 mg/L. it is probable that MTs participation in detoxification mechanisms are due to fortuitous interactions of foreign cations with the normal homeostasis mechanism for zinc and perhaps copper. Extensive knowledge from direct study of non-mammalian organisms is needed to determine whether MT can be used for environmental monitoring purposes (Petering et al.6 and 0. (1991). teratogenic effects were also observed in common carp at much lower copper concentrations: 0. downward curvature of the caudal region and undeveloped body behind the yolk sac were observed in these hatchlings (Kaur and Virk 1980). and by handling or not feeding fish.051 mg/L at pH 7. According to Cosson et al. and a small or absent swim bladder (Stouthart et al. The development of common carp was also affected by copper.

Centroponidae. Gastropoda. rainbow trout. chinook salmon. Ictaluridae. fathead minnow. However. Cypriniformes. respectively). Perciformes. and Ceriodaphnia dubia) were derived. Amphipoda. Appendix 1). Annelida. The minimum "non-fish" data requirements for deriving a full acute guideline (Alberta Environmental Protection 1996) are therefore amply met. fathead minnow. Ephemeroptera.12 mg/L copper resulted in an 50% mortality (Dobbs et al. The range of the Daphnia pulex data was large (45 to 230 mg/L CaCO3). These data were therefore not considered in deriving a relationship between water hardness and acute copper toxicity. 1994. Rotatoria. the range of water hardness for the bluegill and guppy data was small (35 to 110 mg/L CaCO3 and 67 to 144 mg/L CaCO3. Only one study provided primary acute data for amphibians: in a 48-hr test of the two-lined salamander (Eurycea bislineata) 1. Because hardness was found to modify copper toxicity. According to the Protocol to Develop Alberta Water Quality Guidelines for Protection of Freshwater Aquatic Life (Alberta Environmental Protection 1996). Decapoda. and rainbow trout. However.4 DERIVATION OF ACUTE AND CHRONIC GUIDELINES 4. Acute copper toxicity values were also available at different water hardness for three invertebrate species: Ceriodaphnia dubia. the minimum fish data requirements for deriving a full acute copper guideline are therefore amply met. the Daphnia data were not used in deriving a relationship between water hardness and acute copper toxicity. Cyprinidae. respectively). relationships between acute copper toxicity and water hardness were investigated.1 Final Acute Value and Alberta Acute Guideline Primary acute toxicity data were available for 29 fish species from five different orders (Salmoniformes. Plotosidae. and Poeciliidae) (Appendix 3). and the number of data points was small (three). Centrarchidae. Diptera. Primary acute toxicity data were available for 24 invertebrate species from 11 different orders (Isopoda. Dapnia magna. Siluriformes. guppies. Atherinoformes) and 10 different families (Salmonidae. and Daphnia pulex. the range of water hardness for the Daphnia magna was small (85 to 143 mg/L CaCO3). Cladocera. the number of the acute toxicity values at low hardness varied almost 10-fold and only one acute toxicity value was available at high hardness. and Plecoptera) (Appendix 4). Regression relationships for the four remaining species (chinook salmon. Therefore. Percidae. Melanotaeniidae. Cyprinidontidae. and the number of data points was small (five and four. Acute copper toxicity values were available at different water hardness for five fish species: bluegill. Some of the basic information is provided in Table 4: the detailed 29 . Trichoptera. However. A natural logarithmic transformation improved the relationships: guidance as outlined in Alberta Environmental Protection (1996) was therefore followed.

Seim et al.2=138.002 <0. alevin pink salmon (Servizi and Martens 1978).002 <0.4879. the available primary acute data were adjusted to a common water hardness (100 mg/L CaCO3).979123) is significant: F1.72=0.001 <0. P<0.616991. The following adjustments in the data from Appendix 2 and 3 were made: • 96-hr LC50 for Hydropsyche betteni was set at 64 mg/L (as opposed to >64) • the total copper LC50s for Paratya australensis and fathead minnow were used • only the LC50s for sensitive lifestages were used: swim-up chinook salmon and steelhead trout (Chapman 1978). fry sockeye salmon (Servizi and Martens 1978) • the LC50s for adult and juvenile steelhead trout (Chapman and Stevens 1978.901 0. Table 4. and V is the pooled slope (0. W is the original acute toxicity value at the original water hardness (X).01 slopes for species are equal: F3.calculations are provided in Appendix 5.759 0. the species mean acute values (SMAV) were calculated as outlined in Alberta Environmental 30 .363 0. 1984) were not used as these were not sensitive lifestages After adjusting the acute toxicity values to a common water hardness of 100 mg/L CaCO3.979123). n r2 0.591 P <0.91816 1.021908 Chinook salmon Fathead minnow Rainbow trout Ceriodaphnia dubia 7 26 30 17 pooled slope (0.2 g pumpkinseed (Spear and Anderson 1975). According to the ancova analysis. 1. Statistical information on regression and ancova analyses (Sokal and Rohlf 1981) for derivation of an acute copper guideline. according to in which Y is the ln-transformed toxicity value adjusted to the water hardness of 100 mg/L CaCO3 (Z). P>0.688565 0. the pooled slope is significant and the slopes for the four different species are similar.03995 1.5 With the pooled slope.01 Slope 0.

at 100 mg/L CaCO3 water hardness) was 0. recreationally and ecologically important species was more sensitive than this calculated FAV. The Alberta acute guideline (at 100 mg/L CaCO3 water hardness) is therefore 0. 31 .066 mg/L (chinook salmon) to 2. The resulting final acute value (FAV.011 mg/L (Caridina) to 139. The GMAV for Caridina sp.294 mg/L (bluegill sunfish). Following the Alberta Environmental Protection (1996) guidance for deriving an acute equation.0320 mg/L. for amphibians 1.871 mg/L (Hydropsyche). The genus mean acute values (GMAV) were calculated as outlined in Alberta Environmental Protection (1996).Protection (1996). 1991) was deleted from the calculation of the final acute value.02 mg/L (2-lined salamander. Appendix 5). This datapoint was eliminated because it was from an Australian species that was more sensitive than all the North American species.0160 mg/L. for invertebrate species from 0. No commercially. the resulting acute copper guideline (in mg/L) is: Figure 1 presents all primary genus mean acute values (adjusted to 100 mg/L CaCO3 water hardness) in relation to the Alberta acute guideline. The SMAVs varied: for fish species from 0. (Williams et al.

32 .

The chronic toxicity data consisted of a no-observed-effect-concentration (NOEC) and a lowest-observed-effect-concentration (LOEC). The 33 . Again.04 >0. Cladocera.827 0. fathead minnow.056 The range in water hardness for all three species was large.01 >0. the fathead minnow data resulted in the only significant relationship between water hardness and chronic copper toxicity (P<0.72 Brook trout Fathead minnow Ceriodaphnia dubia 4 6 4 0. the relationship between copper toxicity and water hardness was investigated. Appendix 6) and for 8 invertebrate species from 5 different orders (Diptera. Chronic copper toxicity values were available at different water hardness for two fish species and one invertebrate species: brook trout. According to the Protocol to Develop Alberta Water Quality Guidelines for Protection of Freshwater Aquatic Life (Alberta Environmental Protection 1996).76 ln-transformed data r2 0. Table 5. Cyprinidae. Trichoptera. Appendix 7). and Ceriodaphnia dubia. the minimum data requirements for deriving a full chronic copper guideline are therefore amply met. Statistical information on regression analyses for a chronic guideline (Sokal and Rohlf 1981). Amphipoda. Pelycopoda. chronic toxicity data are available only for low and high water hardness and not for any intermediate water hardness.08 P >0.127 0.70 0.Alberta Chronic Guideline Final Chronic Value Primary chronic toxicity data useful for deriving a chronic guideline were available for 11 fish species from three different families (Salmonidae. Esocidae.05).77 <0.05 0.64 <0. The geometric mean of the NOEC and LOEC values (MATC) was calculated and used in further analyses. The results of the regression analyses presented in Table 5. As illustrated in Figure 2. However. n untransformed data r2 P >0.

333 1. 1985 Bluntnose minnow Fathead minnow Ceriodaphnia dubia Chironomus tentans Daphnia magna The minimum ACR requirement (primary ACR for fish.381 3.604 9.349 1.075 18.583 5. ACR does not seem to increase or decrease with the acute toxicity of a species (Figure 3). 1989 Nebeker 1984b Blaylock et al.48 5. a water hardness relationship for chronic toxicity data was not derived.933 4.182 3. 1995/1996 Servizi and Martens 1978 Benoit 1971 Servizi and Martens 1978 Horning and Neiheisel 1979 Pickering et al. ACR 8. ACR varies widely within a species (almost an order of magnitude for fathead minnow with similar water hardness. Therefore.735 13 Water Hardness (mg/L CaCO3) 25 83 45 83 200 202 31 204 36 100 94 179 36 85 Reference Marr et al. 1976 Carlson et al. the ACR data are not conclusive: • • • • the ACR seems to increase with water hardness for Ceriodaphnia. Table 6. A chronic guideline equation relating chronic toxicity to water hardness can be calculated from the acute guideline by applying an acute-to-chronic ratio (ACR) (Alberta Environmental Protection 1996).514 52. 1986 Spehar and Fiandt 1986 Belanger et al. invertebrate and the acutely sensitive rainbow trout: Alberta Environmental Protection 1996) is therefore met. 1977 Mount and Stephan 1969 Geckler et al. Species Rainbow trout Sockeye salmon Bluegill Pink salmon Primary acute-to-chronic ratios (ACR) from copper toxicity studies.073 22. Table 6). However.917 7. ACR between species varies over a factor of 10 (Table 6). 1989 Belanger et al.chronic toxicity data did not indicate a relaionship between copper toxicity and water hardness. but not for fathead minnow. Many primary studies provide ACR values (Table 6). 34 .

007 mg/L copper to protect rainbow trout. The calculations are presented in Appendix 8 and result in a final chronic value (FCV) of 0. an ACR is not used to adjust the acute guideline equation against water hardness to a chronic guideline equation.01 mg/L (Birge and Black 1979).Therefore. Because the chronic toxicity data for brook trout and Ceriodaphnia dubia indicated no relationship between water hardness and chronic toxicity and an ACR adjustment to the acute guidelines could not be used. recreationally and ecologically important in Alberta. SMCVs varied for fish species from 0.0095 mg/L. Two species had an SMCV lower than the final chronic value: Daphnia pulex with an SMCV of 0. The FCV would therefore protect trout embryos from teratogenic effects and no adjustments to the FCV were therefore made.053 mg/L (Chironomus. Because rainbow trout is a commercially. Figure 4 presents all primary chronic GMCVs in relation to the Alberta final chronic value.006 mg/L and rainbow trout with an SMCV of 0. Appendix 8). no relationship with water hardness was developed for a chronic guideline. the final chronic value was adjusted to 0. The genus mean chronic values (GMCV) were calculated as outlined in Alberta Environmental Protection (1996). 35 .00755 mg/L copper.060 mg/L (northern pike) and for invertebrate species from 0. The species mean chronic values (SMCV) were therefore not adjusted for hardness. The most sensitive teratogenic effects were observed on rainbow trout embryos at copper values greater than 0.006 mg/L (Daphnia pulex) to 0. SMCVs were calculated according to Alberta Environmental Protection (1996).00755 mg/L (rainbow trout) to 0.

buffers and metals that could potentially compete with copper for uptake by algae. Bishop and Perry 1981). In the medium without EDTA. Lemna minor (duckweed. Many different growth media were used in the plant tests. 1995). flow-through tests with measured concentrations. 1995). Ivorra et al. Chlamydomonas reinhardtii (green alga. These factors could reduce toxicity to copper (Steemann-Nielsen et al. Some of these media contained chelators. Ivorra et al. 1969. Vavilin et al.019 36 . 1995). and Chlorella pyrenoidosa (green alga. or static tests of short duration. static tests without a significant decline in copper concentrations during the test. 1991). Only the primary studies were rated: the studies without chelators. The only primary copper toxicity studies are with Staurastrum species (desmids. the copper concentrations reducing 50% of growth (EC50) were 0.Final Plant Value Many of the plant studies are unsuitable for derivation of the final plant value. Garvey et al.

respectively (Ivorra et al. most primary chronic toxicity values are performed in water with a hardness between 50 and 200 mg/L CaCO3 (Appendix 8). However.6 mg/L.009 mg/L.01 mg/L (Vavilin et al. However. chronic toxicity should not be less stringent than acute toxicity (acute guideline would be more stringent than the chronic guideline at water hardness less than 43 mg/L CaCO3). This restriction will not greatly affect the use of the guideline in Alberta because surface water in Alberta is generally hard. Root length of Lemna minor was most affected by copper addition: EC50 was 0. respectively (Garvey et al. Population growth of Chlamydomonas was not affected at copper concentrations up to 0. 1995).064 mg/L. The data in softer water (lower hardness) vary and are not conclusive. The next most sensitive value was the 0. The lowest result was an LOEC value of 0. Alberta Chronic Guideline The Alberta chronic guideline is the lower of the final chronic value (0.2 mg/L. Only a few lakes in specific regions of Jasper National Park.010 mg/L).048 mg/L and 0. respectively (Bishop and Perry 1981). The restriction for using the copper guideline is added because: • • few data are available at water hardness below 50 mg/L CaCO3.01 mg/L was therefore adopted as the final plant value.007 mg/L.01 mg/L LOEC value for decreased PSII activity and decreased tolerance to photoinhibition. The lowest value is the final chronic value. Although this test is not a "standard" toxicity endpoint. The final plant value is the lowest concentration with an important aquatic plant species resulting in a biologically significant effect. 37 . Frond growth and growth rates were reduced 50% at 0.015 mg/L for Staurastrum chaetoceras and S. 1995). manfeldtii. The chronic toxicity data span a water hardness range from 26 mg/L CaCO3 to over 200 mg /L CaCO3.009 mg/L for deflagellation of Chlamydomonas.007 mg/L) and the final plant value (0. encystment and deflagellation were affected at 0. This chronic guideline however should only be applied to surface waters where hardness is equal to or greater than 50 mg/L CaCO3.8 mg/L and and less than 0. The value of 0. 1991). Deflagellation however was not considered a biologically significant endpoint. the Alberta chronic guideline is therefore 0. the Canadian Shield area (extreme northeast region of Alberta) and certain northern upland regions (Caribou and Birch Mountains) have low alkalinity and water hardness. A decrease of photosystem II (PSII) activity and tolerance to photoinhibition was observed in Chlorella pyrenoidosa at a copper concentration of 0. it is a measurement of a biologically significant process.


Application of the Alberta Copper Guideline

Most of the toxicity studies cited in this document are carried out in laboratory water with low complexing capacity. In contrast, surface water samples generally have much higher complexation capacities than laboratory water. Total copper measurements in surface water therefore consist largely of non-toxic forms (Sections 2.2 to 2.4). Little dissolved copper (containing the toxic copper species) is present and therefore only a small fraction of total copper in surface water would be actually toxic. Therefore total copper concentrations in surface water below the copper guideline indicate a lack of copper toxicity. The toxic copper fraction would be a small fraction of total copper and would therefore be well below the copper guideline. When total copper concentrations in surface water exceed the copper guideline the reverse argument however cannot be made. A measurement of total copper provides no information on the concentration of the toxic copper forms. In these cases, the concentration of the toxic copper forms could be either less or greater than the copper guideline. The following guidance is therefore provided to use and apply the copper guideline in an accurate and meaningful manner.

Preferred Approach To properly asses the potential presence of copper toxicity, it is important to monitor the toxic form of copper in surface water. The best method to determine toxic forms is to analyse dissolved copper in water (i.e., copper in a sample filtered through a 0.45 :m membrane filter). Other methods (copper ion electrode potentiometry and electrochemical methods) may determine the more toxic copper forms compared to dissolved copper analyses. However, these methods do not include all the toxic copper species and are not routinely used in either toxicity tests (used to derive the copper guideline) or in ambient monitoring programs.

Although most copper in toxicity tests is added as a toxic, ionic form and laboratory water has low complexing capacity, some of the copper changes during the test to a non-toxic form. Most toxicity endpoints used in the copper guideline are based on total copper or total acid-extractable copper. A comparison of paired toxicity results expressed as total copper and dissolved copper indicated that in acute and chronic tests 52 to 95% of total copper was dissolved (Appendix J, USEPA 1994). A conversion factor of 0.96 is therefore recommended to adjust the total copper guideline to a dissolved copper guideline (USEPA. 1995. Interim Final Rule. Water Quality Standards. Establishment of Numeric Criteria for Priority Toxic Pollutants. State's Compliance Review of Metals Criteria. Federal Register May 4, 1995. 40CFR Part 131). This conversion factor is used to adjust the copper guidelines (expressed as total copper or acid-extractable) derived in Sections 4.1 and 4.2 to dissolved copper. Dissolved copper measurements in surface water determined by clean techniques should be compared to the following dissolved copper guidelines:


Dissolved Acute Guideline (mg/L) at 100 mg/L CaCO3 at other hardness 0.015988*0.96=0.0153 (0.015) e0.979123ln(hardness)-8.68579

Dissolved Chronic Guideline (mg/L) 0.007544*0.96=0.0072 (0.007) 0.007

The use of clean techniques in determining dissolved copper concentrations is essential (Appendix L, USEPA 1994). These clean techniques prevent contamination of the dissolved sample through proper sample collection, quality assurance and quality contol procedures, and laboratory techniques. Clean techniques also prevent contamination of the filtered sample from copper contained in the membrane filters (filters should be soaked in acid until they are metalfree).

Alternative Approach If clean techniques cannot be used to determine reliable and accurate dissolved copper concentrations, acid-extractable copper measurement should be determined. This fraction is more similar to copper measurements in the laboratory tests used to determine the copper guideline than total copper. These acid-extractable measurements should be compared to the guidelines calculated in Sections 4.1 and 4.2:

Acute Guideline (mg/L) Chronic Guideline (mg/L)

e0.979123*ln(hardness)-8.64497 0.007

As outlined above, environmental concentrations measured as acid-extractable copper exceeding the Alberta guidelines may not indicate the presence of copper toxicity. For those situations where environmental concentrations exceed the Alberta guidelines, the possibility for negative environmental effects could be determined further in two ways:



Use of clean techniques to determine the "true" dissolved copper concentrations. If the dissolved copper concentrations exceed the dissolved copper guideline, potential negative effects on instream biota may be present. Determine a site-specific guideline as outline in the protocol for deriving Alberta guidelines for the protection of freshwater aquatic life (Alberta Environmental Protection 1996). If the environmental concentrations exceed the site-specific guideline, negative effects on instream biota may be possible.


