Dissolved organic carbon reduces the toxicity of copper to germlings of the macroalgae, Fucus vesiculosus

This study investigates the effects of waterborne copper exposure on germling growth in chemically defined seawater. Germlings of the macroalgae, Fucus vesiculosus were exposed to a range of copper and dissolved organic carbon (DOC as humic acid) concentrations over 14 days. Germling growth was found to be a sensitive indicator of copper exposure with total copper (TCu) and labile copper (LCu) EC(50) values of approximately 40 and 20 microg/L, respectively, in the absence of added DOC. The addition of DOC into the exposure media provided germlings with protection against copper toxicity, with an increased TCu EC(50) value of 117.3 microg/L at a corrected DOC (cDOC from humic acid only) concentration of 2.03 mg/L. The LCu EC(50) was not affected by a cDOC concentration of 1.65 mg/L or less, suggesting that the LCu concentration not the TCu concentration was responsible for inhibiting germling growth. However, at a cDOC concentration of approximately 2mg/L an increase in the LCu EC(50) suggests that the LCu concentration may play a role in the overall toxicity to the germlings. This is contrary to current understanding of aquatic copper toxicity and possible explanations for this are discussed.     

Effects of dissolved organic carbon concentration and source, pH, and water hardness on chronic toxicity of copper to Daphnia magna

The effects of pH (5.3-8.7), water hardness (CaCO3 at 25-500 mg/L), dissolved organic carbon (DOC) concentration (1.6-18.4 mg/L), and DOC source on the chronic toxicity of copper to Daphnia magna were investigated by using a multifactorial, central composite test design. Natural dissolved organic matter (DOM) was collected at three sites in Belgium and The Netherlands by using reverse osmosis. For a total number of 35 toxicity tests performed, 21-d no-observed-effect concentrations (NOECs) of copper based on reproduction ranged from 29.4 to 228 microg/L and 21-d concentrations of copper causing 50% reduction of reproduction (EC50s) ranged from 41.5 to 316 microg/L. Statistical analysis revealed that DOC concentration and pH had a significant effect on copper toxicity but hardness (at the levels tested) did not. In general, an increase in pH or DOC resulted in a linear increase of 21-d NOEC and EC50 values. All DOMs (originating from three different sources) reduced copper toxicity to the same extent. Multiple linear regression analysis on the results of all 35 toxicity tests revealed that DOC concentration is the most important factor for chronic toxicity of copper to D. magna, explaining about 60% of the observed variability, whereas pH only explained about 15% of the observed variability. Regression models were developed (with DOC and pH as parameters) that were capable of predicting NOECs and EC50s within a factor of 1.9 from observed NOEC and EC50 values obtained with eight natural surface waters spiked with copper. Until future research further elucidates the mechanisms underpinning the observed bioavailability relations, these empirical regression models can become a first simple tool for regulatory applications.     

Influence of natural organic matter source on copper toxicity to larval fathead minnows (Pimephales promelas): implications for the biotic ligand model

The influence of dissolved natural organic matter (NOM) source on copper toxicity was investigated with larval fathead minnows (Pimephales promelas) in reconstituted moderately hard water. Ninety-six-hour static renewal toxicity tests were conducted to investigate an assumption of the biotic ligand model (BLM) that NOM source does not need to be considered to adequately predict copper toxicity. The nine different NOM isolates used in these toxicity tests were chemically well-characterized substances that were obtained by reverse osmosis as part of an NOM typing project based in southern Norway. Three median lethal concentration (LC50) values were estimated for toxicity tests conducted with each NOM, at nominal dissolved organic carbon (DOC) concentrations of 2, 5, and 10 mg/L. Tests also were conducted in dilution waters in which no NOM was added. Regression analyses were conducted to compare NOM-specific (specific NOM source) LC50s versus DOC concentration relationships to each other, as well as to the overall LC50 versus DOC concentration relationship. Statistical differences were found regarding the effects of NOM source on copper toxicity. Similar analyses were conducted with humic acid (HA) concentrations and spectral absorbance, and differences in the effect of NOM source on copper toxicity were similarly concluded. These results do not support the assumption that copper toxicity can be adequately predicted by utilizing DOC concentration, regardless of NOM source. Evaluation of relationships between LC50 values and other NOM characteristics revealed that despite significant differences due to NOM source on copper toxicity, DOC and HA concentrations were the most effective parameters in explaining variability in LC50 values. When BLM-predicted LC50 values were compared to observed LC50 values, predicted values showed reasonable agreement with observed values, but some deviations occurred due to NOM source and DOC concentration.     