Soft Water The chronic copper guideline does not apply to water with a hardness less than 50 mg/L CaCO3. Additional research is required to determine conclusively chronic toxicity of copper at low hardness.


the information on chronic toxicity in soft water (water hardness less than 50 mg/L CaCO3) is limited and inconclusive. 41 . Additional research is required to improve the database and to allow development of a chronic guideline for soft water. However.5 DATA GAPS Extensive information is available regarding the acute toxic effects of copper on aquatic biota.

094*H+2 :g/L e0.464 :g/L e0. a comparison of the various guidelines with the Alberta guidelines at specific hardness values is presented in Table 8. In addition.64497 mg/L 2 :g/L 0.979123*lnH-8. respectively. Type chronic acute Guideline 7 :g/L e0.465 :g/L chronic 5 :g/L 10 :g/L chronic acute 2 :g/L 0.465 :g/L 1 and 5 :g/L1 6 and 22 :g/L1 10 and 40 :g/L1 28 and 112 :g/L1 10 mg/L 50 mg/L 100 mg/L 300 mg/L <50 mg/L >50 mg/L <60 mg/L >60 mg/L Hardness (H in mg/L CaCO3) >50 mg/L Jurisdiction Alberta (1996) CCREM (1987) Ontario (1994) Saskatchewan (1988) British Columbia (Singleton 1987) USEPA (1984)/ Quebec (1990)/ Manitoba (Williamson 1988) FAO (Alabaster and Lloyd 1982) 1 chronic acute tentative 50th percentile and 95th percentile.8545*ln(H)-1. The Alberta acute and chronic guidelines are similar to copper guidelines in other jurisdictions.2*e0.9422*ln(H)-1.6 COPPER GUIDELINES FROM OTHER JURISDICTIONS Copper guidelines for the protection of freshwater aquatic life from other jurisdictions are summarized in Table 7. the Alberta guidelines derived with the Alberta protocol are environmentally protective and practical (Alberta Environmental Protection 1996). Copper guidelines for the protection of freshwater aquatic life in other jurisdictions.8545*ln(H)-1. the Alberta guideline is based on an up-to-date literature review and therefore is more current than other guidelines. However. 42 . Table 7. low temperature. Because most guidelines vary with water hardness. adjustments can be made for the presence of organic matter.04*H :g/L 0. harmful substances and other species.

2 Water Hardness (mg/L CaCO3) 100 16. Jurisdiction 50 Alberta USEPA/ Quebec/ Manitoba British Columbia 8.2 7 6. Comparison of freshwater aquatic life guidelines for copper (in :g/L) from various jurisdictions.5 34.0 5 30.8 49.0 300 46.7 200 31.9 Guideline Type Acute 7 7 2 5 6.0 17.2 Chronic Alberta CCME Ontario USEPA/ Quebec/ Manitoba/ Saskatchewan British Columbia FAO 10 2 1/5 10 4 6/22 10 8 10/40 10 12 28/112 43 .8 7 4.Table 8.1 9.2 5 21.5 11 7 2.3 30.8 20.3 5 11.

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12 pH: measured.05 7-d LC50 0.04 28-d LC50 0. T: 26.2-8. CuSO4 24-hr LC50 0.61 48-hr LC50 5.6 (5.5. DO: 6.8.389 M-D. S Horne and Dunson 1994 hatch 4-d post-hatch hatch 4-d post-hatch 4-wk SR (2/d). S Birge and Black 1979 pH: 6. S Khangarot et al.05 4-d LC50 3. DO: near sat 100 (93-105) M(NR).2-7.96 3-d LC50 0.09 g S.2-7. Alk: 135 (120-160). 1994 Fowlers toad hatch 4-d post-hatch hatch 4-d post-hatch embryo SR (2/d).31 96-hr LC50 5.8-2. DO: near sat 100 (93-105) M-D.7 N. DO: moderate aeration 197 M-D. Alk: 9798.8-7.2-7. T: 25.5 (5.4 142-145. CuSO4 SR (2/d). DO: 6.04 96-hr LC50 0.86-6.5 240 (210280) N. T: 10.87. CuSO4 pH 7.04 48-hr LC50 5. T: 20-24. S Birge and Black 1979 Rana tigrina 0. S Birge and Black 1979 Marbled salamander Microhyla ornata pH: 7. Alk: artificial soft water pH: 7. S Birge and Black 1979 Gray tree frog pH: 7. Species Acute and chronic copper toxicity data on amphibians. T: 20.4 (7.446 96-hr LC50 0. P Dobbs et al. DO: 8. S Rao and Madhyastha 1987 Microhyla ornata 1-wk SR (1/d) pH: 6.04 3-d LC50 0. DO: near sat 100 (93-105) M-D.5-26.8. T: 20-24.8. DO: 8. CuSO4 pH 7. T: 20+1. Lifestage Test Type Toxicity Endpoint (mg Cu/L) Environmental Conditions Hardness Classificati on Reference Primary Studies Two-lined salamander Secondary Studies Bufo melanosticus tadpole.2-7.5-26. CuSO4 SR (2/d).5).8.2-8.59 8-d LC50 0.315 pH: 7.5 (7. T: 20-24. CuSO4 SR (1/d 4-d LC50 0.32 3-d LC50 35. Alk: 50-60.86-6. S Rao and Madhyastha 1987 Narrowmouthed toad hatch 4-d post-hatch SR (2/d).6).5 N.74 96-hr LC50 5. T: 20-24.8). 100 mg S. DO: near sat 100 (93-105) M-D. T: 20-24. S de Zwart and Slooff 1987 76 .5 N.8) 185 (165215) Nl. 1.2-7. CuSO4 S pH: 7. 1981 Xenopus laevis 3-4wk old larvae S 48-hr LC50 1. T: 25.94.2 cm.2.4-7.5) pH: 8+0.38 24-hr LC50 5. Alk: 9798. Alk: 165 (140-190). T: 29-34.8. S Khangarot and Ray 1987a 40 mm S 48-hr LC50 1.94.Alk: 180. DO: 9=0. DO: 80% Sat 100-120 M.99 7-d LC50 26. S Birge and Black 1979 Jefferson salamander Leopard frog pH: 4.4 142-145.Appendix 1.843 48-hr LC50 0.5 (24-27.1-7.77 24-hr LC50 6.06 7-d LC50 0.09 96-hr LC50 0.06 8-d LC50 0.

U Lande and Guttman 1973 Xenopus laevis female SR (1/d) 30-d NOEC 0.5.15 M-D. U 13-80 N.Alk: 290+32. U Porter and Hakanson 1976 Rana pipiens 30-d LC50 0.0 pH: 7. T: 20. M=Measured Concentrations. T: 22 Khangarot et al.Species Lifestage Test Type Toxicity Endpoint (mg Cu/L) Environmental Conditions Hardness Classificati on Reference Unsuitable studies Bufo boreas SR (1/2d). T: 19. FT=Flow-Through. 77 . 1985 embryo-larval 72-hr LC50 0. DO: 6. U Fingal and Kaplan 1963 Legend: Test Type: Environmental Conditions: Hardness: Classification: S=Static. T: 13-16. T: 19-21 NR. DO: 6. but significant decrease over test duration. Water Hardness in mg/L CaCO3.039 pH: 6. C=Calculated P=Primary. U Kaplan and Yoh 1961 Rana hexadactyla Rana pipiens 20 mm 96-hr LC50 0. T= Water Temperature oC. Alk: 24-40. CuSO4 adults SR (1/d) . NR=Not Reported. DO=Dissolved Oxygen in mg/L unless otherwise stated.02 pH: 5-6.0016% pH: 5.6.001% 30-d LOEC 0. M-D= Measured Concentration. CuSO4 S 61-d NOEL 0.2-7. S=Secondary.2.6. CuSO4 SR (1/d). SR=Static Replacement. Alk: tapwater not 100% aq.73+0. U=Unsuitable. N=Nominal.2 pH: 5.7.2-6.4+1. Alk=Alkalinity in mg/L CaCO3.0015% dechlorinated tapwater N.9+1.

774 4-d EC50 0.6 pH: 7. Species Copper toxicity data on freshwater algae and plants. Hard: 120-130 M.9. 1995 Staurastrum manfeldtii 150 uE/m2/s M. P Ivorra et al.429 4-d EC50 <0.5 N.P Ivorra et al. 1980 140 ft candle S pH: 8-8. Hard: 45-50 Gerloff's Chu 2RP.9.25 pH: 8-8. T: 22. 12-hr LOEC 0. Hard: 45-50 Gerloff's Chu 2RP.032 4-d EC50 0. N Maloney and Palmer 1956 140 ft candle S 14-d LOEL growth 0. Alk:59 .9. Alk:45-50.3.9. T: 22. T: 30 Gerloff's Chu 2RP.2.019 4-d EC50 0.064 encystment 72-hrNOEL 0. T: 22.0-7.0-7.Appendix 2.009 PSII act.2. 1995 FT. Hard: 45-50 pH: 6. Alk:45-50. 1995 Chlamydomonas reinhardtii 28 Lux pH: 8.25 ? photosynthesis EC50 2. 1991 Chlorella pyrenoidosa Lemna minor 120 umol/m2/s CuSO4 pH: 6. CuSO4 7-d EC50 root length 0. Alk:45-50.2.1 T: 20 T: 20 lakewater complete med. compl-EDTA lakewater complete med. CuSO4 pop growth 72-hr LOEL>0. P Vavilin et al.2-7. acicularis Ankistrodesmus braumii Chlamydomonas communis Chlamydomonas paradoxa Chlorella variegata Chlorella vulgaris 140 ft candle S 14-d LOEL growth 0.034 72-hrLOEC 0. Alk:45-50.015 S. T: 22. N N Maloney and Palmer 1956 Hassall 1963 78 .006 20-d growth LOEL 0.25 pH: 8-8.010 pH: 7. compl-EDTA no EDTA M.048 deflagellation 72-hrNOEC 0. Hardn: 76 M. T: 22.8-8.51 pH: 8-8.1 T: 20 pH: 7. N Maloney and Palmer 1956 140 ft candle S 14-dLOEL growth 0. Hard: 45-50 Gerloff's Chu 2RP. P Garvey et al.4 T: 20 pH: 7.51 T: 20 Ohad (1967) N Laube et al.6. Alk:45-50. N Maloney and Palmer 1956 140 ft candle 1x105 cells/L S S 14-d LOEL growth 0.Hard: 45-50 Gerloff's Chu 2RP.8.1-6.EDTA 8. T: 35 Tanuya med.2. N Maloney and Palmer 1956 8x104 cells/mL CuNO3 20-d growth NOEL 0.9.T: 20+1.063 14-d LOEL growth 0. Lifestage/ Light Test Type Toxicity Endpoint (mg Cu/L) Environmental Conditions Medium Classification Reference Primary studies Staurastrum chaetoceras 150 uE/m2/s 4-d EC50 0.005 72-hrLOEL 0.2.034 4-d EC50 0.3 pH: 8-8. P Bishop and Perry 1981 Non-primary studies Ankistrodesmus falcatus Ankistrodesmus falcatus.

T: 22.9. N Maloney and Palmer 1956 140 ft candle S 14-d LOEL growth 0.9. -EDTA Arnon A5 3RP.06 pH: 8-8. T: 24 pH: 5.3x106 cells/mL 6/7 Lux S. Hard: 45-50 Gerloff's Chu medium 2RP.2. 1994 Chlorella sp.05 T: 18-20 pH: 8.2. Alk:45-50. Alk:45-50. 1969 CuSO4 S 4x104 cells/mL S 72-hr cell div. Alk:45-50. 165. 20kLux. 8. Hard: 45-50 Gerloff's Chu 2RP.51 pH: 8-8. Hard: 45-50 Gerloff's Chu 2RP.006 T: 21.2. N Maloney and Palmer 1956 140 ft candle S 14-d LOEL growth 0.9. enr. T: 22. CuSO4 growth to stat. T: 20 10% Bristol Bristol Osterlind NR N N Wong 1989 Wong and Beaver 1980 Steeman-Nielsen et al.9.9. phase LOEC 0.51 pH: 8-8.02 pH: 22 BG11 Chlorococcum botryoides Chlorococcum humicola Coccomyxa simplex Coelastrum probscideum Gloeocystis grevillei Mesotaenium caldariorum Oocystis lacustris 140 ft candle S pH: 8-8. N Maloney and Palmer 1956 79 .2.2. Alk:45-50. T: 22. N Maloney and Palmer 1956 140 ft candle S 14-d LOEL growth 0.2.2. T: 23 Art.51 pH: 8-8.005 T: 20 Osterlind B-EDTA Steeman-Nielsen and KampNielsen 1970 N Brady et al. T: 22. T: 22. Hard: 45-50 Gerloff's Chu 2RP. T: 22. N Maloney and Palmer 1956 140 ft candle S 14-d LOEL growth 0.05 division NOEL 0. Hard: 45-50 Gerloff's Chu 2RP. Alk:45-50.2 mg/L 20-hr photosynthesis EC49 0. Alk:45-50.127 pH: 8-8. CuNO3 N Gachter et al.9.02 pH: 6. N Maloney and Palmer 1956 140 ft candle S 14-d LOEL growth 0. T: 22.Species Lifestage/ Light 8000 Lux Test Type Toxicity Endpoint (mg Cu/L) Environmental Conditions Medium Classification Reference Chlorella vulgaris Chlorella ellipsoida Chlorella fusca Chlorella fusca Chlorella pyrenoidosa Chlorella pyrenoidosa S.127 pH: 8-8. IC50 >200 4-hr LOEL 0. N Maloney and Palmer 1956 140 ft candle S 14-d LOEL growth 0. IC50 16 72-hr cell div.5 96-hr LOEL 25 14-d LOEL growth 1. MBL medium pH: 7 Nutrient N Stauber and Florence 1989 Chlorella sp.2.6 start.4 uE/m2/s CuSO4 96-hr NOEL 2. Hard: 45-50 Gerloff's 2RP. EPA medium T: 21.9. NR N Foster 1977 Kanazawa and Kanazawa 1969 S 10 cells/mL 1. IC50 24 72-hr cell div.8x10 cells/L 7 4 survival 0. 1973 Chlorella sp. Hard: 45-50 Gerloff's Chu 2RP.095 mg/L 20-d growth LOEL 0. 100-150 hr 0. soft water T: 21. Alk:45-50.

0476 pH: increased to 8. 1992 S survival 0. N Maloney and Palmer 1956 1. 1974 S/SR.05 mg/L 1-3 hr LOEL 0. 1975 S 300-hr 2 ng/L pH: 7. N N Maloney and Palmer 1956 Gibson 1972 S. CuSO4 14-d LOEL growth 0.05 pH: 7.6x106 cells/L Test Type Toxicity Endpoint (mg Cu/L) Environmental Conditions Medium Classification Reference Oocystis marsonii Scenedesmus quadricauda Scenedesmus quadricauda Scenedesmus quadricauda Scenedesmus quadricauda Scenedesmus quadricauda Scenedesmus basilensis Scenedesmis obliquus Scenedesmus capricornutum Scenedesmus sp. 1993 CuSO4 T: 22 N Brady et al. Alk:45-50. Alk:45-50.054/0.09 mg/L 10% Bristol ? Wong 1989 5x104 cells/mL CuCl2 21-d growth LOEL 0.09 mg/L 96-hr NOEL 25 mg/L 96-hr LOEL 100 T: 22 10% Bristol BG11 NR N Wong 1989 Brady et al.55.5 shaken 100rpm NR Christensen and Nyholm 1984 CuCl2 4-7 d incipient inh.4 uE/m2/s 104 cells/mL SAAM N Christensen and Scherfig 1979 EC50 0.9 agitated N Bartlett et al. N Radetski et al.8 min. T: 22.N Arsenault et al. Hard: 45-50 Gerloff's Chu 2RP. Selenastrum sp.Species Lifestage/ Light 140 ft candle 2. 0.8-1. S S.05 mg/L T: 18-20 Bristol N Wong and Beaver 1981 140 ft candle S 14-d LOEL growth 0. Hard: 45-50 Gerloff's Chu 2RP.51 pH: 8-8. Alk:8.085 pH: 6. 1994 80 . 1995 survival 0. 1994 Selenastrum capricornutum Selenastrum capricornutum Selenastrum capricornutum Selenastrum capricornutum Selenastrum sp.0 T: 20-22 N Khobot'yev et al.9. T: 22. 165.2x106 cells/mL 165.048 T: 24+2 LC/ISO 3RP.CuSO4 1-3 hr NOEL 0. Hard: 14. CuCl2 10-d EC33 1.2.10 2RP.9. Alk:45-50. 0.2.C Verwey et al.15 mg/L 96-hr NOEL 25 96-hr LOEL 100 21-d EC50 cell vol. N Maloney and Palmer 1956 140 ft candle S 14-d LOEL growth 4. 15 mg/L NaHCO3 BG11 3RP. T: 24.2.1 pH: 8-8.2. T: 22. Hard: 45-50 T: 20 Gerloff's Chu Chu No.0 pH: 8-8. CuSO4 S CuSO4 72-hr grwoth EC50 14-d no irreversible damage 0. T: 23 Art+EDTA M.1-7.4 uE/m2/s S.

Hard: 45-50 2RP. Alk:45-50. Hard: 45-50 2RP.127 pH: 8-8. Alk:45-50. Hard: 45-50 Gerloff's Chu 2RP. 1975 Fogg and Westlake 1953 growth 20-d NOEL 0.2. T: 22.32 10-d EC90 1.127 pH: 8-8. N Maloney and Palmer 1956 S 10-d no irreversible damage 0. Alk:45-50.5 E100 4 mg/L T: 20 N Gibson 1972 OD 0. N Maloney and Palmer 1956 140 ft candle S 14-d LOEL growth 1.10. Hard: 45-50 2RP.006 20-d LOEL 0. N Maloney and Palmer 1956 140 ft candle S 14-d LOEL growth 0. Alk:45-50. T: 22. T: 22.02 pH: 8-8.51 pH: 8-8.2. T: 22. Alk:45-50.9. Hard: 45-50 2RP.01 OD0.2. N Maloney and Palmer 1956 Achanthes linearis #1 140 ft candle S 14-d LOEL growth 0.9.2. N Maloney and Palmer 1956 140 ft candle S 14-d LOEL growth 0. T: 22. Hard: 45-50 2RP. Alk:45-50. T: 22. Alk:45-50.2. N Maloney and Palmer 1956 Cylindrospermum licheniforme Microcystis aeruginosa Nostoc mescorum 140 ft candle S 14-d LOEL growth 0.51 pH: 8-8. T: 22.005 1-hr IC50 0.2. Hard: 45-50 Gerloff's Chu medium Gerloff's Chu medium Gerloff's Chu medium Gerloff's Chu medium Gerloff's Chu medium Gerloff's Chu medium Gerloff's Chu medium Gerloff's Chu medium 2RP. Hard: 45-50 2RP.25 pH: 8- Hard: 45-50 2RP.0 rate of movement EC50 0. 1995 Anabaena variabilis Anabaena cylindrica Anabaena 7120 8x104 cells/mL CuNO3 T: 20-22 N NR Kobot'yev et al.2.2 CuSO4 pH: 8 inorg.127 pH: 8-8. 1980 Calothrix braunii 140 ft candle S pH: 8- pH: 8-8.2.9. Hard: 45-50 Gerloff's Chu medium T: 20 2RP. N Maloney and Palmer 1956 81 . Alk:45-50.063 14-d LOEL growth 4.9. N Peterson et al. Alk:45-50. T: 22. T: 22.9.127 pH: 8-8. N Maloney and Palmer 1956 Plectonema nostocorum Symploca erecta 140 ft candle S 14-d LOEL growth 0. N Maloney and Palmer 1956 Phormidium tenue 140 ft candle S 14-d LOEL growth 0.Species Lifestage/ Light 140 ft candle Test Type Toxicity Endpoint (mg Cu/L) Environmental Conditions Medium Classification Reference Sphaerella lacustris Stigeoclonium nanum Anabaena flosaquae Anabaena flosaquae S 14-d LOEL growth 0.9.25 nitrogen fixation 16-hr IC90 0.07 T: 20 BGII medium N Laube et al. Alk:45-50. T: 22. N Maloney and Palmer 1956 140 ft candle S 14-dLOEL growth 0.

NaCl N N Rosko and Rachlin 1977 Mishra et al. T: 20 N N Khare and Bisen 1991 Stanley 1974 French and Evans 1988 Myriophyllum spicatum 300 fc Amphora coffaeformis 130 umol/m2/s root weight 32-d IC50 0.9. 1968 Brown and Rattigan 1979 Brown and Rattigan 1979 Byl et al.06 pH: 5+0.9 Guillard f/2 (chelators) M-D 82 .1.sucrose.9.25 96-hr EC50 6. T: 22.cov.815 O2 evolution 48-hr IC50 0.32 multipl.127 growth 120-hr IC50 0.4-7. Hard: 45-50 2RP.14 multiplic.2. Alk:45-50.5uM EDTA modified Chu synthetic M Jenner and Janssen-Mommen 1993 Cylindrospermum 10 W/m2 S S Cu2O/CuCl2 T: 24+1 T: 20 pH: 8.2. T: 22.18 5min PSII inhibit.2. T: 22.1 pH: 8-8. N N N N N Maloney and Palmer 1956 Patrick et al.1. N Maloney and Palmer 1956 Nitzschia palea #2 140 ft candle S 14-d LOEL growth 0. T: 21+1 T: 24+1 Bristol Pbuffer. T: 22.2. Alk:45-50.2 90-d NOEL 0. Hard: 45-50 2RP. T: 22. T: 25 Hoagland +EDTA Anabaena flos-aque S CuSO4 T: 20 Medium D N Young and Lisk 1972 Scenedesmus quadricauda Chlorella vulgaris Nostoc muscorum 100uE/m2/s CuCl2 T: 27 Bringmann and Kuhn 1980 33d growth EC50 0.1 7-d TT 1. 14-d EC50 0. N Maloney and Palmer 1956 140 ft candle S 14-d LOEL growth 0. Alk:45-50.13 growth LOEL 1 growth NOEL 0. N Maloney and Palmer 1956 140 ft candle S 14-d LOEL growth 0. CuSO4 14-d LOEL growth 0.2.2-2.06 pH: 8-8.001 growth 90-d LOEL 0. EC50 0.127 pH: 8-8.6 MIC4.00 lux S S T: 24 HEPES buffer HEPES buffer 7-10 cm shoot length CuSO4 pH: growth 0. 14-d EC50 0.9.01 5-d NOEL 0. N Maloney and Palmer 1956 Nitzschia palea #3 Nitzschia linearis Elodea canadensis Lemna minor Hydrilla verticillata 140 ft candle S S.51 pH: 8-8. 1993 Lemna minor 80 umol/m2/s laminar flow system surf. Hard: 45-50 Gerloff's Chu medium Gerloff's Chu medium Gerloff's Chu medium Gerloff's Chu medium Gerloff's Chu medium synthetic medium 2RP. NOEL 0. Hard: 45-50 2RP. 1994 16.1 POD activity 5-d LOEL 0. Alk:45-50.Species Lifestage/ Light 140 ft candle Test Type Toxicity Endpoint (mg Cu/L) Environmental Conditions Medium Classification Reference Achanthes linearis #2 Gomphonema parvulum Nitzschia palea #1 S 14-d LOEL growth 0.15 14-d plant damage 0.795-0. Hard: 45-50 2RP.25 pH: 8-8. Alk:45-50.19 pH: 7+0. T: 23+1 Gorham+ 2.

RP=Replicated P=Primary. FT=Flow-Through. SR=Static Replacement.2 96-hr growth EC50 0.042 pH: 8.8-3. 1985 NOEC 0. C=Calculated. T: room temp inorg.5 MIC 5.EDTA N Lee et al. minimum med N Den Dooren 1965 Chlorella vulgaris Selenastrum capricornutum Anacystis nidulans T: 20+1 T: 20+1 OECD OECD M-D M-D Blaylock et al.02 3-4 mo LOEL 0.1 6000 Lux CuSO4 12-d growth EC30 0. but significant decrease over test duration.25. M=Measured Concentrations.Species Lifestage/ Light 130 umol/m2/s Test Type Toxicity Endpoint (mg Cu/L) Environmental Conditions Medium Classification Reference Amphora hyalina S Cu2O/CuCl2 96-hr EC50 5. NR=Not Reported. N=Nominal.318 10-d growth LOEC 0.1.2/2 LOEC 2/20 S.3 EC50 0. T= Water Temperature oC. Hard=Water Hardness in mg/L CaCO3. LOEC 0.1. 1993 Anacystis nidulans Chroococcis paris Lemna paucicostata Hepes+pBQ BG11 Hoagland N N N Gupta and Singhal 1995 Les and Walker 1984 Nasu and Kugimoto 1981 Legend: Test Type: Environmental Conditions: Classification: S=Static. DO=Dissolved Oxygen in mg/L unless otherwise stated. U=Unsuitable.3 pH: 7. M-D= Measured Concentration.0-5. T: 25+1 +/.4 pH: 7. CuCl2 6-d PSIIact. T: 25 T: 26 pH: 5.04 S S 96-hr growth EC50 0. 1985 Blaylock et al. Alk=Alkalinity in mg/L CaCO3. T: 20 Guillard f/2 (chelators) M-D French and Evans 1988 Selenastrum capricornutum Chlorella vulgaris Porcella EPA method N Miller et al. 1985 growth 3-4 mo NOEL 0. S=Secondary. 83 .

T: 11-13. DO: light aeration 14 M. CuSO4 FT 96-hr ILL 0.5. DO: 6. Alk: 156. T: 22+1. T: 17 14 M.9 100-120 46 M. P Benoit 1975 Dobbs et al. Alk: 42 pH: 7. P Brown bullhead Checkered rainbowfish Chinook salmon 39 mm juveniles FT.1.8-9. T: 20.5-7.3 96-hr LC50 0.8 cm FT. DO: 7+1.9 pH: 7.025 T: 3.6.88-8.9-1. 1985 Thompson et al. P M. P Geckler et al.2 M. DO: diffused air 20 M. P Geckler et al.54 96-hr LC50 0.31.9 mg/L 200 M.74 mg/L 45+0.2-59. CuSO4/Cu Cl2 FlT. T: 23-25.1 pH: 7.5. P Finlayson and Verrue 1982 84 . P M.0.8-4.9-6.17-0.69. 1976 Williams et al. Alk: 43+1. CuSO4 FT FT. CuCl2 FT.8.85-6. T: 25. P Blacknose dace Bluegill Bluegill FT.4).032 pH: 7.3 (7-7.9-8.9 196-205 45 202 M. P Sprague and Ramsay 1965 Sprague 1964b Atlantic salmon FT 200 hr ILL 0. CuCl2 96-hr LC50 0.5-6.1. T: 23-25. P M.9-8. DO: >5. T: 20+1. T: 15-20.32 96-hr LC50 1. 1976 McKim and Benoit 1971 Brungs et al. P M.Appendix 3. Alk: 156. Alk: 148-161 pH: 5.1-7.15. CuSO4 96-hr LC50 0. Alk: 148-161 Alk: 82 pH: 6. 1991 3.34 96-hr LC50 0.4-11.9-8. CuSO4 96-hr LC50 0.5 pH: 7-8.3-7. DO: 6. T: 27+0.032 pH: 7.19 pH: 7. Lifestage Test Type Toxicity Endpoint (mg Cu/L) Environmental Conditions Hardness Classification Reference 8. Alk: 23.186 pH: 7. P M. 1980 Bluegill Bluegill Bluegill 35 g. 1976 Blaylock et al.6+1.8.19 96-hr LC50 0.168-0.8 cm FT.6+1.1 mg/L 48-hr LC50 4. T: 20. Alk: 148-161 pH: 7. Alk: 12. T: 23-25.7) cm 47 mm 35.8. T: 12.8-7.8+1 mm 49mm 48-hr ILL 0. P Horning and Neiheisel 1979 Geckler et al. DO: 6.2-32. 1994 Trama 1954 Bluntnose minnow 96-hr LC50 0.6.2 (7.5 mg/L 196-205 85 21. T: 23. 1973 Bluntnose minnow Brook trout Brown bullhead 84 mm 14 mo old 7 mo 2 yr FT.5.1.3 96-hr LC50 0.9) cm 8. DO: 90% Sat 20-22 M.2 pH: 7.5 (6. 12 cm 35mm 1-9 g FT. T: 15. Alk: 5 196-205 25-30 M.1.5 (pH control).5. Alk: 50-60. P M. P Carson and Carson 1972 Atlantic salmon 9.23 pH: 7. CuSO4 96-hr LC50 1. CuSO4 FT 96-hr LC50 0.100 96-hr LC50 0. CuSO4 S S. Species Primary Studies Atlantic salmon Acute copper toxicity data on freshwater fish. DO: 80% Sat pH: 4. P M. Alk: 3-6.048 pH: 7. DO: >4. CuSO4 FT.2-10.

8 mg/L) pH: 7.079/0.8.85-6. Alk: 148-161 31 196-205 M. DO: measured pH: 8.5-8.7 (6.15. DO: aerated (6-10. T: 22. T: 22.49 48-hr LC50 0. P M. T: 10. T: 27+0.075 96-hr LC50 0.038 96-hr LC50 0.46g 1.0037 96-hr LC50 0. DO: 10. CuCl2 pH: 7.74 202 M. Alk: 30-31.2+0. P Chakoumakos et al. T: 20.7 (6. CuSO4 FT.46 96-hr LC50 0.026 96-hr LC50 0. P Chapman 1978 Chiselmouth Coho salmon FT.8+0.8-7.2 g FT. DO: measured Hardness 13 46 182 359 Classification M. CuSO4 pH: 7.070/0. DO: 7. Alk: 125.143 96-hr LC50 0. T: 9.64.026 96-hr LC50 0.2. DO: 80% Sat pH: 7. P Andros and Garton 1980 Lorz and McPherson 1976 Geckler et al.056/0. DO: 7. P Nelson et al. P Mount and Stephan 1969 Geckler et al.01 96-hr LC50 0.8. P Reference Chapman and McCrady 1977 Chinook salmon Alevin 0. Alk: 20.05g Swim-p 0.3 47. 1991 Nelson et al.7-8. T: 12. CuCl2 96-hr LC50 0. Alk: 243.9) pH: 7. 1976 Fathead minnow Fathead minnow S FT. DO: 8. T: 10-12. CuSO4 FT 72-hr LC50 0.5. Alk: 22+2.4. T: 12. T: 23-25.9-7. P M. 1977 Fathead minnow Fathead minnow FT FT.367 205 (202-208) M.5-7.8.12. Alk: 48. 1994 Nelson et al.7 g FT.1.23g Parr 11. T: 12.6-11.085 96-hr LC50 (T/D/CU2+) 0. 1986 Fathead minnow 6-mo old 6-wk old 10-20mm 56 mm 47 mm 3 wk old 1-d pH: 7.58.0157 196-205 26.94.074 pH: 7. CuSO4 FT. CuCl2 96-hr LC50 0.6. T: 12. P M.06-0.019 96-hr LC50 0.44 96-hr LC50 0. 1979 Eel-tailed catfish Fathead minnow juveniles 1-d FT FT.4 (23-30) M.1. Alk: 68-78. Alk: 35 . Alk: 12. P Pickering et al. DO: measured pH: 8. Alk: 43.35 g Test Type FT Toxicity Endpoint (mg Cu/L) 96-hr LC50 0.09 96-hr LC50 0.025 96-hr LC50 0. T: 12. DO: 7.125 Environmental Conditions pH: 7.075/0.3 23+1 M.2-7.008/0.31 96-hr LC50 0. 1986 85 .25 g yearling FT 96-hr LC50 0.49 96-hr LC50 0. P Dobbs et al. T: 23-25.2+0. T: 22.5. 1986 Fathead minnow 1-d pH: 8.1 (19-24). P Cutthroat trout 4. Alk: 5 pH: 6.9 20-30 95 (89-99) M. DO: measured pH: 7.58g Smolt 32. P M. CuSO4 pH: 6.3 pH: 6.2.Species Chinook salmon Lifestage 1. T: 25.7-8.284 96-hr LC50 (T/D/CU2+) 0.9) pH: 5.007/0.2 M. 1976 Chakoumakos et al. Alk: 50-60. DO: 7.2 (NaCl2) M. P M. Alk: 178 (173-188). Alk: 148-161 pH: 7. Alk: 20-30. T: avg 23-24.5. Alk: 148 100-120 45 M.9 pH: 7. CuCl2 SR.1- 1979 Creek chub Cutthroat trout 64 mm 5. P Williams et al.00095 96-hr LC50 (T/D/CU2+) 0.9.0013 25-30 49.

Alk: 17 44 M. CuSO4 FT. CuSO4 FT. CuCl2 Toxicity Endpoint (mg Cu/L) 96-hr LC50 (T/D/CU2+) 0. CuSO4 FT.0004 48-hr LC50 0. Alk: 26.0020 96-hr LC50 (T/D/CU2+) 0. T: 22.0053 96-hr LC50 (T/D/CU2+) 0.00. CuSO4 FT. 1986 Fathead minnow 1-d pH: 7. P M.4 45 M.0016 96-hr LC50 (T/D/CU2+) 0. 1986 Fathead minnow 1-d pH: 7. CuSO4 FT.071/0. Alk: 155 46.06.046/0. 52 43. Alk: 161 44 M. CuSO4 FT.8 45. CuSO4 FT.00056 96-hr LC50 (T/D/CU2+) 0. T: 22.021/0.18 pH: 7. 1986 Fathead minnow Fathead minnow 30 d. DO >90% Sat. CuSO4 Fathead minnow 1-d 96-hr LC50 (T/D/CU2+) 0.4-8.9+1 M.84. T: 22.055 96-hr LC50 0.06. Alk: 42.00079 96-hr LC50 (T/D/CU2+) 0.157/0. Alk: 43. P Nelson et al. Alk: M. 1986 Fathead minnow 1-d pH: 8.0420.095/0.050/0. T: 22. CuNO3 FT.004 96-hr LC50 (T/D/CU2+) 0. P Nelson et al. 1986 Fathead minnow 1-d pH: 8.35. P Nelson et al.066/0. T: 22. DO: 7. P Nelson et al.119/0. 1986 Fathead minnow 1-d pH: 8.5-8.079/0.032/0. 1996 96-hr LC50 0.15. Alk: 42 44 M. T: 22.051/0.3 Hardness 255 (MgCl2) Classification M.0021 96-hr LC50 (T/D/CU2+) 0.096 Environmental Conditions pH: 8. 1986 Fathead minnow 1-d pH: 7. P Jop et al. DO: >70% sat. P Reference Nelson et al.4+1. CuSO4 FT. CuSO4 S. T: M.0043 96-hr LC50 (T/D/CU2+) 0. P M.2 M.082/0.00057 96-hr LC50 0.039/0. T: <22-28.19 g pH: 7.048/0.109/0.16.4.Alk: 42. T: 22. T: 22. Alk: 43. 1986 Fathead minnow 1-d pH: 8. P Nelson et al.022/0.060/0.1. 1986 Fathead minnow Fathead minnow 25-35 d <24 hr FT.1 243 (CaCl2) M. T: 20+2. 1986 Fathead minnow 1-d pH: 8. T: 22. Alk: 42.57. P Nelson et al. CuSO4 FT.Species Fathead minnow Lifestage 1-d Test Type FT. 1993 Erickson et al.0054 96-hr LC50 (T/D/CU2+) 0. P Nelson et al. 0. P Nelson et al.00067 96-hr LC50 (T/D/CU2+) 0.0019 96-hr LC50 (T/D/CU2+) 0. T: 22.6 47 M.046/0. P Nelson et al. 1986 Spehar and Fiandt 1986 FT.019/0.P Carlson et al. Alk: 318 45 M.023/0. 1986 Fathead minnow 1-d pH: 7. P Nelson et al. P Nelson et al. P Nelson et al. Alk: 44. CuSO4 FT. Alk: 55.022/0.5 46.028/0.4 45.13.068/0. 45-60 45 M. 1986 Fathead minnow 1-d pH: 8. T: 22. Alk: 150 45 M.136/0. T: 25+3. T: 22.93.040/0. 1986 Fathead minnow 1-d pH: 7.2 M. Alk: 30-45 pH:8. CuSO4 pH: 7.0107) 86 . CuSO4 FT.019/0.074 (0. T: 22.9.3 pH: 7.