Acute and Chronic Copper Toxicity to a Saltwater Cladoceran <Emphasis Type="Italic">Moina monogolica</Emphasis> Daday

The objective of this study was to evaluate the sensitivity of a saltwater cladoceran Moina monogolica Daday to copper toxicity. Acute and chronic toxicity tests were conducted according to the American Society for Testing and Materials (ASTM) guidelines. The 24- and 48-h LC(50)s and their 95% confidence intervals (CIs) were calculated as 154.21 (135.50-182.05) microg Cu/L and 106.07 (99.77- 112.36) microg Cu/L , respectively, based on measured copper concentrations. When compared with different phyla or classes of estuarine organisms, M. monogolica had moderate sensitivity and was suitable to be used as an indicator organism in the Changjiang estuary. Eight end points of longevity, number of broods, brood size, total reproduction, time to first brood, intrinsic rate of natural increase (r(m)), net reproductive rate (R(0)), and mean generation time (T) used to evaluate chronic effects were affected at chronic copper concentrations. Comparisons of chronic effects showed that toxicity mechanisms of dissolved copper are different from those of dietary exposure. The EC(20)s, EC(50)s, and their 95% CIs of end points were calculated using linear regression equations. The geometric mean generated the maximum-acceptable-toxicant concentration of 6.74 microg Cu/L between the no-observed-effect concentration of 5.06 and the lowest-observed-effect concentration of 8.99 microg Cu/L for brood size, total reproduction, r(m), and R(0), and 12.1 microg Cu/L between 8.99 and 16.29 microg Cu/L for longevity and number of broods as the end points, respectively. The EC(20) of R(0) appeared to be the most sensitive at 3.82 microg Cu/L among the end points. Results showed that aquatic organisms were possibly negatively affected at sites of higher copper concentrations in the Changjiang estuary. Further research is needed to evaluate the direct or indirect effects of copper more comprehensively to protect aquatic organisms and their habitats in the Changjiang estuary.     

Influence of water chemistry on the acute toxicity of copper and zinc to the cladoceran Ceriodaphnia cf dubia

This study determined the influence of key water chemistry parameters (pH, alkalinity, dissolved organic carbon [DOC], and hardness) on the aqueous speciation of copper and zinc and its relationship to the acute toxicity of these metals to the cladoceran Ceriodaphnia cf dubia. Immobilization tests were performed for 48-h in synthetic or natural waters buffered at various pH values from 5.5 to 8.4 (other chemical parameters held constant). The toxicity of copper to C. cf dubia decreased fivefold with increasing pH, whereas the toxicity of zinc increased fivefold with increasing pH. The effect of DOC on copper and zinc toxicity to C. cf dubia was determined using natural fulvic acid in the synthetic water. Increasing DOC was found to decrease linearly the toxicity of copper, with the mean effect concentration of copper that immobilized 50% of the cladocerans (EC50) value 45 times higher at 10 mg/L, relative to 0.1 mg/L DOC at pH 6.5. In contrast, the addition of 10 mg/L DOC only resulted in a very small (1.3-fold) reduction in the toxicity of zinc to C. cf dubia. Copper toxicity to C. cf dubia generally did not vary as a function of hardness, whereas zinc toxicity was reduced by a factor of only two, with an increase in water hardness from 44 to 374 mg CaCO3/L. Increasing bicarbonate alkalinity of synthetic waters (30-125 mg/L as CaCO3) decreased the toxicity of copper up to fivefold, which mainly could be attributed to the formation of copper-carbonate complexes, in addition to a pH effect. The toxicity of copper added to a range of natural waters with varying DOC content, pH, and hardness was consistent with the toxicity predicted using the data obtained from the synthetic waters.     