T: 20+1.5 g FT. DO: 7989% sat pH: 7. Alk: 62. 1991 Servizi and Martens 1978 Pumpkinseeds FT.6 g FT. CuSO4 96-hr LC50 0. CuCl2 96-hr LC50 1.1. Alk: 144.33 g FT. P Andros and Garton 1980 Orangethroat darter Pennyfish Pink salmon 44 mm juveniles newly hatched alevin fry 2. P M. Alk: 21.31 mg/L pH: 7.2 g FT.33 (7. T: 25+0.0210.3 52 (45-96) M. T: 27+0. Alk: 3. P Pumpkinseeds 7.077 96-hr LC50 0. CuCl2 96-hr LC50 1. T: 8. P Geckler et al.0.5).1. P Spear and Anderson 1975 Spear and Anderson 1975 Spear and Anderson 1975 Spear and Anderson 1975 Hickie et al.5-8. T: 7. P M. P Anderson and Weber 1975 Spear and Anderson 1975 Hazel and Meith 1970 Guppy 0.6.6. T: 8. Alk: 85+2. Alk: 85+ P Rainbow darter 41 mm FT. CuCl2 96-hr LC50 0.0.087 96-hr LC50 0.5.4) M. P Chynoweth et al.1 g FT.3 pH: 7. P King salmon 0.1-7.32 10. Alk: 20-30. T: 21 (20-22.5.8-7. T: 25. Alk: 31 pH: 7.143 96-hr LC50 0.30 pH: 7. Alk: 148-161 125+5 M.6. Alk: 124 144 M.9-8. CuSO4 196-205 M. 1976 Williams et al. T: 5. Alk: 148-161 pH: 5.85 96-hr LC50 0. 1976 87 . Alk: 85+2.9.1 (82.112 96-hr LC50 0.16-0. P Rainbow trout alevin SR (1/2d) 144-hr LC50 0.5.9-8. P Reference Fogels and Sprague 1977 Goldfish 3. DO: avg 75% sat pH: 7.138 67 88 M. 1993 Pumpkinseeds 1. T: 23-25. T: 20+1.3 44 M.5 (60.29 g LC50 0. T: 23-25. P Geckler et al.8.4) pH: 7.9. DO: 7. CuSO4 FT 96-hr LC50 0. P Northern squawfish 1.5.018 144-hr LC50 0. DO: 7989% sat pH: 7. DO: near saturation pH: 7. Alk: 3.94 125+5 M.018 pH: 6. 1976 Guppies 0. DO: Saturated 196-205 25-30 83.0.3. Alk: 200-255.868.9.199 pH: 7.8. CuCl2 20-30 M.984. Alk: 20-30. T: 25.6 (7.05-8.2.04 96-hr LC50 0. T: 20+1.24 125+5 M. T: 13-14. T: 25. T: 11.6-11.2.1-7.Species Flagfish Lifestage 0. Alk: 5 pH: 7. T: 25. Alk: 36 Hardness 350-375 Classification M.2.2. DO: 7989% sat pH: 5.47 (5. CuCl2 96-hr LC50 1.1.019 96-hr LC50 0.6 pH: 7. DO: 8.1-0.6-11.12-0.0.2+0.2+0.4.67 125+5 M.1-9.139 pH: 7+0. P Pumpkinseeds 4. DO: 99% sat 124 M.0-8. P Tsai and McKee 1980 Guppies 10-21 d FT 96-hr LC50 0. Alk: 85+2. CuCl2 96-hr LC50 1.8).2+0.6 pH: 4.1-6 cm FT. DO: 8.3 g FT 10-d after hatch LC50 0.27 Environmental Conditions pH: 8.85-6.2. DO: 7989% sat pH: 7.2).55-7.3 g Test Type FT Toxicity Endpoint (mg Cu/L) 96-hr LC50 1. T: 20+1.3 M.2 g FT.023 96-hr LC50 0.15.3).

pH: 9. CuSO4 FT. Alk: 85+2. T: 15.58 96-hr LC50 0.Species Rainbow trout Lifestage embryo 12mm Test Type SR (1/d) Toxicity Endpoint (mg Cu/L) 96-hr LC50 0. T: 9. T: 10+1.87 15-d LC50 0.89 14-d LC50 0.19 125+5 M. pH: 5.0-8. DO: >90% sat. 1995 88 .2-7. DO: >70% sat pH: 7.3-18.7. DO: 7495% sat pH: 7. DO: >90% sat. DO: well aerated pH: 7. T: 15.030 96-hr LC50 0. P M. DO: >90% sat. Alk: 84. T: 15-15. Alk: 170. T: 15. Alk: 170.274-0. T: 15.3-7. DO: 9. Alk: 170. pH: 4. P Rainbow trout 3. P Marr et al.6.4.2-9. pH: 9. DO: >90% sat. T: 15.059 96-hr LC50 0. Alk: 170. CuCl2 96-hr LC50 0. DO: >90% sat pH: 8. pH: 8. P Howarth and Sprague 1978 Rainbow trout norm to 10 g fish FT.5. Alk: 85+2. pH: 7. pH: 7.8+0.1. DO: >90% sat. PH: 6. T: 15.0.8-9. pH: 8.9 g FT. DO: >90% sat.049 96-hr LC50 0. CuCl2 M. CuSO4 6-d LC50 0.8+0.7-7.75 96-hr LC50 0. P Rainbow trout Rainbow trout 28. DO: 7. pH: 6. pH: 7.5). Alk: 84.0. P Brown et al 1974 Calamari and Marchetti 1973 Miller and Mackay 1980 Rainbow trout 8-15 g FT 49 (46-54) M. DO: 80-90% sat. Alk: softwater Stephan 1975 46-48.9. DO: >90% sat. pH: 6. pH: 7.3-7.018 370 369 361 366 364 101 101 100 98 30 31. DO: >90% sat. CuSO4 M.21 125+5 M.T: 13+1.4 (+0. T: 15.5. P Rainbow trout juvenile FT. Alk: 200-255. Alk: 28 (24-31).381 346-386 M. Alk: 85+2. Alk: 36. P Howarth and Sprague 1978 Rainbow trout <1g FT. T: 15. CuCl2 96-hr LC50 0. P Reference Giles and Klaverkamp 1982 Spear and Anderson 1975 Brown and Dalton 1970 Fogels and Sprague 1977 Rainbow trout 176 g FT.5 pH: 7.085 96-hr LC50 0. P M. T: 15.8.2 Hardness Classification M. Alk: 25.5 31 30 25 M.349 96-hr LC50 0.3-7. Alk: 36. DO: 7495% sat pH: 7. Alk: 212-236.3. P Rainbow trout Rainbow trout 13-15 cm 12-16 cm FT FT 72-hr LC50 0. T: 15.048 250 290-310 M. T: 15. Alk: 36.393 96-hr LC50 0.1 g FT. T: 10+1.3. T: 15. T: 14.1. CuCl2 96-hr LC50 0.191 96-hr LC50 0.0. Alk: 84. T: 15. DO: 7495% sat pH: 7. P Spear and Anderson 1975 Spear and Anderson 1975 Dixon 1980 Rainbow trout 29.047 96-hr LC50 0. DO: >90% sat. T: 12-15.1.9-15. T: 10+1. T: 10.2 pH: 5. pH: 7. CuSO4 M. DO8.9.102 240 350-375 M. P Howarth and Sprague 1978 Rainbow trout norm to 10 g fish FT. DO: avg 75% sat.35-7.154 96-hr LC50 0.200 125+5 M.825 96-hr LC50 0. .167 96-hr LC50 0. DO: >90% sat.9 g SR (6-hr) FT 48-hr LC50 0. T: 15. T: 15. P Rainbow trout norm to 10 g fish 96-hr LC50 0.0.6. Alk: 170. Alk: 200-210.8+0. pH: 9. Alk: 36. DO: >90% sat.4 Environmental Conditions pH: 7.344 96-hr LC50 0.5 g 1.059 96-hr LC50 0. DO: >90% sat. DO: >90% sat.

1-8.36-3.4-7. T: 18-21.0042 96-hr LC50 0.79 96-hr LC50 1.1. T: 23-25.Species Sockeye salmon Lifestage newly hatched alevin fry smolt 4. T: 25.4.018 96-hr LC50 0.0 96-hr LC50 6.9 96-hr LC50 0. T: 28.01 g FT FT. Alk: 148-161 196-205 249+17 196-205 M. CuSO4 FT FT.8-5. 1976 Solbe and Cooper 1976 Geckler et al. Alk: 11.868.0-8.9.24 Environmental Conditions pH: 7. P Weinstein 1978 Secondary Studies American eel S.8).4 (10. T: 15-16.6 g FT. S M. DO: >90% Sat pH: 4.2.6 (7.0066 120 9. Alk: -0.17-0.057 pH: 7.9+0.9-8.125 T: 3.2) 96-hr LC50 0.2 (7-11). Alk: 81.2+0. CuCl2 96-hr LC50 0.3.9-9. DO: 9.9. T: 11. Alk: 1. 1973 Wilson 1972 89 .5 (60. T: 9. Alk: 30. CuSO4 96-hr LC50 0. DO: 10.4 96-hr LC50 0.DO: >90% Sat pH: 5.7.29 4-d LC50 0. S Zitko et al. CuSO4 N.6-12) pH: 7. T: 17. 1976 Zebrafish FT pH: 8. 1986 Steelhead trout Steelhead trout juveniles fry 2. T: 12.7-6.1.024-0.9 55 53 41.2-0.010 96-hr LC50 0. P Stone roller Stone loach Striped shiner 60 mm 8.3 23+1 M. P P M.8-4. T: 15-16. P M. T: 12+1.24 128 M.7-12.2. S Buhl and Hamilton 1990 Atlantic salmon Atlantic salmon 8.08 96-hr LC50 0. T: 24.13 (0. T: 23-25.2).57+0.028 96-hr LC50 0.06. P Fogels and Sprague 1977 Zebrafish 0. CuNO3 96-hr LC50 6.068 pH: 8. T: 12. CuSO4 96-hr LC50 0.9 pH: 7. Alk: 200-255.5-8.2+0. T: 5.1. T: 15-16. DO: avg 75% sat pH: 7.5 pH: 7. Alk: 126. P Chapman and Stevens 1978 Seim et al. 1984 Cusimano et al.1 (82. Alk: 34+8.4) Classification M.1 cm 55 mm 55 mm 0. DO: Saturated Hardness 83. P Reference Servizi and Martens 1978 Steelhead FT 96-hr LC50 0.29-0. Alk: 4 14 8-10 M.1.55-7.1-0.025 96-hr LC50 0. DO: >96% sat pH: 7. DO: 6.5 g Alevin Swim-up Parr Smolt Adult Test Type Toxicity Endpoint (mg Cu/L) 96-hr LC50 0. P Geckler et al.131 96-hr LC50 0.029 96-hr LC50 0.3 N.69 mg FT. Alk: 148-161 pH: 8.19 96-hr LC50 0.3-10 pH: 96-hr LC50 0.149 pH: 7.7.15 96-hr LC50 0. Alk: 62.2 M. S Rehwoldt et al. DO: 87% Sat 350-375 M.017 96-hr LC50 0.DO: 11. 1972/71 Arctic grayling fry alevin juvenile S.26+0.984. P Chapman 1978 Steelhead FT pH: 7. DO: 6. DO: >90% Sat 42+12 M.8 cm 2-3 yr old parr FT S >96-hr ILL 0.7.8 pH: 6. Alk: 22+2.7 96-hr LC50 0.9-8.8.003-0.

751 96-hr C50 0. not aerated T: 15 52 20 400 365 209 N.08-8. T: 24.2-11. start 7. T: 20+1 50 100 300 55 53 50 100 300 460-465 N.2 96-hr LC50 10 pH: 8.275 48-hr LC50 0. Alk: 43.6 g 0.6 g S. Alk: 18.5 cm/g S.6. 1972/71 Bluegill 7 (5-11) cm S.02 96-hr LC50 0. S Brown trout yolk-sac fry 21-d LC50 0. DO: >70% Sat N. S N. 1954 Bluegill Bluegill 0. CuCl2 S 96-hr LC50 1. DO: 6. T: 17. S Rehwoldt et al. Alk: 144. synth.27 g S. DO: 6.118 48r LC50 0. DO: 7. Alk: 72.1-7.2 cm FT. DO: aerated Hardness 14 Classification N.9 g 1-2 g S S S. CuSO4 SR (1/d). T: 28. S 20 N. S Reference Grande 1967 Banded killifish 55 53 46 101 190 N.86 48-hr LC50 3 48-hr LC50 7 48-hr LC50 44 Environmental Conditions pH: 6.68 96-hr LC50 1. T: 20.5-5. T: 28.Species Atlantic salmon Lifestage fry 4-6cm <20 cm Test Type SR (1/d).04 96-hr LC50 0. DO: >4 mg/L. CuSO4 pH: 7. T: 20.4).09 3-d hatch LOEL 0. DO: 6. S Peres and Pihan 1991a Catla catla 2. DO: 5-9 pH: 7. T: 10.75 96-hr C50 0. CuSO4 N.8 96-hr LC50 0.2. S Thurnbull et al.25 96-hr LC50 0. CuNO3 Toxicity Endpoint (mg Cu/L) 21-d LC50 0. CuNO3 pH: 7. T: 24.30 pH: 7.5 cm/g S. T: 25. DO: > 3 mg/L pH: 7. DO: aerated pH: 8. S Hildebrand and Cushman 1978 Peres and Pihan 1991b Carp 3.0 N. S Carp S. DO: > 3 mg/L T: 18+2. DO: aerated pH: 8.4 96-hr LC50 0. S Inglis and Davis 1972 Tarzwell and Henderson 1960 Inglis and Davis 1972 Inglis and Davis 1972 Cairns and Scheier 1968 Pickering and Henderson 1966 Sprague 1968 Bluegill Bluegill Bluegill Bluegill 0.5-3. Alk: 48. S Brook trout 5. 1972/71 Carp 3. S Rehwoldt et al. CuSO4 S.8.4. 14 N. medium.2.9-8.04 21-d LC50 0. T: 20. T: 20+1. T: 29-30.8.29 48-hr LC50 0.5 pH: 8.9 pH: 7. dil.3.115 48-hr LC50 0.05 14 NR.6 g 3. DO: > 3 mg/L pH: 8. CuCl2 N.8 mg/L. T: 26 50 M-NR.T: 17.66 mg/L N. S N. CuSO4 96-hr LC50 0.5 48-hr LC50 0.3.9 pH: 7.5-5. T: 24. S NR.84 96-hr LC50 0. DO: 6. S Grande 1967 Carp eggs 3-d hatch NOEL 0.5-8.3-8.5 pH: 7. CuNO3 pH: 8.5 (7. Alk: 48. T: 14-16 pH: 8.4. T: 10 pH: 6.3 pH: 8. S Ahmad and Datta Munshi 1987 90 . Alk: 48.4 pH: 8. CuSO4 SR (1/d) 10-d LC50 0.73+0.81 48-hr C50 0.04 pH: 6.4.

Alk: 90-230 120-336 diss Cu M. Alk: 18 20 360 N.9 g 3.09.7 kg FT 96-hr C50 0. not aerated pH: 7. DO: >90% Sat pH: 8.046 20+1 N.1-8. S 91 . CuSO4 SR pH: 7.5 (7.4) start 8. CuSO4 7-d LC50 5. CuSO4 Toxicity Endpoint (mg Cu/L) 96-hr C50 0. DO: >4 mg/L. Alk: 16. Alk: 18. DO: >4 mg/L. S Reference Straus and Tucker 1993 Channel catfish SR (2/d) M-D. T: 17-22. start 7. DO: 8-8. CuSO4 SR (1/d) pH: 7. Alk: 88 pH: 7. T: 20-24.53 LC50 1.5. Alk: 127.6-0. T: 17+0.4 50 19 (14-26) NR. Alk: 76.019-0.2.29+0.0-8. S Chapman and Stevens 1978 Buhl and Hamilton 1990 Coho salmon alevin juvenile S. DO: >90% Sat pH: 8. S Deshmukh and Marathe 1980 Tarzwell and Henderson 1960 Brungs et al.25-6. T: 15 (13-16).8mg/L. T: 25.9 33+4 M. S Mount 1968 Tarzwell and Henderson 1960 Birge and Black 1979 Goldfish eggs/larvae SR (2/d).3. T: 27. S Pande and Shukla 1992 Khangarot et al.04-7.0 g 2. Alk: 29+1. T: 9.14/1. S Fathead minnow 2-6.2 g eggs 4-d post-hatch 0.032 96-hr C50 0. T: 13.35).7+0. Alk: 118. T: 18-22.62 96-hr C50 0.8.47 LC50 0. Alk: 22+1.9.0-8.5.055 96-hr LC50 0. CuSO4 96-hr C50 0. T: 17+0.3 N.5. S NR.9 cm S 96-hr TL50 0.5 Environmental Conditions pH: 7.2.3 (6.5+1. Alk: 29 (2533). T: 25.023-0. T: 20-24. T: 4-27.7. Alk: 239.5.T: 17+0.87 g 50 g Test Type S.2-7.66/0.56 96-hr LC50 6.7 pH: 7. start 7. S Colisa fasciatus Common carp 1.2 pH: 7.3.1-7.8mg/L.2.017 Cu2+ pH: 7. DO: 8. Alk: 90 211 170 N.8-8.035 mg/L 96-hr LC50 1. Alk:300. Alk: 30. T: 12+1.7-11.4. DO: 6. DO: moderate aeration 197 M-D.4 (8.3 g 3.6 g SR (1/d) SR (1/d). S Fathead minnow 1-2 g S pH: 7.1. not aerated pH: 7. S N.063 41.983 96-hr C50 7. Alk: 95-122. 1983 Cyprinus carpio 78-195 mg 2880-3630 mg 96-hr C50 0. S Birge and Black 1979 Chinook salmon Clarias batraches S. 1976 Fathead minnow pH: 8. T: 21.5 (7. T: 12+1.8 pH: 7.9+0. DO: mod aerated. DO: 9.054 48-hr C50 41.4) start 8.1).9 96-hr C50 0.98 (diss.058-0.T: 17+0.4.3 mg/L pH: 6.2 pH: 7.05 mg/L 200 20 M?.015-0. DO: >90% Sat pH: 8.2.76 pH: 7.5.4 144-188 N. Cu) 96-hr LC50 0. S N.954 96-hr LC50 0.53. S Coho salmon adult 2.8.2-7. S Pickering and Henderson 1966 Fathead Minnow Fathead minnow adult FT 96-hr LC50 0.1-7.4-2.731 96-hr LC50 0. DO: 7. sat Hardness 16 83 161 287 100 (93-105) Classification N. Alk: 160 pH: 7. DO: >90% Sat pH: 7.5. S Hamilton and Buhl 1990 Mukherjee and Bhattacharya 1977 Buckley 1983 Coho salmon 6g SR (1/d) 96-hr C50 0.Species Channel catfish Lifestage 3. Alk: 360 400 NR.118 96-hr LC50 0.021 96-hr LC50 0.

087 96-hr LC50 0.4 144-188 N.08-8.7-74 g 324-463 g 0.764 240 (210-280) N. DO: 8-8. DO: 79-89% sat. S Pande and Shukla 1992 Mukherjee and Bhattacharya 1977 Liepolt and Weber 1958 SR SR 48 hr.sat 253 N. T: 20-24.8.46+0.2 g S 96-hr LC50 0. DO: >4 mg/L.68-0. S Largemouth bass SR (2/d) pH: 7. Alk: 95-122.3-8. T: 27. Alk: 165 (140-190). sat 100 (93-105) M-D. T: 10.5) pH: start 7.3 96-hr LC50 1. CuNO3 7-d ILL 0. DO: >4 mg/L.1. DO: 6.4 cm FT M-NR. S Labeo rohita 40-50 mg 3700-5600 mg eggs 4-d post-hatch 5. Alk: 118.70 460-465 N.97 96-hr LC50 6.24-1. Alk: 18.046 96-hr LC50 0.2-2.8-4. CuSO4 96-hr LC50 0.2+0. DO: 7.5-6.6 g 5+0.3-7.3 g 7.Species Goldfish Lifestage 1-2 g Test Type S Toxicity Endpoint (mg Cu/L) 96-hr LC50 0.94 96-hr LC50 0. S Pumpkinseed 96-hr LC50 2. T: 27.8.9-176 g FT 96-hr LC50 0. Alk: 85+2.81 g SR (1/d) 96-hr LC50 0.56 96-hr LC50 0.5 g 5.1-0. T: 17-22.3 (45-79). T: 13-22.4 96-hr LC50 1.1+0.1 (25.6.21 125+5 M-NR. T: 21. S Guppies 0.5 (27-41) N.6+0.1-7. T: 29-30. S Lebistes reticulatus SR (1/d) pH: 7.8+0. Alk: 18. DO: 5. start 7.8-8. DO: 7.8 mg/L.4).5 mg/L pH: 7.2. 1981 Guppies 0. 310+0. not aerated pH: 7. Alk: 95-122.5 (4.5 (24-27. S Anderson and Spear 1980a 92 .4-7.2-7.047 96-hr LC50 0. 55 53 125+5 N. S Rehwoldt et al.8-7.8-29). DO: mod aerated.186 g S.5).036 Environmental Conditions pH: start 7.275 96-hr LC50 0.67 96-hr LC50 1.5 (7.2. CuSO4 S. CuSO4 96-hr LC50 0.1 pH: 7.5 (7.571 pH: 8.T: 17. not aerated pH: 7. DO: 8.9).6 (5.9 pH: 7. CuNO3 CuSO4 Cu3OCl SR (1/d) pH: 7.295 96-hr LC50 6.52 (7. DO: aerated.5 pH: 7.1-7. Alk: 52. T: 17-22. DO: 74-95% sat. S Reference Pickering and Henderson 1966 Khangarot et al. T: 26.3 mg/L pH: 7.5 (7.4). Alk: 228+1. S Deshmukh and Marathe 1980 Mosquitofish ?.8). S Pickering and Henderson 1966 Ahmad and Datta Munshi 1987 Deshmukh and Marathe 1980 Birge and Black 1979 Labeo rohita 2.66-1.080 96-hr LC50 0.27 g S.1. start 7. DO: 8-8. S Joshi and Rege 1980 Mystus vittatus Ophicephalus punctatus Phoxinus laevis 60 g pH: 7. 1980 Rainbow trout 3.4 144-188 N. S Anderson and Spear 1980a Puntius conchorius S pH: 8. DO: 6.8-8.036 20 N.16 96-hr LC50 0. 1972/71 Pumpkinseeds 1.5.9) 31. DO: 6. Alk: 90 50 170 NR.7 48-hr LC50 70 pH: 7.7 96-hr LC50 2. S Pant et al.2.74 96-hr LC50 1.112 N. Alk: 85+2. T: 25.0 Hardness 20 Classification N.2 g 2. T: 28.1.3-7. T: 20+1.19-0.7 g 43. T: 10+1.48 96-hr LC50 0.8 mg/L. T: 25. S N.

Species Rainbow trout

Lifestage 0.36 g

Test Type SR (1/d) CuSO4 SR

Toxicity Endpoint (mg Cu/L) 48-hr LC50 0.12 48-hr LC50 0.11 72-hr LC50 1.10 7-d LC50 0.044 48-hr LC50 0.27

Environmental Conditions pH: 6.5; T: 10-11; Alk: 100 pH: 7.5; T: 10-11; Alk: 100 T: 16-17; DO: aerated T: 17-18; DO: aerated pH: 7.8; T: 17; Alk: 250; DO: air saturation

Hardness 250

Classification NR, S

Reference Shaw and Brown 1974

Rainbow trout

7.6 cm

320 15-20 320

N, S

Lloyd 1961b

Rainbow trout

12.5 cm


N, S

Herbert and Van Dyke 1964 Hale 1977

Rainbow trout

51-76 mm



LC50 0.253

pH: 6.4-8.3; Alk: 82-132; DO: 4.8-9

field study, N, S 14 20 40 320 NR, S

Rainbow trout

ILL 0.037 ILL 0.050 ILL 0.09 ILL 0.50 yolk-sac fry SR (1/d), CuSO4 SR (1/d), CuSO4 S, CuSO4 21-d LC50 0.04 pH: 6.4; T: 10

Lloyd and Herbert 1962

Rainbow trout


N, S

Grande 1967

Rainbow trout

10 cm

7-d inc. lethal 0.50 ILL 0.07-0.13 96-hr LC50 0.036 96-hr LC50 0.014 96-hr LC50 0.11

pH: 7.6-7.0; T: 10+0.2; DO: aerated, sat

253 20 41.3

N, S

Liepolt and Weber 1958

Rainbow trout

alevin juvenile embryo/alevin 4d post hatch yolk-sac fry

pH: 7.1-8; T: 12+1; Alk: 30.9

N, S

Buhl and Hamilton 1990

Rainbow trout

SR (2/d), CuSO4 SR (1/d), CuSO4 S, CuSO4

pH: 7.2-7.8; T: 12-13; DO: moderate aeration, near sat. pH: 6.4; T: 10

100 (93-105)

M-D, S

Birge and Black 1979

Rainbow trout

21-d LC50 0.04


N, S

Grande 1967

Rasbora deniconiusneilger Steelhead trout Striped bass

3.8 g

96-hr LC50 0.203

pH: 7.5 (7.4-7.8); T: 26.5 (24-27.5); Alk: 165 (140-190); DO: 6.6 (5.8-7.5) T: 12; DO: 10 pH: 8.1;T: 20+2; Alk: 30 pH: 7.9; T: 20+2; Alk: 262 pH: 8; T: 28; DO: 6.9 pH: 7.8; T:17; DO: 6.5 pH: 8.2; T: 21; Alk: 35; DO: 7.8 pH: 8; T: 28; DO: 6.9 pH: 7.8; T:17; DO: 6.5

240 (210-280)

N, S

Khangarot et al. 1981

8.7+1.4cm 63 d old


96-hr LC50 0.020-0.025 96-hr LC50 0.1 96-hr LC50 0.27 96-hr LC50 4.0 96-hr LC50 4.3 96-hr LC50 0.62 96-hr LC50 6.4 96-hr LC50 6.2

30-66 40 285 55 53 64 55 53

M, S N, S

Knittel 1980 Palawski et al. 1985

Striped bass

S, CuNO3

N, S

Rehwoldt et al. 1972/71

Striped bass White perch

2.7 g

S, CuSO4 S, CuNO3

N, S N, S

Wellborn 1969 Rehwoldt et al. 1972/71




Test Type

Toxicity Endpoint (mg Cu/L)

Environmental Conditions




Unsuitable/Unclassified studies Blue gourami adult S 96-hr LC50 0.091 pH: 7.4; T: 26-28; DO: 10 N, U Roales and Perlmutter 1974 Thurnbull et al. 1954 Hedtke et al. 1978 pH: 7.2-7.4; T: 8.7-11.4 20 NR,U Chapman 1973 Hedtke et al. 1978 Hedtke et al. 1978 250 Ministry of Technology 1973 NR, U pH: 7.4; T: 12 pH: 7.7; T: 16 pH: 7.7; T: 25; Alk: 81 pH: 7.8T: 25Alk: 81 20-25 100 130 300 NR, U Wong 1989 Chapman 1973 Haider 1966 Anderson et al. 1978 Anderson et al. 1978

Bluegill Coho salmon Coho salmon Coho salmon Coho salmon Rainbow trout

7 (5-11) cm 56-d adult 130-d 151-d

S, CuSO4

48-hr LC50 49 96-hr LC50 0.06 96-hr LC50 0.046 96-hr LC50 0.166 96-hr LC50 0.212 96-hr LC50 0.85

pH: 6.9-7.5; T: 20; Alk: 33-81; DO: aerated


N, U

Rainbow trout Steelhead trout Tench Zebrafish Zebrafish juvenile

0.3 96-hr LC50 0.02 0.08-0.15 LC50 0.24 LC50 0.67

Legend: Test Type: Toxicity Endpoint: Environmental Conditions: Classification:

S=Static, SR=Static Replacement, FT=Flow-Through; T=expressed as total copper, diss= expressed as dissolved copper, Cu2+= expressed as cupric ion T= Water Temperature oC, Alk=Alkalinity in mg/L CaCO3, DO=Dissolved Oxygen in mg/L unless otherwise stated; Hard=Water Hardness in mg/L CaCO3; M=Measured Concentrations, M-D= Measured Concentration, but significant decrease over test duration, N=Nominal, NR=Not Reported; C=Calculated; RP=Replicated P=Primary, S=Secondary, U=Unsuitable.

Appendix 4.
Species Primary Studies Asellus meridianus Cambarus robustus Campeloma decisum Caridina sp.

Acute copper toxicity data on freshwater invertebrates.
Lifestage Test Type Toxicity Endpoint (mg Cu/L) Environmental Conditions Hardness Classification Reference

4-6 mm intermoult adult 11-27 mm


48-hr LC50 1.2-2.5 24-96-hr LC50 0.83-3.48 96-hr LC50 1.7 mg/L

T:20+3; HMSO med. pH: 7.0-6.1; T: 25+1; Alk: 10-12; DO: 7.5-8.3 pH: 7.7; T: 15; Alk: 42-43; DO: 9.5-9.7

25 10-12 44-45

M, P M, P M, P

Brown 1976 Taylor et al. 1995 Arthur and Leonard 1970



96-hr LC50 0.003-0.004

pH: 5.85-6.15; T: 27+0.5; Alk: 5


M, P Australia M, P

Williams et al. 1991

Ceriodaphnia dubia

<12 hr


adult 5-6d

48-hr LC50 0.019-0.027 48-hr LC50 0.024-0.053 48-hr LC50 0.079-0.099 48-hr LC50 0.079-0.127 48-hr LC50 0.063-0.071 48-hr LC50 0.066

pH: 7.72+0.2; T: 25+1;Alk: 39.7 pH: 8.15+0.06; T: 25+1; Alk: 69.6 pH: 8.31+0.03; T: 25+1;Alk: 140.1 pH: 8.31+0.03; T: 25+1; Alk: 140.1 pH: 8.15+0.06; T: 25+1; Alk: 69.6 pH: 8.2 (8-8.5); T: 25+2; Alk: 97+9.3; DO: >70% pH: 7.7;T: <22-28; Alk: 55; DO: 7.6 pH: 7.5; T: <22-28; Alk: 38; DO: 7.6 pH: 6; T: 25; Alk: 144.3+8.4 pH: 8; T: 25; Alk: 144.3+8.4 pH: 9; T: 25; Alk: 144.3+8.4 pH: 6; T: 25; Alk: 74.2+6.1 pH: 8; T: 25; Alk: 74.2+6.1 pH: 9; T: 25; Alk: 74.2+6.1 pH: 6; T: 25; Alk: 121.9+8.2 pH: 8; T: 25; Alk: 121.9+8.2 pH: 9; T: 25; Alk: 121.9+8.2 pH: 6.8-7.2; T: 20; DO: >80% Sat

45 94 179 179 94.1 100+7.9

Belanger et al. 1989

Ceriodaphnia dubia

<24 hr

S, CuNO3

M, P

Spehar and Fiandt 1986

Ceriodaphnia dubia

<4 hr

S, CuCl2

48-hr LC50 0.019 48-hr LC50 0.020 48-hr LC50 0.056 48-hr LC50 0.084 48-hr LC50 0.093 48-hr LC50 0.014 48-hr LC50 0.028 48-hr LC50 0.031 48-hr LC50 0.052 48-hr LC50 0.076 48-hr LC50 0.091 48-hr LC50 0.7

52 36 182.0+10.1

M, 2RP, P

Carlson et al. 1986

Ceriodaphnia dubia


SR (1/d)

M, P

Belanger and Cherry 1990

Ceriodaphnia dubia


SR (1/d)


M, P

Belanger and Cherry 1990

Ceriodaphnia dubia


SR (1/d)


M, P

Belanger and Cherry 1990

Chironomus riparius Chironomus riparius Chironomus tentans

2nd instar

SR (1/d)


M, P

Taylor et al. 1991

2nd instar


48-hr LC50 1.17

pH: M; T: 20; Alk: 50-60; DO: 80% Sat


M, P

Dobbs et al. 1994

2nd instar

FT, CuCl2

96-hr LC50 0.773

pH: 7.4; T: 19.5; Alk: 60-67


M, P

Nebeker et al. 1984b


T: 15. CuSO4 S 44-45 100-120 M. T: 19.69 pH: 7.9 pH: M. 1993 Dobbs et al.016 (Cu2+) 96-hr LC50 0. DO: >80% Sat pH: 7.02 151+9 44-45 M.Species Chironomus tentans Chironomus tentans Daphnia magna Daphnia magna Lifestage 3rd instar Test Type FT. CuCl2 96-hr LC50 1. DO: 80% Sat pH: 8.5-9.5-8. P West et al. 1993 Dobbs et al. Alk: 30-45 pH: M.18-0.7.7 pH: M.3.7. Alk: 103.2). P M.9-7. CuCl2 Toxicity Endpoint (mg Cu/L) 96-hr LC50 1.1-7.8-7. Alk: 50-60.7. P M.1) M.026 48-hr LC50 0. T: 20.028 72-hr LC50 0. Alk: 50-60. T: 22+1. T: 12+1. 1994 Borgmann and Ralph 1984 West et al. DO: 80% Sat 100-120 180 44-47 100-120 M. P (2RP) Physa integra Physella sp. DO: 8.031 96-hr LC50 >64 14-d LC50 32 48-hr LC50 0. DO: aeration. P M.0 (11.446 Environmental Conditions pH: 7. T: 22. P M.3. DO: 80% Sat pH: 8. CuSO4 48-hr LC50 0. CuO CuNO3 S S 48-hr LC50 0.101 10-d LC50 0.9 pH: 7.1-22. Alk: 9.26). DO: 7.3.223 LC50 0.9. CuCl2 S. Alk: 60-67 84 M.8 45-60 100-120 57. CuSO4 S FT. T: 15. 1984b FT <24 hr SR (1/2d).039 48-hr LC50 0.1 (2. P M. T: 20. 6. 1994 Daly et al. DO: 80% Sat pH: 6. P Dobbs et al. 8mg/L 44-47 44-46 M. DO: aerated pH: 7.7 M. CuSO4 S 10-d LC50 0.109 pH: 7.1-22. CuSO4 pH: 7.0136 14-d LC50 0. 1984b 4th instar FT.3 pH: 7.37 96-hr LC50 0. T: 15.02 96-hr LC50 0. 1985 Daphnia magna Daphnia pulex Daphnia pulex Daphnia pulex <24 hr 24 hr + 10 hr <24 hr <24 hr 48-hr LC50 0.6. Paratya australiensis 30-40 mm adult 17.4. 12. 1991 Arthur and Leonard 1970 7-14d FT. P M. T: 20+1. T: 3-9 (<0.5. DO: 9. P Nehring 1976 SR (1/d) FT.035 48-hr LC50 2.5 Alk: 82 120-130 85 M.5-8.5-9.037 72-hr LC50 0. P Bishop and Perry 1981 Blaylock et al. T: 22. Alk: 50-60. Alk: 45-46. Alk: 30-70 (<10).3. P Reference Nebeker et al. Alk: 45-46. P Taylor et al.49-7.5.4. P M.037 96-hr LC50 0.0-7. P Nebeker et al. P M.5) pH: 6. P Lewis 1983 Jop et al. T: 20. 4-7 mm <10mm t FT. T: 20.003 48-hr LC50 0. P Arthur and Leonard 1970 Dobbs et al.96 (6. DO: 6. Alk: 42-43. DO: 7-12 (<0. 1994 Winner 1985 Ephemerella grandis Gammarus pulex Gammarus pseudolimneaus Hyalella azteca Hydropsyche betteni 3-5 mm adult FT. Alk: 115 143+9.9-7. T: 18.5. T: 20.13 pH: pH: 7.2-7.5). Alk: 40.2. P M.2 (one exp.3). Alk: 50-60. 1993 Warnick and Bell 1969 Isonychia bicolor Keratella cochlearis 6-8 instar S CuCl2 FT.5-8. pH: 7.5-23. 1990a Lumbriculus variegatus 7 mg Orconectes sp. T: 19.4-8. Alk: 60-67 Hardness 84 Classification M. P M.3. T: 20+2. DO: 6. DO: 9. Alk: 42-43.0259 72-hr LC50 0. 1994 96 .6-.034(tot)/0.5 115 230 30-70 (<10) M. CuSO4 pH: M.