Effects of using synthetic sea salts when measuring and modeling copper toxicity in saltwater toxicity tests

Synthetic sea salts are often used to adjust the salinity of effluent, ambient, and laboratory water samples to perform toxicity tests with marine and estuarine species. The U.S. Environmental Protection Agency (U.S. EPA) provides guidance on salinity adjustment in its saltwater test guidelines. The U.S. EPA suggests using commercial sea salt brands, such as Forty Fathoms (now named Crystal Sea Marinemix, Bioassay Grade), HW Marinemix, or equivalent salts to adjust sample salinity. Toxicity testing laboratories in Canada and the United States were surveyed to determine synthetic sea salt brand preference. The laboratories (n = 27) reported using four brands: Crystal Sea Marinemix (56%), HW Marinemix (22%), Instant Ocean (11%), and Tropic Marin (11%). Saline solutions (30 g/L) of seven synthetic sea salts were analyzed for dissolved copper and dissolved organic carbon (DOC) content. Brands included those listed above plus modified general-purpose salt (modified GP2), Kent Marine, and Red Sea Salt. The synthetic sea salts added from < 0.1 to 1.2 microg Cu/L to the solution. Solutions of Crystal Sea Marinemix had significantly elevated concentrations of DOC (range = 5.4-6.4 mg C/L, analysis of variance, Tukey, alpha = 0.05, p < 0.001) while other brands generally contained < 1.0 mg C/L. The elevated DOC in Crystal Sea Marinemix was expected to reduce copper toxicity. However, the measured dissolved copper effective concentration 50% (EC50) for Crystal Sea Marinemix was 9.7 microg Cu/L, similar to other tested sea salts. Analysis indicates that the organic matter in Crystal Sea Marinemix differs considerably from that of natural organic matter. On the basis of consistently adding little DOC and little dissolved copper, GP2 and Kent Marine are the best salts to use.     

Toxicity of atrazine to the estuarine phytoplankter Pavlova sp. (Prymnesiophyceae): increased sensitivity after long-term, low-level population exposure

Phytoplankton are potentially more at risk to the adverse effects of herbicides than many other organisms in estuarine ecosystems. The focus of this study was to characterize the toxicity of a widely used herbicide, atrazine, to a single species of phytoplankton. The nanoplankter Pavlova sp. was grown under controlled laboratory conditions and was used to elucidate short-term, high-level population effects of atrazine. Secondly, a long-term, multigenerational population exposure was performed with a low level of atrazine followed by an additional short-term, high-level exposure on the same population with no recovery period. The 96-h growth rate of 50% effective concentration (EC50) for Pavlova sp. was 147 [microg/L (95% CI = 116.4-178.7 microg/L). Long-term exposure at 20 [microg/L for four (batch culture) growth cycles (approximately 20 generations) had no significant effect on the growth rate of Pavlova sp. except during the fourth growth cycle. However, a subsequent short-term, high-level 96-h exposure inoculated from the long-term, low-level exposed population showed increased sensitivity to atrazine (96-h growth rate EC50 = 96.0 microg/L, 95% CI = 90.2-103.7 microg/L). Multigenerational exposure to atrazine appeared to render phytoplankton significantly more sensitive (35%) to atrazine effects. Given the documented persistence of atrazine in surface waters, long-term exposure to low levels of atrazine without recovery may lead to shifts in species sensitivity and potential alterations in phytoplankton population dynamics.     

Influence of multigeneration acclimation to copper on tolerance, energy reserves, and homeostasis of Daphnia magna straus

A multigeneration acclimation experiment was performed with Daphnia magna exposed to copper to assess possible changes in tolerance and to establish the optimal concentration range (OCEE) of this species. The hypothesis was tested that as the bioavailable background concentration of an essential metal increases (within realistic limits), the natural tolerance (to the metal) of the acclimated/adapted organisms and communities will increase. During 18 months the daphnids were exposed to six different, environmentally relevant, copper background concentrations ranging between 0.5 and 100 microg Cu L(-1) (7 x 10(-15) and 3.7 x 10(-9) M Cu2+). An increase in acute (effect concentration resulting in 50% immobility: 48-h EC50) and chronic copper (effect concentration resulting in 50% or 10% reproduction reduction: 21-d EC50, 21-d EC10) tolerance was observed with increasing exposure concentration. The 48-h EC50 increased significantly from 204 +/- 24 microg Cu L(-1) to 320 +/- 43 microg Cu L(-1). A nonsignificant change from 48.0 (47.9-48.0) microg Cu L(-1) to 78.8 (66.3-93.6) microg Cu L(-1) was noted in the chronic toxicity assays. The optimal concentration range was assessed using different biological parameters (i.e., net reproduction [R0]), energy reserves (Ea), body length measurements, filtration rates, and body burdens. After three generations of acclimation the OCEE ranged between 1 and 35 microg Cu L(-1) (2 X 10(-14) to 80 x 10(-12) M Cu2+). Body burden measurements revealed an active copper regulation up to 35 microg Cu L(-1) (80 pM Cu2+). It can be concluded that acclimation of D. magna to copper does occur in laboratory experiments, even at realistic copper background concentrations (10(-11) - 10(-9) M Cu2+). However, it is suggested that this phenomenon is of less importance in the context of regulatory risk assessments. An optimal copper concentration range for D. magna was observed between 1 and 35 microg Cu L(-1) (10(-14) - 10(-11) M Cu2+), indicating that copper deficiency can occur in routine laboratory cultures.     

Relevance of generic and site-specific species sensitivity distributions in the current risk assessment procedures for copper and zinc

Species sensitivity distributions (SSD) were constructed using acute toxicity data of various cladoceran species collected in five different aquatic systems. The aim of this research was to study the relative acute cladoceran community sensitivity in different aquatic systems. Current risk assessment procedures are based upon hypothetical communities and do not take into account variation in species composition and tolerance between aquatic communities. Two metals, copper and zinc, were used as model toxicants. To establish comparative sensitivity, a standard medium (International Organization for Standardization [ISO]) was used. The generic SSD (log-normal distribution) based on toxicity data obtained in this standard medium for all species (collected at all sites) resulted in a hazardous concentrations that protects 95% of the species occurring in a (hypothetical) ecosystem (i.e., hazardous concentration protecting 95% of the species of the hypothetical ecosystem [HC5]) of 6.7 microg Cu L(-1) (90% confidence limits: 4.2-10.8) and 559 microg Zn L(-1) (375-843). This generic SSD was not significantly different from the site-specific SSDs (i.e., constructed with species only occurring at a specific site). Mean community sensitivity (the geometric mean of 48-h 50% effective concentration [EC50] values of species within a community) among sites varied within a factor of 2 (between 17.3 and 23.6 microg Cu L(-1) for Cu and between 973 and 1,808 microg Zn L(-1) for Zn), and HC5s varied within a factor of 4 for copper (between 4.5 and 17.3 microg Cu L(-1)) and 7 for zinc (between 194 and 1,341 microg Zn L(-1)). For copper, the HC50 of our generic SSD was significantly lower than the one based on literature toxicity data of cladoceran species (which were recalculated to the hardness of our standard medium). In contrast, no significant differences were observed between the generic SSD and the literature-based SSD for zinc. It is suggested that the community sensitivity of different cladoceran populations is similar among aquatic systems and is not dependent on the species composition.     

Ion-release kinetics and ecotoxicity effects of silver nanoparticles

The environmental toxicity associated with silver nanoparticles (AgNPs) has been a major focus in nanotoxicology. The Ag(+) released from AgNPs may affect ecotoxicity, although whether the major toxic effect is governed by Ag(+) ions or by AgNPs themselves is unclear. In the present study, we have examined the ecotoxicity of AgNPs in aquatic organisms, silver ion-release kinetics of AgNPs, and their relationship. The 48-h median effective concentration (EC50) values for Daphnia magna of powder-type AgNP suspensions were 0.75?μg/L (95% confidence interval [CI]?=?0.71-0.78) total Ag and 0.37?μg/L (95% CI?=?0.36-0.38) dissolved Ag. For sol-type AgNP suspension, the 48-h EC50 values for D. magna were 7.98?μg/L (95% CI?=?7.04-9.03) total Ag and 0.88?μg/L (95% CI?=?0.80-0.97) dissolved Ag. The EC50 values for the dissolved Ag of powder-type and sol-type AgNPs for D. magna showed similar results (0.37?μg/L and 0.88?μg/L) despite their differences of EC50 values in total Ag. We observed that the first-order rate constant (k) of Ag(+) ions released from AgNPs was 0.0734/h at 0.05?mg/L total Ag at 22°C within 6?h. The kinetic experiments and the toxicity test showed that 36% and 11% of sol-type AgNPs were converted to the Ag(+) ion form under oxidation conditions, respectively. Powder-type AgNPs showed 49% conversion rate of Ag(+) ion from AgNPs. We also confirmed that Ag(+) ion concentration in AgNP suspension reaches an equilibrium concentration after 48?h, which is an exposure time of the acute aquatic toxicity test.     