41/0. pH: 7. P Carlson et al.3 pH: 7.6.9-7. 1993 Gauss et al. Lifestage Test Type FT. DO: 80% Sat 52 100-120 adult 6-8 instar S. Alk: 30-35. T: 25 pH: 7.25. DO: 6. S N. T: 22. S O'Sullivan et al.2 50 N.1 pH: M. T: 25. DO: >5 50 45 N.9+1.5. Alk: 70.1-22.6+0.74 10-d LC50 0.6. S Rehwoldt et al.SSW3 pH: 6.1.2 48.9-8.0167 96-hr EC50 0. 1973 Biomphalaria glabrata FT.019 24-hr LC50 0.5) pH: 7.052 (tot/Cu2+) 24-hr LC50 0. 6.1. CuNO3 96-hr LC50 0. 1986 S. T: 20. S LC50 0. Alk: 55. 1985 42. S control?.2-7. S Porta and Ronco 1993 neonate neonates S.1-6.1. 1986 Dobbs et al. CuSO4 CuSO4 24-hr LC50 0.6+1. CuSO4 FT. DO: aerated pH: 7. T: 21+1.4-7. DO: 6.0982 40-48 44-47 M.3+1.2 pH: 7.28 (tot/Cu2+) 24-hr LC50 0. Alk: 43-45. DO: 6. Alk: 45-46.018 48-hr LC50 0. T: <22-28. T: 14 (13-17).7.453 M.7 109.9 Environmental Conditions Hardness Classification M. S Snell and Persoone 1989 Ferrando et al. T: 25.4-7.3. T: 25 pH: 8. T: 3-9 (<0.0365 96-hr EC50 0. Alk: 60-70 pH: 7.5. DO: 7. CuCl2 48-hr EC50 0.0+0. 2RP Elnabarawy et al.0) pH: 7.023 pH: 8.3+1.9 96-hr LC50 9. CuSO4 48-hr EC50 0. T: 25 pH: 7.3 (6. CuSO4 N.8: T: 25.1-13. T: 18.1+0. CuCl2 S 48-hr LC50 0.059 immobility 96-hr EC50 0. CuNO3 <4 hr S 96-hr LC50 6. S Khangarot and Ray 1989 Chironomus decorus Chironomus tentans Chironomus tentans 4th instar 2nd instar (12 d) 1st instar (12 hr) S. T: 20. S N. T: 17. T: 23+1. Alk: 25 (20-33).0-7. Alk: 32. Secondary Studies Acroneuria lycorias Amnicola sp.3-7.56/0. CuSO4 48-hr LC50 0.6).037 pH: 7.8.76 pH: 7. CuSO4 S.5). synthetic freshwater M. 1973 Mount and Norberg 1984 <24 hr S. P Reference Nehring 1976 pH: 7.1.3. Alk: 230+10 240+10 N.3).2 (one exp. S Rehwoldt et al.9 DO: pre-aerated pH: 7. Alk: 40-54.7+0. Alk: 50-60.5-8. Alk: 111.4. P M.9 97 .S Warnick and Bell 1969 adults eggs adult S. CuSO4 Toxicity Endpoint (mg Cu/L) 14-d LC50 10.3 24-hr LC50 0.8. DO: 6. Alk: 30-70 30-70 (<10) (<10).4+1. 1992 S.5 (5. 1994 S 96-hr LC50 8.Species Pteronarcys californica Scapholeberis sp. S Kosalwat and Knight 1987 West et al. Alk: 60-70 80-100 80-100 NR. 25 (18-35) N. pH: 8.017 pH: 7. DO: 7-12 (<0.5. S. T: 25. T: 21+1. DO: aeration 8 mg/L 44-40 M-D.2 172.327 pH: 6. 1989 Brachionus calyciflorus Brachionus rubens Brachionus calyciflorus Caddis fly Ceriodaphnia reticulata Ceriodaphnia reticulata Chironomus tentans <2 hr S.8+0.022 (tot/Cu2+) 24-hr LC50 0. T: 17.3.11/0. T: 21+1.5-8. Stenonema sp.

1987 Daphnia magna 6-24 hr SR (3/wk) pH: 7. DO: Sat pH: 7.6 (5. T: 20. DO: aerated pH: 8-8. DO: 6. T: 20.2. DO: 5.4 pH: 8. S N. 1986 Oikari et al.2 Porcella EPA med. S N. T: 20.093 24-hr LC50 0. CuNO3 CuCl2 S S CuSO4 96-hr LC50 4.03 96-hr LC50 0.8).240 (235-260) 415).4-7.4 T: 20. DO: 8.027 48-hr LC50 0. 1992 Khangarot and Ray 1987b Daphnia magna Daphnia magna Daphnia magna Daphnia magna Daphnia magna Daphnia ambigua Daphnia parvula Daphnia magna Daphnia magna Daphnia magna <8 hr 6-24 hr 6-24 hr 12 hr <24 hr 12 hr 12 hr <24 hr <24 hr S.036 72-hr LC50 0.086 Immob 48-hr EC50 0.041 48-hr EC50 0. DO: aerated pH: 7. fed.7. DO: 7.064 72-hr LC50 0.041 N.2-9.4 pH: 8. S N.2-6.2-9. S N. Alk: 0.081-0. S Rehwoldt et al. pH: 8.S N.5. S M. Alk: 21. S N. Chironomus tentans Crayfish Lifestage Test Type SR?. synthetic medium pH: 7.0065 72-hr LC50 0. Alk: 60-67. Alk: 60-70 80-100 N.5) 240 130-160 130-160 240+10 10 250 N. T: 20.4. T: 20+1.3.6 (7.2-6.0677 72-hr LC50 0.Species Chironomus thummi Chironomus sp. T: 10+0.4- (7. T: 20 Hardness 253 50 71 100-125 Classification N. T: 17. Alk: 100-119.5 96-hr LC50 0. S N.7-11. T: pH: 8.7). DO: 4 pH: 7.58 meq/L. Alk: 100-119. CuSO4 S S S S.022 48-hr LC50 0. T: 17.298 96-hr LC50 3 mg/L Environmental Conditions pH: 7. artificial med. CuCl2 intermoult adult 30.FT. S M. CuSO4 S.5. CuSO4 24-hr LC50 0. change pH: 7. S. artificial medium pH: 8. DO: no sign.2 pH: 7. CuCl2 S. T: 20.072 48-hr EC50 0. T: 13 (11. S M. 1973 Miller et al. DO: 8.5) pH: 7. fed.37 N.8. Alk: 400. S Ferrando et al.5-14. S N. S N.4-7.5. DO: 8. T: 20+0. T: 23+1.6 EC50 0. Alk: 230+10 pH: 6.2. DO: 5. S Reference Liepolt and Weber 1958 Rehwoldt et al.2-9. CuCl2 S S. S N. 2RP N. Alk: 100-118. DO: 6. 1992 98 .3-11. S N. 1973 Nebeker et al.6 (5. S Khangarot et al. T: 20.5 pH: 7. Alk: 100-119.007 48-hr EC50 0. T: 28-30 130-160 50 N. 1984b Hubschman 1967 1st instar SR (2/d).093 T: 25 pH: 7. 1977 Borgmann and Charlton 1984 Winner and Farrell 1976 Winner and Farrell 1976 Elnabarawy et al. T: 20.6. S N.0+0. S Baudouin and Scoppa 1974 Damsel fly Daphnia pulex Daphnia magna Daphnia magna Daphnia similis 12-hr 0-24 hr S.8-8.089 mg/L 48-hr LC50 0.5).032 96-hr LC50 0. T: 10+0.34 48-hr LC50 0. T: 13.5. CuSO4 48-hr Threshold 0. S Daphnia magna S. CuSO4 CuSO4 S. CuNO3 Toxicity Endpoint (mg Cu/L) 7-d lethal threshold 0. CuSO4 35 mm 0.5. 1985 Winner and Farrell 1976 Borgmann and Ralph 1983 Soundrapandian and Venkataraman 1990 Anderson 1948 Hickey and Vickers 1992 Dave 1984 Winner et al.2-9.5.62 mm S Cyclops abyssorum 48-hr LC50 2. Alk: 400 (390.1.7-11.7-11.536 48-hr LC50 0.

CuSO4 S 7-d lethal threshold 0. T: 15.91 48-hr LC50 0. T: 10+0.75.27 mm S.6.2-9. DO: near saturation Hardness 45 Classification N. Alk: 230+10 pH: 8. S N.33. DO: 6.2. Alk: 40-42. T: 21.109 96-hr LC50 0. S Wurtz and Bridges 1961 SR?. DO: aerated Elnabarawy et al. CuSO4 CuSO4 7-d lethal threshold 0.25. DO: 5-6 pH: 8-8.5mm S 96-hr LC50 0.32 48-hr LC50 0.073 Environmental Conditions pH: 7.2.58 meq/L. T: 17.5.4 pH: 7.3-1).5 72-hr NOEL 0 72-hr LC100 0.1 154 137-171 M-D. S NR.5.039 48-hr LC50 0.021 N. CuSO4 SR (1/d). DO: aeration 8 mg/L 44-40 pH: 7. T: 10+0. 1973 Judy 1979 Stephenson 1983 Gammarus pulex SR CuSO4 S. DO: aerated 253 N.86 pH: 8. S Rehwoldt et al. S Hickey and Vickers 1992 Warnick and Bell 1969 Baudouin and Scoppa 1974 pH: 7. DO: 10. CuCl2 Toxicity Endpoint (mg Cu/L) 3-wk LC50 0.01 96-hr LC50 0.4 253 N.2. S Liepolt and Weber 1958 Brown 1980 Limnodrillus hoffmeisteri S pH: 7.85.6. DO: no significant change pH: 7. DO: 10. Alk: 21. 1976 Gyraulus circumstriatus Heptagenia lateralis Hydrobia jenkinsi 3-4. 12 mg/L pH: 8. CuCl2 96-hr LC50 0.7. CuNO3 S.43 mm S Gammarus sp. S N.85.5.50 10 N.2.39 48-hr LC50 0. T: 11. T: 23+1.2 pH: 7. T: 18. CuCl2 S S 48-hr EC50 0. S Liepolt and Weber 1958 Goniobasis livescens Goniobasis livescens 96-hr LC50 0.0+0. S Reference Biesinger and Christensen 1972 Daphnia magna <24-hr SR T: 20 S (info test solution) 240+10 130-160 N.108 100 N.6 (dropped 0. S N.6. 1986 Winner and Farrell 1976 Baudouin and Scoppa 1974 Deleatidium sp.005 pH: 8. S N.Species Daphnia magna Lifestage 12 hr Test Type SR (7d).9 50 206 mg/L 249 104 0. change pH: 7. Ephemerella subvaria Eudiaptomus padanus 3-6mm S.102 pH: 7. S N. DO: no sign. DO: aerated pH: 7.5 pH: 7. S Arambasic et al.33. S Wurtz and Bridges 1961 99 . Alk: 0.031 72-hr LC50 0.7-11.06 without food 0. Alk: 115.5. 1983 Cairns et al. 2RP N.044 48-hr LC50 with food 0.58 meq/L.3.5. T: 20. Alk: 0. Alk: 42. CuSO4 S 96-hr LC50 0. T: 7. Alk: 100-119: DO: 8. T: 15.086 48-hr LC50 0. S Paulson et al. T: 15. T: 18. DO: 8-9 dropped to 6-8 mg/L pH: 7.2. DO: aerated.2. T: 10+0. T: 22 100 N. T: 23.5+2.9 pH: 8. S M-D.5. 1995 Daphnia pulex Daphnia pulex Daphnia hyalina <24 hr 12 hr 1. T: 10+0.25-0.4-8. S. Gammarus fasciatus Gammarus pulex S.19 96-hr LC50 0.0098 48-hr LC50 0.8.

0. Alk: 234 pH: 7. S Reference Pardue and Wood 1980 CuSO4 96-hr LC50 0. T: 26.6.15 pH: 7.5 (7.8.3 T: 23-24 T: 22+1 190-220 N.5 (24-27.32.088 pH: 7.5-8. U Anderson 1944 Wong 1989 100 . Alk: 7.6 (dropped 0.14 96-hr LC50 0.51 Environmental Conditions pH: 7.083 mg/L pH: 7. T: 21. T: 20+2.5+2. DO: 7.0.4-7.5) pH: 8-8.5 (7.09 96-hr LC50 0. S N.8). 1981 S.5-8.14 96-hr LC50 0. DO: 7.034 96-hr LC50 0.2&6. T: 15. T: 23. CuSO4 96-hr LC50 0. S Khangarot et al. S Cairns et al. T: 26.5) S 32-hr LC50 0. CuSO4 96-hr LC50 0. T: 20+2. DO: 6. T: 24-25.4-7. 1981 Lymnaea emarginata CuSO4 48-hr LC50 0. 1964 S CuSO4 S. Alk: 24 pH: 7.5 (24-27.7 96-hr LC50 1. T: 10+0. CuSO4 pH: 7. 1974 Physa heterostropha Physa & Stagnicola sp.5-8.89 SR.916 g N. T: 24-25.2 mg/L 261 mg/L 253 N.2.63 48-hr LC50 4. S Pardue and Wood 1980 Bushnell 1974 Hatakeyama 1988 soft water N. T: 20. Alk: 165 240 (210-280) (140-190).3 Hardness 190-220 Classification N. Plumatella emarginata 2-3 d Plumatella casmiana Polypedilum nubifer 1st instar 2-3rd instar 4th instar - S. Alk: 9. CuSO4 96-hr LC50 0.8.4-8.5. CuNO3 SR (1/2d) S S.6 (5. 1976 Nais sp. DO: 7. 1973 Daly et al.1 pH: 7. S Rehwoldt et al. Paratya australiensis Pectinatella magnifica 2-3 d Philodina acuticornis S.034 pH: 7.21 48-hr LC50 0. Alk: 30.069 96-hr LC50 0. CuSO4 96-hr LC50 0.8).5). S Wurtz and Bridges 1961 Howard et al. DO: 6. DO: 6.05 48-hr LC50 0. DO: aerated pH: 7.3 NR. S N. Alk: 54-67 137-171 N.5 96-hr LC50 48-hr LC50 0.9. S N. DO: aerated 34. T: 24-25.4-8. CuSO4 S. T: 20.85. S N.16 T: 25 U no info.4-7. CuSO4 48-hr LC50 0. 1990a Pardue and Wood 1980 Buikema et al. DO: >40% Sat 30 N.5 pH: 7. S N.2&22.3-1). CuSO4 7-d lethal threshold 0. T: 17. S N.3 pH: 7.4-7. T: 20+1.Species Lophopodella carteri Lumbriculus variegatus Lymnaea accuminata Lifestage 2-3 d Test Type S Toxicity Endpoint (mg Cu/L) 96-hr LC50 0.3 pH: 7.038 0.240 (210-280) 190). Alk: 115.85. Alk: 165 (140. S Brkovic-Popovic and Popovic 1977 Tubifex rivulorum Viviparous bengalensis Unsuitable Studies Daphnia magna Daphnia <8 hr old 1.8-7. T: 22 100 131 N.8.50-1.55 g S. DO: 8-9 dropped to 6-8 mg/L pH: 7.2 pH: 6.4-8.1. S Liepolt and Weber 1958 Khangarot et al.6 (5. S Tubifex tubifex SR (24-hr).6.5). S Baily and Liu 1980 0.1 50 17 190-220 25 mg/L 81 mg/L N.8-7.25-0.

Species Daphnia pulex Lamellidens marginalis Moina irrasa


Test Type

Toxicity Endpoint (mg Cu/L) LC50 0.05-0.1

Environmental Conditions T: 20

Hardness 215


Reference Ivekovic 1932

5-6 cm

SR (1/d)


LC50 5.0


Raj and Hameed 1991

<24 hr


48-96-hr 48-96-hr 48-96-hr

LC50 6.03-3.3 LC50 8.09-6.06 LC50 12.61-7.43

pH: 5; T: 20; distilled pH: 6.5; T: 20; distilled pH: 8; T: 20; distilled pH: 7.3; T: 22 pH: 7.3; T: 22 pH: 7.8; T: 22 pH: 7.3; T: 22 pH: 7.4; T: 22 pH: 7.45; T: 30+1; Alk: 18; DO: 6.76 20 20 100 100 10 52

N, U

Zou and Bu 1994

Physa heterostropha

3-6mm 3-6mm 12-15mm


48-hr LC50 0.019 96-hr LC50 0.016 48/96-hr LC50 0.013 48/96-hr LC50 0.069 96-hr LC50 0.035 96-hr LC50 2.4

NR, U NR, U NR, U NR, U N, U N, U

Wurtz 1962

Physa & Stagnicola sp. Viviparus bengalensis 2.8-3.5 g

S, CuSO4 S, CuSO4

Howard et al. 1964 Seth et al. 1990

Legend: Test Type: Toxicity Endpoint: Environmental Conditions: Classification:

S=Static, SR=Static Replacement, FT=Flow-Through; T=expressed as total copper, diss= expressed as dissolved copper, Cu2+= expressed as cupric ion T= Water Temperature oC, Alk=Alkalinity in mg/L CaCO3, DO=Dissolved Oxygen in mg/L unless otherwise stated; Hard=Water Hardness in mg/L CaCO3; M=Measured Concentrations, M-D= Measured Concentration, but significant decrease over test duration, N=Nominal, NR=Not Reported; C=Calculated; RP=Replicated P=Primary, S=Secondary, U=Unsuitable.


Appendix 5. Computations for the acute Alberta copper guideline.


Computational layout for ANCOVA: notations as used in Box 14.10 (Sokal and Rohlf 1981). Ceriodaphnia Chinook salmon 6 4.601996 8.748168 6.023679 0.688565 4.147693 5 0.454304 0.090861 Fathead minnow 25 27.11695 11.6754 10.71988 0.91816 9.842564 24 17.27438 0.719766 Rainbow trout 29 72.34533 50.75116 52.77864 1.03995 54.88713 28 17.4582 0.623507

df SSY SSX SSXY bY?X explained SS df SSY?X MSY?X

16 6.877687 3.894139 3.97945 1.021908 4.06663 15 2.811057 0.187404

Pooled regression slope bwithin = 73.50165/75.06886 = 0.979123 Explained variance SS (within) = (73.50165)2/75.06886 = 71.96716 Unexplained variance Ed2Y?Xwithin = 110.942-7196716 = 38.9748 s2Y?Xwithin = 38.9748/75 = 0.519664 Fs = 71.96716/0.519664 = 138.4879; highly significant s2Y?X = 37.99795/72 = 0.527749 SSamong b's = 0.976849 MSamong b's = 0.976849/3 = 0.325616 Fs = 0.325616/0.527749 = 0.616991; not significant

EEd2Y?X = 37.99795



Computations Species Mean Acute Values (SMAV) and Genus Mean Acute Values (GMAV). LC50 values are in mg/L and water hardness in mg/L CaCO3.
LC50 hardness set Z=100 adj LC50 Y 110 0.020008 1.02021 25 11 44 1.905474 2.691545 1.334469 6.722594 14.75445 3.797979 SMAV 1.02021 6.722594 14.75445 3.797979 GMAV 1.02021 6.722594 14.75445 3.797979

2-lined salamander asellus cambarus campeloma

caridina ceriodaphnia ceriodaphnia ceriodaphnia ceriodaphnia ceriodaphnia ceriodaphnia







Dobbs et al. 1994 Brown 1976 Taylor et al. 1995 Arthur and Leonard 1970 Williams et al. 1991 Belanger et al. 1989 Belanger et al. 1989 Belanger et al. 1989 Belanger et al. 1989 Belanger et al. 1989 Belanger and Cherry 1990 Belanger and Cherry 1990 Belanger and Cherry 1990 Belanger and Cherry 1990 Belanger and Cherry 1990 Belanger and Cherry 1990 Belanger and Cherry 1990

1.12 1.73 1.699529 1.7

0.003 0.021354 0.035665 0.088436 0.100165 0.06688 0.056

27 45 94 179 179 94.1 182

-4.52714 -3.06467 -3.273 -2.99553 -2.871 -2.64531 -3.46874

0.010812 0.046669 0.037893 0.05001 0.056642 0.070984 0.031156




























871 0. 1986 Carlson et al. 1984a Bishop and Perry 1981 Blaylock et al.406401 0.70034 -3.11321 -0.19 0. daphnia magna daphnia magna daphnia magna Daphnia pulex Daphnia pulex Daphnia pulex Daphnia pulex Daphnia pulex Ephemerella gr.04466 0.016585 0.71239 -5.024715 0. 1993 Dobbs et al.044682 0.044526 0.003 0. 1985 Lewis1983 Jop et al.024715 0.705923 1.223 45 45 110 -2.026 0. 1994 Nebeker et al.066 0.02 0.203131 0.16887 -3.773 0.916895 0.06708 SMAV GMAV 0.02 100 52 36 151 110 84 125 85 143 52 110 57.76018 0.06775 139.024277 0.091 113.036043 0.018318 0.024419 0.0136 0.9117 -0. 1993 Warnick and Bell 1969 Dobbs et al. 1986 Taylor et al.88109 -3.06775 139.037 0.005691 0.152423 0.076 hardness set Z=100 adj LC50 Y 113.019 0.04466 ceriodaphnia ceriodaphnia ceriodaphnia ceriodaphnia chironomus rip.90041 -3.10818 0.028 0. 1994 0.406401 0.035538 0.203131 104 .054383 0.006017 0.065755 0.406401 0.5 115 230 46 151 44 -2.871 0.080319 0. chironomus ten.99987 -5.32304 -2. 1994 Winner 1985 Winner 1985 Winner 1985 Nehring 1976 Taylor et al.0259 0. chironomus rip.39016 -3.70187 0. 0.044682 0.94072 -1.804523 Hyallella azteca Hydropsyche b.13 0. Isonychia b.5939 0. 0.52175 0.6 -2.033703 0.066 0.02 0.871 0.063683 -0.69193 4.11168 -3.467582 0.7 1.033231 0.LC50 ceriodaphnia Belanger and Cherry 1990 Belanger and Cherry 1990 Spehar and Fiandt 1986 Carlson et al.17 0. Gammarus pulex G.08676 -4.06775 139.7181 -3.031 64 0. 1995 Dobbs et al.13051 -1.037 0.203131 0. pseudolimn.6 -2.916895 0.016075 0. 1991 Arthur and Leonard 1970 West et al.

404032 3.102523 cutthroat trout 0.181728 Blacknose dace bluegill bluegill bluegill bluegill bluegill 0.37711 -0. 1986 Dobbs et al. 1979 G e c kler et al.367 205 -1.192737 0.027905 0.035 2.162332 1. 1994 Nehring 1976 Carlson et al. 1990a Arthur and Leonard 1970 Dobbs et al.795204 2.85009 0. 1976 Blaylock et al.1 4.034146 0.057839 0.57057 0. 1994 Daly et al.76957 -1.877147 1.3 1 1.44035 0.453 0. 1993 Dobbs et al.099288 25.17139 0.74 200 85 35 45 110 46 -1.192737 0.23966 0.018 0.08713 0.81811 0.162332 0.025 110 46 52 110 14 -2.86815 0.70525 0.056804 SMAV 0.46072 -2.109 11.192737 0.8 0.158837 0.205873 0. 1994 Trama 1954 0.459212 0.64643 -2.76381 0.524231 2.158837 0.162332 2.23966 0.23966 0.582826 sunfish 1.145282 0.0157 20 26.30973 3.08713 Physella Pteronarcys Scapholeberis Stenonema Atlantic salmon 0.076492 2.048 0.2938 1.034146 0.4 -1. 0. 1985 T h o mp s o n et al.51695 0.412638 0. Orconectes Paratya Physa integra 0.365295 0.412638 Salmo sp.LC50 Keratella c.076492 2.37 0.32 1.42149 1.056804 Lumbriculus v.158837 0.034146 0. 1979 Chakoumak is et al.099288 25.039 45 110 17 44 -2.032 14 -1.228417 -3.08713 0. 1980 Benoit 1975 Dobbs et al.056804 GMAV 0.076492 2. Borgma nn and Ralph 1984 West et al.099288 25.034 0.23207 0. 1994 Carson and Carson 1972 Sprague and Ramsay 1965 Sprague 1964a Chakoumak is et al.916877 0.101 hardness set Z=100 adj LC50 Y 180 -2.219379 Atlantic salmon Atlantic salmon cutthroat trout 0.88518 -1.412638 0.3 0.511977 105 .

1986 Nelson et al. 1986 Nelson et al.00337 0. 1991 Nelson et al. 1986 Pickering et al.9531 -2.43837 -0.075 0.47 0.645086 0.079 0.44557 -1.218548 0.645086 0.157 0.343121 0.85516 -1.218548 0.54 0.048081 0.085 0. 1976 Dobbs et al.52075 -2.1 0. 1973 Geck l e r et al. 1986 Nelson et al.75647 -3. 1994 Nelson et al.306326 e a d e a d e a d e a d e a d e a d e a d e a d e a d 0. 1977 Pickering et al. 1976 Williams et al.048 0.99799 -2.049887 0.15826 0.284 0.44 0.44353 0.091431 0.29486 -0.179 0.182 0.13384 -1.2 47.996632 0. 1976 Williams et al.469 0.1 45 45 -1.31 0.39203 -1.306326 0.236092 0.39217 -1.645086 0.258696 0. 1986 1.578343 0.12459 minnow 0.54759 -1.84986 -1.132944 106 .578343 0.06 0.236114 0.18311 -4.022 200 200 110 45 255 243 45. 1977 Mount and Stephan 1969 Geckler et al.156427 0. 1986 Nelson et al.008 0.3521 -1.44344 -1. rainbowfish chiselmouth creek chub eel-t catfish F a t h minnow F a t h minnow F a t h minnow F a t h minnow F a t h minnow F a t h minnow F a t h minnow F a t h minnow F a t h minnow F a t h minnow F a t h minnow F a t h minnow F a t h minnow F a t h minnow e a d e a d e a d e a d e a d 0.03488 0.273936 0. 1986 Nelson et al. 1976 Geckler et al.LC50 pumpkinseeds Spear and Anderson 1975 McKim and Benoit 1971 Brungs et al.157259 0.49 0.223207 0.016021 0.157259 0.075 45 202 200 27 24 200 27 49.143 0. 1991 Andros and Garton 1980 Ge c k l er et al.578343 0.235611 0.172653 0.119 0.130844 0.2 202 202 31 -1.996632 GMAV Brook trout brown bullhead brown bullhead Ch.49966 -1.15826 0.06967 -3.306326 0.218548 0.03375 -1.24 hardness set Z=100 adj LC50 SMAV Y 125 -0.019195 0.157259 0.248571 0. 1986 Nelson et al.

27 200 362 -1.21224 0.72354 -1.055 0.79714 -1.75749 -1.5691 0.3 52 -0.360379 goldfish 0.360379 0.165772 0.0206 0.1564 0.146095 0. 1976 Fogels and Sprague 1977 Tsai and McKee 1980 Chynoweth et al.82185 -1.55004 -3.095 0.046858 0.082 0. 1986 Nelson et al.85534 -1.161726 0. 1976 Chynoweth et al.141859 Bluntnose minnow Flagfish 0.214952 0.096 0.112 0.156045 0.023 0. 1996 Jop et al.5637 0.144242 0.07452 -2. 1986 Spehar and Fiandt 1986 Nelson et al.112601 107 .146095 guppies 0.178433 0.88441 0.139 124 -2.14835 0.032 0.85761 0.26015 -1.34 1.70276 -2. 1986 Nelson et al. 1986 Nelson et al.23 hardness set Z=100 adj LC50 Y 44 -1. 1976 Anderson and Weber 1975 Spear and Anderson 1975 0. 1986 Erickson et al. 1986 Nelson et al.53734 -2.104335 0.34146 0.048987 0.18 0.138 0.360379 0.116676 SMAV GMAV 0. 1993 Horning a n d Neiheisel 1979 Geckler et al.2 45.022 0. 1986 Nelson et al. 1986 Nelson et al.074 0.113939 0.172478 0.2 47 52 43.5691 guppies guppies guppies 0. 1986 Carlson et al.17209 -3.9 44 46.223 67 88 144 -1.151919 44 46.051 0.01619 -1.93626 -1.06702 0.068 0.2 45 45 52 200 -1.06064 -2.LC50 F a t h e a d minnow F a t h e a d minnow F a t h e a d minnow F a t h e a d minnow F a t h e a d minnow F a t h e a d minnow F a t h e a d minnow F a t h e a d minnow F a t h e a d minnow F a t h e a d minnow F a t h e a d minnow F a t h e a d minnow Bluntnose minnow Nelson et al.066 0.1839 0.5691 0.

025 46 -2.33091 0.85 0.064789 0.104289 0.02 0.019 0.893642 rainbow trout 0.32 0.1 -2.080887 0.3 10.080887 darter 0.097892 0.018 0.277495 GMAV 0. darter rainbow darter pennyfish chinook salmon Andros and Garton 1980 Geckler et al.52432 -2.3 44 -1.11245 0.77913 0.81811 -1.162332 0.070451 0. 1976 Williams et al.065911 0.175917 0. 1991 Finlayson and Verrue 1982 Chapman a n d McCrady 1977 Chapman a n d McCrady 1977 Chapman a n d McCrady 1977 Chapman a n d McCrady 1977 Chapman 1978 Hazel and Meith 1970 Lorz and McPherson 1976 Servizi and Martens 1978 Hickie et al.087 83.5147 0. 1993 Hickie et al.73774 -0. 1976 G e c kler et al.067 23 44 95 -2.080113 0.431195 0.60754 0.65284 0.032 hardness set Z=100 adj LC50 Y 24 -2.264569 0.431195 0.4 10.070451 pink salmon 0.LC50 n o r t h e r n squawfish orangethr.147496 SMAV 0.125 359 -3.053474 chinook salmon 0.01 13 -2.019 0.79181 -1.73662 -2.92856 0.080887 200 200 27 21 -0.26059 0.91395 0.09 182 -2.277495 0.050073 chinook salmon 0. 1993 Giles and Klaverkamp 1982 Spear and Anderson 1975 0.21 125 -1.073715 chinook salmon chinook salmon 0.99428 0.035761 chinook salmon king salmon coho salmon 0.077 0.28195 -1.104289 rainbow trout rainbow trout rainbow trout 0.162332 0.277495 Oncorhynchus 0.166658 0.8412 -1.168784 108 .029 0.

825 366 -1.393 365 370 -2.231599 0.06243 0.14917 0.87922 0.3381 0. 1974 Calamari a n d Marchetti 1973 Miller and Mackay 1980 Spear and Anderson 1975 Spear and Anderson 1975 Dixon 1980 Howarth and Sprague 1978 Howarth and Sprague 1978 Howarth and Sprague 1978 Howarth and Sprague 1978 Howarth and Sprague 1978 Howarth and Sprague 1978 0.82792 0.2 125 -1.19 125 -1.097879 rainbow trout 0.028944 rainbow trout rainbow trout 0.119123 109 .154 369 -3.119123 rainbow trout 0.44189 -1.323 0.5424 0.119123 rainbow trout 0.042888 rainbow trout 0.167 364 -3.047133 0.LC50 rainbow trout Brown and Dalton 1970 Fogels and Sprague 1977 Brown et al.58 0.21496 0.109157 rainbow trout 0.15271 rainbow trout rainbow trout 0.46275 0.160747 rainbow trout 0.19221 0.048 49 -2.32402 0.3978 -2.30355 rainbow trout 0.05477 0.102 362 -3.75 hardness set Z=100 adj LC50 Y 240 -1.344 361 -2.236481 0.090918 0.096511 rainbow trout 0.349 101 -1.14487 0.89 250 300 -1.345616 0.318264 SMAV GMAV rainbow trout 0.

017 0.63555 -3. 1976 Solbe and Cooper 1976 G e c kler et al.621428 0.068253 0.7 1.85896 0.0042 0.151849 rainbow trout 0.059 31 -1.87877 0.47574 0.91655 -1.29 0.6357 0.LC50 rainbow trout Howarth and Sprague 1978 Howarth and Sprague 1978 Howarth and Sprague 1978 Howarth and Sprague 1987 Howarth and Sprague 1978 Howarth and Sprague 1978 Howarth and Sprague 1978 Marr et al.191 98 -1.2 9.155835 stone roller stone loach striped shiner 0.4651 0.83996 0.028956 0.54198 -3.018 0.2 9.88487 0. 1995 Chapman 1978 Cusimano et al.66003 -2.28653 0.621428 110 .119123 rainbow trout steelhead steelhead steelhead steelhead Sockeye salmon 0.32772 0.0028 0. 1986 Cusimano et al.621428 0. 1976 0.1 -2.5 -1.049 31.152778 0.07168 0.13 25 23 9.68349 0.0066 0.043434 0.03 30 -2.069946 0.085 rainbow trout 0.147114 0.059 hardness set Z=100 adj LC50 Y 101 -2.155835 0.147114 0.2 83.68453 -1.185725 rainbow trout 0. 1986 Servizi and Martens 1978 G e ckler e t al.24991 -0.28653 0.058428 SMAV GMAV rainbow trout 0.085 100 -2.194816 rainbow trout 0.047 30 -1.13652 -2.097518 rainbow trout 0. 1986 Cusimano et al.225 200 249 200 -1.28653 0.147114 0.

188469 0.66882 0.16343 0.042281 SMAV GMAV 0.LC50 zebrafish Fogels and Sprague 1977 Weinstein 1978 0.24 128 -1.089267 zebrafish 111 .089267 0.149 hardness set Z=100 adj LC50 Y 362 -3.

5691 0.06775 0.147114 0.645086 ln GMAV -3.304997 0.099288 0.093023 0.C Computation Final Acute Value and intercept of the Alberta acute guideline.192737 0.215666 0.48302 P 0.152499 0.046512 0.146095 0.024277 0.10868 -13.089267 0.264569 0.034146 0.37711 -3.033231 0.58907 11.4428 0.203131 0.04466 0.157259 0.076492 0.799967 -4.264135 0.218548 0. Rank 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 GMAV 0.43975 3.663873 46.406401 0.132944 0.15826 0.056804 0.069767 0.145282 0.412638 0.8252 11.360379 0.023256 0.080887 0.162332 0.232558 sqrtP 0.6083 lnGMAV^2 13.2925 -3.71823 -3.40427 -3.097892 0.621428 0.015988 -8.28653 0.40487 9.306326 0.031975 0.64497 112 .08713 0.277495 0.937297 s^2 s L A VAF CMC 14.578343 0.

Rank 34 35 36 37 38 39 40 41 42 GMAV 0.804523 1.23966 139.511977 2.722594 14.797979 6.158837 3.75445 25.871 ln GMAV lnGMAV^2 P sqrtP 113 .02021 1.

8 M. P Sauter et al. Alk: 172.077 pH: 7-8. Lifestage Test Type Toxicity Endpoint (mg Cu/L) Environmental Conditions Hardness Classification Reference 12 cm.6. 30 g larvae FT 22mo survival.4 36+1.2 45.2 pH: 7-8. 0-1 d FT pH: 6.027. P Benoit 1975 Bluntnose minnow FT.0174.1. T: 10+1. T: 11 (4. P McKim et al.1.9-8).008 hatch LOEL 0. DO: 8.3 M. NOEL 0.4+0.88-8. DO: 10+0.0325 60 d mortality. DO: 7+1. P McKim and Benoit 1971 Channel catfish eggs. 2-3 d FT pH: 7.017 8 mosurvival.5+7.9 186. Alk: 41.007 mortality LOEL 0. hatchability eggs NOEL 0.31.021. DO: >5.7+0.8+3. LOEL 0. Alk: 27. NOEL 0.049 mortality LOEL 0.4+1.5-7.3+38.1+1. DO: aerated 45.072.3+2.2 45+0. 2nd gen survival NOEL 0. Alk: 177.6 (38. spawning. P Sauter et al.growth.growth. LOEL 0. Alk: 150-286.spawn: NOEL 0.8.027 22 mo survival alevins/juv NOEL 0.1 M. LOEL 0. P Sauter et al. Alk: 43+1.162 90 d survival: NOEL 0.9+34.013. P Horning and Neiheisel 1979 Brook trout eggs. NOEL 0.013.9 M.2 187+22 M.012. 1976 Channel catfish eggs.018 60 d mortality. 1976 Brook trout 15 cm. T: 5.013 60-d standing crop LOEL 0.6+30. P Sauter et al.9. T: 10+1. Alk: 34.6. 0-1 d FT pH: 6.4.074. DO: 7+1.9 mg/L 172-230 M.077.005.049. growth NOEL 0.010. LOEL 0. Alk: 43+1. Species Primary Studies Bluegill sunfish Chronic copper toxicity data on freshwater fish.022 60-d growth NOEL 0. LOEL 0. T: 16-27.4-7. T: 22+1.040 growth NOEL 0.019 pH: 7.005 hatch LOEL 0.7 37. CuSO4 60-d growth. 1976 Brook trout FT. Alk: 42.7 M. LOEL 0.7-7. 27 g FT pH: 7. 1978 Brook trout eggs.1. LOEL 0.1. NOEL 0.1-21). DO: 11.044 NOEL 0. growth NOEL 0. LOEL 0.09.5 (6.119 egg prod LOEL 0. 1976 114 . 2-3 d FT pH: 7.8. T: 23-28. T: 13-28. CuSO4 pH: 7.003c. DO: 11+1. T: 22+1.6+0.Appendix 6.018 60-d growth NOEL 0.3-7.4+1.5-44).4 (40-48) M. LOEL 0.8. DO: 7.6-7.