Influence of dissolved organic matter source on silver toxicity to Pimephales promelas

In the environment, the formation of organic and inorganic silver complexes can decrease Ag bioavailability (toxicity) to aquatic organisms. However, current water quality regulations do not consider the protective effects of water quality parameters such as dissolved organic carbon (DOC) concentration. To determine the effect of DOC concentration and source on silver toxicity, nine different natural organic matter isolates were used in 96-h static-renewal toxicity tests with fathead minnow (Pimephales promelas). The 96-h dissolved silver median lethal concentrations (LC50) among different sources of dissolved organic matter varied by up to fivefold (4.5-23.3 microg/L). Further, toxicity tests with organic matter from the site with the lowest 96-h LC50 value suggested only limited additional attenuation of silver toxicity when DOC concentration was increased from 5.1 to 14.0 mg/L. With this site excluded, we found little more than a twofold difference among 96-h dissolved Ag LC50s for the remaining sources (10.1-23.3 microg/L). However, significant toxicological differences among sites remained. It was apparent that organic matter from different sources varied both chemically and toxicologically, but no conclusions could be drawn that related compositional variation to observed Ag toxicity for these isolates.     

Chronic toxicity of copper and ammonia to juvenile freshwater mussels (Unionidae)

The objectives of the present study were to develop methods for conducting chronic toxicity tests with juvenile mussels under flow-through conditions and to determine the chronic toxicity of copper and ammonia to juvenile mussels using these methods. In two feeding tests, two-month-old fatmucket (Lampsilis siliquoidea) and rainbow mussel (Villosa iris) were fed various live algae or nonviable algal mixture for 28 d. The algal mixture was the best food resulting in high survival (>or=90%) and growth. Multiple copper and ammonia toxicity tests were conducted for 28 d starting with two-month-old mussels. Six toxicity tests using the algal mixture were successfully completed with a control survival of 88 to 100%. Among copper tests with rainbow mussel, fatmucket, and oyster mussel (Epioblasma capsaeformis), chronic value ([ChV], geometric mean of the no-observed-effect concentration and the lowest-observed-effect concentration) ranged from 8.5 to 9.8 microg Cu/L for survival and from 4.6 to 8.5 microg Cu/L for growth. Among ammonia tests with rainbow mussel, fatmucket, and wavy-rayed lampmussel (L. fasciola), the ChV ranged from 0.37 to 1.2 mg total ammonia N/L for survival and from 0.37 to 0.67 mg N/L for growth. These ChVs were below the U.S. Environmental Protection Agency 1996 chronic water quality criterion (WQC) for copper (15 microg/L; hardness 170 mg/L) and 1999 WQC for total ammonia (1.26 mg N/L; pH 8.2 and 20 degrees C). Results indicate that toxicity tests with two-month-old mussels can be conducted for 28 d with >80% control survival; growth was frequently a more sensitive endpoint compared to survival; and the 1996 chronic WQC for copper and the 1999 chronic WQC for total ammonia might not be adequately protective of the mussel species tested. However, a recently revised 2007 chronic WQC for copper based on the biotic ligand model may be more protective in the water tested.     

Effect of initial cell density on the bioavailability and toxicity of copper in microalgal bioassays

Algal toxicity tests based on growth inhibition over 72 h have been extensively used to assess the toxicity of contaminants in natural waters. However, these laboratory tests use high cell densities compared to those found in aquatic systems in order to obtain a measurable algal response. The high cell densities and test duration can result in changes in chemical speciation, bioavailability, and toxicity of contaminants throughout the test. With the recent application of flow cytometry to ecotoxicology, it is now possible to use lower initial cell densities to minimize chemical speciation changes. The speciation and toxicity of copper in static bioassays with the tropical freshwater alga Chlorella sp. and the temperate species Selenastrum capricornutum (Pseudokirchneriella subcapitata) were investigated at a range of initial cell densities (10(2)-10(5) cells/ml). Copper toxicity decreased with increasing initial cell density. Copper concentrations required to inhibit growth (cell division) rate by 50% (72-h median effective concentration [EC50]) increased from 4.6 to 16 microg/L for Chlorella sp. and from 6.6 to 17 microg/L for S. capricornutum as the initial cell density increased from 10(2) to 10(5) cells/ml. Measurements of anodic stripping voltammetry-labile, extracellular, and intracellular copper confirmed that at higher initial cell densities, less copper was bound to the cells, resulting in less copper uptake and lower toxicity. Chemical measurements indicated that reduced copper toxicity was due primarily to depletion of dissolved copper in solution, with solution speciation changes due to algal exudates and pH playing a minor role. These findings suggest that standard static laboratory bioassays using 10(4) to 10(5) algal cells/ml may seriously underestimate metal toxicity in natural waters.     