Alk: 30-31. DO: 7.104 mg/L hatch LOEL 0.2. Alk: 42. growth. LOEL 0. Alk: 96-99. Alk: 42.08.3-7.0106.5-8.984. DO: 11.010 hatch LOEL 0.037.9+0.6 (7.6+0.5).033. P Pickering et al.8 M.025. LOEL 0.4+1.4+0. NOEL 0.8 M. DO: >96% sat 249 M.4+0.033 32 d growth MATC 0.9. T: 5.9 (7..1 (82.2 83. T: 12.0184 1-yr Reprod NOEL 0. 1976 Lake trout FT.8-7.5 (60.5. 6 wk old FT pH: 6.3-7.4+1. NOEL 0. Alk: 126. DO: 11.7 (7.4) 45.025 30-d standing crop LOEL 0. T: 15.2 45. NOEL 0. 1978 Pink salmon eggs FT.9 (7.9. T: 19-25.024. NOEL 0.2 45. P McKim et al.078 NOEL 0.015.042 spawning LOEL 0.061. 1978 Rainbow trout FT. 7 d Test Type SR (1/d).Species Fathead minnow Lifestage 1-4. T: 5.038 11 mo.0062 11 mo.024. T: 25+3. Alk: 62. P McKim et al.2-7.55-7. NOEL 0. Alk: 42.022 30-d standing crop LOEL 0.8). DO: 11. CuSO4 pH: 7. P Spehar and Fiandt 1986 Mount and Stephan 1969 Fathead minnow Start 1020mm.26+0.9. Alk: 42.1 (82.2). NOEL 0.0106.72 204 M.4+1.8). Alk: 62. P Servizi and Martens 1978 McKim et al.6 (7. DO: >70% 45.032.05 survival NOEL 0. T: 10.55-7. T: 16-25.8 M. T: 20-24. LOEL 0.9-7.2.5-8. 1978 Northern pike FT. CuSO4 pH: 7.1. DO: 6. 1984 Stone Loach 8.8-68. P Servizi and Martens 1978 Steelhead trout eggs FT pH: 7.4) M. EC50 0. CuNO3 pH: 7.9.5- P Fathead minnow 4-wk old FT pH: 7. LOEL 0.hatch NOEL 31 M. LOEL 0.055. mort.3-10 120 M.5 cm (start) FT pH: 7. LOEL 0. growth . P Sockeye salmon eggs FT. CuSO4 M.2 1 yr egg prod. CuSO4 pH: 7.7+1. DO: Sat pH: 7.4 198 (182216) M. DO: avg 7. CuSO4 Toxicity Endpoint (mg Cu/L) 7-d growth NOEL 0.5 (60.8 M. Alk: 161 (150-170).9. CuSO4 pH: 7.037 60-d standing crop LOEL 0.egg prod. T: avg 23-24.1 cm FT pH: 8.4-0. DO: 9.1.2).egg prod NOEL 0.3-7. DO: Sat 83. LOEL 0. P Solbe and Cooper 1976 115 .9).4+1.5-8.3+0. P Mount 1968 Fathead minnow 30 d FT.8+0. T: 11.2).4+1.74 202 M.mort.8+0. T: 5. NOEL 0.12.5+0.7-12. P Geckler et al.046 63-d LC50 0. P Seim et al.2-7. LOEL 0.25 Environmental Conditions pH: 8.2-0.3.4-7. DO: 7.4+0.037 78-d growth EC50 0.984. Alk: 130 Hardness 218 Classification M.5.8-68.4+1. P Reference Pickering and Lazorchak 1995 Fathead minnow FT pH: 7.042.0184 spawning.095 spawning. 1977 Fathead minnow 1-1.

8-7. CuSO4 pH: 6.9.4+1.021.5. S Stevens 1977 Fathead minnow 3.02 35d hatch LOEL 0.02 6 & 24 mo.7 35+1.8 cm FT.8).04 survival LOEL Hardness 45.3 (7. T: 27. DO: 9.8 M. T: 10 14 N. CuSO4 35 d hatch LOEL 0.4+0.5 20.02 pH: 7.4. S Grande 1967 Rainbow trout eggs 100 NR. U Calamari and Marchetti 1970 Sauter et al. P Reference McKim et al. T: 14.013 Environmental Conditions pH: 7.3.0181. 1978 Secondary Studies Atlantic salmon 38 d eggs 0-27 d eggs SR (1/2d). FT=Flow-Through. hatch LOEL 0. 0 d SR (1/2d). LOEL 0. Natural stream water FT.8 (1953).69 g FT. CuCl2 pH: 7. CuSO4 10-d egg prod/viability NOEL 0. CuSO4 MS Brungs et al. U Legend: Test Type: S=Static. DO: 5-13 31. Alk: 81.1-7.9 (2079.08 survival NOEL 0.012 pH: 6.01. LOEL 0.7. CuSO4 Toxicity Endpoint (mg Cu/L) 30-d standing crop LOEL 0. 116 . DO: near sat 44 M.02 30-d survival LOEC 0. DO: 9.29-0. T: 0-30.S Weinstein 1978 Unsuitable studies Common carp eggs CuSO4 hatch NOEL 0.5). 2 d FT incubation 9-12 d.047 pH: 6. 1976 Zebrafish 0. S Grande 1967 Coho salmon 45-50mm FT.Species White sucker Lifestage Test Type FT.9+0. egg prod. T: 13-14.04 growth LOEL 0.8-7. T: 10 14 N. NOEL 0.5-8.12 T: 25+1 U Kaur and Virk 1980 Goldfish T: 15. DO: 11.1-13. S Goettl et al.3-7.02.6 (8.30-d LC50 0. LOEL 0. SR=Static Replacement. NOEL 0.2.4+1.18 pH: 6.S Hazel and Meith 1970 Rainbow trout eggs. 1976 King salmon 27 d hatch NOEL 0. Alk: 42.8) pH: Classification M. LOEL 0. Alk: 24. Alk: 56-248. NOEL 0. NOEL 0.5 220 ?. Alk: 34+1.1. T: 12. hatch NOEL 0. T: 15+1. DO: 87% Sat 128 N/M erratic.9 (12. Alk: 21. LOEL 0.0139 9 mo.9+0.034.9. 1976 Walleye eggs. NOEC 0.012 survival LOEL 0.5) 88-352 M.

DO=Dissolved Oxygen in mg/L unless otherwise stated. M=Measured Concentrations. N=Nominal. Cu2+= expressed as cupric ion T= Water Temperature oC. Alk=Alkalinity in mg/L CaCO3. diss= expressed as dissolved copper. 117 . but significant decrease over test duration. M-D= Measured Concentration. U=Unsuitable. Hard=Water Hardness in mg/L CaCO3. RP=Replicated P=Primary. C=Calculated.Toxicity Endpoint: Environmental Conditions: Classification: T=expressed as total copper. NR=Not Reported. S=Secondary.

LOEL 0. Alk: 45. LOEL 0.7 77. 1989 Ceriodaphnia dubia 2-8 hr SR 7-d reproduction NOEL 0.Appendix 7.5 mm <4hr SR SR. LOEL 0. Alk: 19 94.037 Alk: 82 85 M.0775 development/emergence NOEL 0. 1986 Ceriodaphnia dubia <24 hr SR. Alk: 69. P Blaylock et al.0139 30-d LC50 0. LOEL 0. T: 22-28. Alk: 26+1 26+1 M. P Belanger et al.0192 30-d LC60 0. CuCl2 Nebeker et al. NOEC 0. LOEL 0.045 HMSO sol.069 surv/repr NOEL 0.0084. adult emergence NOEL 0. T: 20 pH: 7. CuCl2 14-d survival EC50 0.01 NOEL 0. T: 15.31-8. T: 20+0. CuSO4 30-d LC50 0. P Nebeker et al. CuCl2 pH: 7.019 20 d LC50 0. Alk: 38. LOEL T: 25+1. Lifestage Test Type Toxicity Endpoint (mg Cu/L) Environmental Conditions Hardness Classificatio n Reference Primary Studies Asellus meridianus Ceriodaphnia dubia 1-1.8 70. DO: M 25 36 M.6.9 pH: 7. DO: >70% sat 100+7. 14-21 mm ad.3-71.3 pH: 8.013 growth EC20 0.2 (8.4.6-60. LOEL 0.006.1+3.15+0.9 pH: 8.0177 30-d growth NOEL 0. LOEL 0. P Van Leeuwen et al.2-7. LOEL 0.084 8 mo.6+6.0-8.01 21-d LC50 0.3. P ad.1 7 d survival/reprod NOEL 0.31+0. Alk: 59.0134 30-d growth LOEL 0. T: 23. P M. T: 15+2. Alk: 140. T: 23. 1985 Daphnia magna SR.9 179+9. 1984b Clistoronia magnifica Copepods (Acanthocyclops & Diacyclops) Corbicula fluminea 5th instar larvae FT.03.44. T: 20.9-24.11 carapace gr NOEL 0.0084 pH: 8.5.9 M. CuNO3 pH: 8.7. Species Chronic copper toxicity data on freshwater invertebrates. 13-17 mm FT.9.038 reprod LOEC 0.1+3. 1984a Borgmann and Ralph 1984 CuCl2 pH: 8. 1988 118 .29.3-46. T: 25+1. Alk: 97+9.9-24. 1990 juv 7. T: 25+2. Alk: 103 180 M.4. CuCl2 pH: 8.5 225 M. P Brown 1976 Carlson et al.032 7-d reprod MATC 0.18-8.013.3 36 M. CuCl2 12-20 d growth red. P pH: 8.36. P Chironomus tentans 4th instar FT.037.042 M. P Spehar and Fiandt 1986 Belanger et al.5).0083.005.3-78 M.3mm Daphnia magna <24 hr SR.

LOEL 0. CuSO4 N. Alk: 74 pH: 8.4 and 98. CuSO4 pH: 8.6.016 10-wk survival LOEL 0.06.005 6 wk survival NOEL 0. T: 20. fed N. T: 20 98 182 114 100-125 3RP. CuSO4 13-17 d growth 4th repr. LOEL 0. LOEC 0.1 LOEL 0. P Borgmann et al.4 13-14 d hatch NOEL 0.041 NOEL 0.S Hubschman 1967 Daphnia magna 12+12 hr SR.CuCl2 Hyalella azteca 0-1 wk SR (1/wk) pH: 7. S Arthur and Leonard 1970 Belanger and Cherry 1990 SR (1/d) pH: 6. T: 25. LOEL 0.018 intr. 1993 Hatakeyama 1988 Polypedilum nubifer eggs FT.015. 1993 Campeloma decisum Ceriodaphnia dubia neonate 1622hr FT M-D.006 5-hr ingestion NOEL 0.0.06 mg/L was 28. LOEL 0. P Reference Daphnia pulex <24 hr SR 42 d NOEC 0. few conc. DO: 8. CuSO4 pH: 7.9-7.06.02 Winner 1985 pH: 8. T: 20.004. Alk: 115 pH: 8. S Crayfish eggs newly hatched newly hatched FT. LOEL 0.125 30-d growth retardation at 0. S Janssen et al. T: 20. T: 25.2-9.08 pH: 6. P SecondaryStudies Bosmina longirostris neonate SR (1/d).4 130-160 N.9-8. Alk: 122 pH: 7.7-11.01.7. growth rate LOEL 0.8-8. T: 25. LOEL 0. T: 15.010 48-hr filtration rate EC50 0.2 LOEL 0.0145 7-d reprod.6.006 NOEC 0. Alk: 90 130 M. 1994 Dreissena polymorpha 1. LOEC 0. Alk: 100-119. LOEL 0.008.9-8. M. instar LOEL 0.025.0025.Species Lifestage Test Type Toxicity Endpoint (mg Cu/L) Environmental Conditions Hardness Classificatio n M. growth NOEL 0. DO: aerated.005.6 % pop.9. T: 25. 91. T: 24+1 68 M.6-2 cm SR (1/d).012.1.017 35-d emergence/survival NOEL 0. LOEL 0.S Winner and Farrell 1976 119 .5.0.125 17-d survival NOEL 0. T: 25.06. NOEL 0.02 5-hr growth NOEL 0.8. T: 20 N.1. Alk: 115 pH: 7.5 115 150 M. EPA (1985) water.010 2-hr swimming LOEL 0. Alk: 144 pH: 9. S Koivisto and Ketola 1995 Brachionus calyciflorus 0-2 hr S pH: 7.03. P Kraak et al. SAT 57.

T: 20.08.4 130-160 N.4 130-160 N.0004. S Hatakeyama and Yasuno 1981 Physa integra FT M-D. CuSO4 - N.4 N.7.0046. LOEL 0. DO: 8.3-11.08-0. DO: 8.06-0. CuSO4 pH: 8. LOEL 0. growth NOEL 0.04. CuSO4 pH: 7. growth NOEL 0.06 pop.5-21.02-c. LOEL 0.06 9 wk 2nd generation growth NOEL 0.04-c.035 mg/L NOEL 0. Alk: 100-119.4 130-160 N.008.5. CuSO4 pH: 8.0008 reproduction LOEL 0. LOEL 0.2-9. CuSO4 pH: 8.16 6-wk growth and survival NOEL 0.06 pop. LOEL 0.7-11.022 21-d survival NOEL 0. LOEL 0.S Soundrapandia and Venkataraman 1990 Daphnia magna <24 hr SR (1/3d). S Paratanytarsus parthenogeniticus 7-d S. NOEL 0.001 reproduction NOEL 0.0004 28-d growth LOEL 0.04. S Arthur and Leonard 1970 120 . LOEL 0. T: 20+1.06 pop.5.06-0.02 reproduction NOEL 0.0148 pH: 7. DO: sat 250 N. T: 20.S Daphnia parvula 12+12 hr SR.005 >70 d survival NOEL 0. LOEL 0. DO: 7.2-9.01. CuCl2 3 wk LC50 0. LOEL 0.7-11. DO: 8. DO: near sat 45 Biesinger and Christensen 1972 Daphnia magna 6-24 hr CuSO4 pH: 8-8.S Gammarus pseudolimnaeus FT M-D. LOEL 0.32.008 6 wk growth and survival NOEL 1977 Daphnia ambigua 12+12 hr SR.7-11.S Reference Daphnia magna SR (7-d). LOEL 0. T: 18.04.S Dave 1984 Daphnia similis 24-hr SR (1/d).Species Lifestage Test Type Toxicity Endpoint (mg Cu/L) Environmental Conditions Hardness Classificatio n N. T: 20.044 EC50 (reproductive impairment) 0.S Winner and Farrell 1976 Winner and Farrell 1976 Winner and Farrell 1976 Arthur and Leonard 1970 Daphnia pulex 12+12 hr SR. growth NOEL 0. T: 23+1 25 M-D.04 pop.04. Alk: 42. LOEL 0.5.008. growth NOEL 0.2-9.64 18-d egg prod. CuSO4 pH: 6.5.0148 18-d growth NOEL 0.S Winner et al. T: 20.9-7. LOEL 0. Alk: 100-119. Alk: 100-118. Alk: 100-119.

Cu2+= expressed as cupric ion T= Water Temperature oC.Legend: Test Type: Toxicity Endpoint: Environmental Conditions: Classification: S=Static. T=expressed as total copper. DO=Dissolved Oxygen in mg/L unless otherwise stated. RP=Replicated P=Primary. SR=Static Replacement. Hard=Water Hardness in mg/L CaCO3. S=Secondary. N=Nominal. but significant decrease over test duration. NR=Not Reported. M=Measured Concentrations. diss= expressed as dissolved copper. M-D= Measured Concentration. U=Unsuitable. C=Calculated. FT=Flow-Through. 121 . Alk=Alkalinity in mg/L CaCO3.

037081 0. 1989 Chironomus Nebeker et al.005 0.01 0.1 45.01 0.037 0.032 0.021024 0.015198 Minnow 0.0106 0. 1976 McKim et al.060246 0. 1976 reprod.024677 0.019596 0.4 36 100 179 94.032 0.emergence 1984b Toxicity Endpoint survival growth standing crop growth survival water hardness 45 37.021024 0.005 0. 1978 standing crop channel catfish Sauter et al.Appendix 8 A Computations for the chronic Alberta copper guideline.013202 0.0046 0.8 45.012 0.078 0. 1986 surv/reprod Ceriodaphnia Spehar and Fiandtreprod 1986 Ceriodaphnia Belanger et al.017889 0.024 0. Stephan 1969 fathead minnow Geckler et al.024 0.05 0.013 0.006325 0. Species bluegill sunfish brook trout brook trout brook trout brook trout Reference Benoit 1975 Sauter et al.029799 0.003873 0.037 0.019812 0. reprod. egg prod.021024 0.5 45. MATC values are the geometric mean of the NOEC and LOEC values in mg/L and water hardness in mg/L CaCO3.0184 0.01 0.029799 0. 1978 standing crop rainbow trout Marr et al.017 0.022 0.0349 0.042 0.0043 0.4 83. channel catfish Sauter et al.053722 0. 1976 McKim and Benoit 1971 lake trout McKim et al.060246 0.034 0.060246 0.030397 0.025 0.4 45.015 LOEL 0.013966 0.0062 0.009747 0.1 36 NOEL 0.016063 0. 1978 standing crop pink salmon S e r v i z i a n d growth Martens 1978 sockeye salmon Servizi and Martensgrowth 1978 rainbow trout McKim et al.005 0. reprod.003181 0.053442 0. 1977 fathead minnow Mount 1968 egg prod.018 0.053722 0.04 0.012 0.028983 0.009984 GMCV 0. fathead minnow Spehar and Fiandt growth 1986 fathead minnow M o u n t a n d growth etc.008798 0.019 0.008 0.045 0.1 83.4 187 45. Neiheisel 1979 northern pike McKim et al.008798 0.055 0.053442 SMCV 0.034 0.022249 0. 1989 Ceriodaphnia Belanger et al.013038 0.006 0.022 0.053442 122 . fathead minnow P i c k e r i n g a n d growth Lazorchak 1995 fathead minnow Pickering et al.007544 0.033 MATC 0. 1978 standing crop Ceriodaphnia Carlson et al.084 0.035355 0.021 0.4 24.018 0.016063 0.0022 0.037 0. 1976 growth/surv.015198 0.4 36 186 218 202 198 45.037081 Oncorhynchus 0.013 0.031113 0. 1976 growth/surv.025 0.007746 0.015716 0.028983 Salvelinus 0.030397 0.028983 0.014697 0.104 0.019 0.003 0. bluntnose minnow H o r n i n g a n d egg prod. 1978 Sauter et al. Computations Species Mean Chronic Values (SMCV) and Genus Mean Chronic Values (GMCV).3 31 204 200 45.044 0. in press growth white sucker McKim et al.017421 0.

014142 B Computation Final Chronic Value and the Alberta chronic guideline.004 0.017421 0.013 0.063797 0.2 0. 1990growth Blaylock et al.surv.00955 P 0./surv Toxicity Endpoint al.01 LOEL 0.726 18.014142 SMCV 0.01 0.7 85 225 57.738428 1.066667 0.060246 ln -4.028983 0.22947 78.318494 -4.025 0.0084 0.85889 20.010806 0.133333 0.258199 0.014142 0.94605 -4.021024 0.013202 0.010806 0.006 0. 1993 Hatakeyama 1988 emerg.010387 0.013987 0.015198 0.02 MATC 0.50002 18.005 0.447214 0.0139 0.Species Clistoronia Corbicula Daphnia magna Daphnia magna Daphnia pulex Daphnia pulex Hyalella Polypedilum Reference Nebeker et 1984a Belanger et al.2696 -17.010387 0.020616 0.010387 0.5 115 130 68 NOEL 0.01 0.666667 sqrtP 0.013987 0.surv/reprod 1988 Winner 1985 surv.010387 0.010806 Daphnia 0.516398 1.010806 0.03 0.emergence water hardness 26 77.005886 0.6918 s^2 s L A FCV ln^2 20.014142 0.365148 0.053442 0.11 0. Winner 1985 surv.017321 0.586959 123 .020616 0.016063 0.020616 0.32735 -4.037 0.5277 -4.007071 0. Rank 1 2 3 4 5 6 7 8 9 10 11 12 13 14 GMCV 0.65122 0.024677 0.56715 -4.017 0. Borgmann et al.004899 0.266667 0.31437 1.020616 0.0083 0. 1985reprod Van Leeuwen et al.033241 GMCV 0.