Development and field validation of a predictive copper toxicity model for the green alga Pseudokirchneriella subcapitata

In this study, the combined effects of pH, water hardness, and dissolved organic carbon (DOC) concentration and type on the chronic (72-h) effect of copper on growth inhibition of the green alga Pseudokirchneriella subcapitata were investigated. Natural dissolved organic matter (DOM) was collected at three sites in Belgium and The Netherlands using reverse osmosis. A full central composite test design was used for one DOM and a subset of the full design for the two other DOMs. For a total number of 35 toxicity tests performed, 72-h effect concentration resulting in 10% growth inhibition (EbC10s) ranged from 14.2 to 175.9 micrograms Cu/L (factor 12) and 72-h EbC50s from 26.9 to 506.8 micrograms Cu/L (factor 20). Statistical analysis demonstrated that DOC concentration, DOM type, and pH had a significant effect on copper toxicity; hardness did not affect toxicity at the levels tested. In general, an increase in pH resulted in increased toxicity, whereas an increase of the DOC concentration resulted in decreased copper toxicity. When expressed as dissolved copper, significant differences of toxicity reduction capacity were noted across the three DOM types tested (up to factor 2.5). When expressed as Cu2+ activity, effect levels were only significantly affected by pH; linear relationships were observed between pH and the logarithm of the effect concentrations expressed as free copper ion activity, that is, log(EbC50Cu2+) and log(EbC10Cu2+): (1) log(EbC50Cu2+)= - 1.431 pH + 2.050 (r2 = 0.95), and (2) log(EbC10cu2+) = -1.140 pH -0.812 (r2 = 0.91). A copper toxicity model was developed by linking these equations to the WHAM V geochemical speciation model. This model predicted 97% of the EbC50dissolved and EbC10dissolved values within a factor of two of the observed values. Further validation using toxicity test results that were obtained previously with copper-spiked European surface waters demonstrated that for 81% of tested waters, effect concentrations were predicted within a factor of two of the observed. The developed model is considered to be an important step forward in accounting for copper bioavailability in natural systems.     

Acute toxicity of copper, ammonia, and chlorine to glochidia and juveniles of freshwater mussels (Unionidae)

The objective of the present study was to determine acute toxicity of copper, ammonia, or chlorine to larval (glochidia) and juvenile mussels using the recently published American Society for Testing and Materials (ASTM) Standard guide for conducting laboratory toxicity tests with freshwater mussels. Toxicity tests were conducted with glochidia (24- to 48-h exposures) and juveniles (96-h exposures) of up to 11 mussel species in reconstituted ASTM hard water using copper, ammonia, or chlorine as a toxicant. Copper and ammonia tests also were conducted with five commonly tested species, including cladocerans (Daphnia magna and Ceriodaphnia dubia; 48-h exposures), amphipod (Hyalella azteca; 48-h exposures), rainbow trout (Oncorhynchus mykiss; 96-h exposures), and fathead minnow (Pimephales promelas; 96-h exposures). Median effective concentrations (EC50s) for commonly tested species were >58 microg Cu/L (except 15 microg Cu/L for C. dubia) and >13 mg total ammonia N/L, whereas the EC50s for mussels in most cases were <45 microg Cu/L or <12 mg N/L and were often at or below the final acute values (FAVs) used to derive the U.S. Environmental Protection Agency 1996 acute water quality criterion (WQC) for copper and 1999 acute WQC for ammonia. However, the chlorine EC50s for mussels generally were >40 microg/L and above the FAV in the WQC for chlorine. The results indicate that the early life stages of mussels generally were more sensitive to copper and ammonia than other organisms and that, including mussel toxicity data in a revision to the WQC, would lower the WQC for copper or ammonia. Furthermore, including additional mussel data in 2007 WQC for copper based on biotic ligand model would further lower the WQC.     

Application of an acute biotic ligand model to predict chronic copper toxicity to Daphnia magna in natural waters of Chile and reconstituted synthetic waters

The objective of the present study was to assess the predictive capacity of the acute Cu biotic ligand model (BLM) as applied to chronic Cu toxicity to Daphnia magna in freshwaters from Chile and synthetic laboratory-prepared waters. Samples from 20 freshwater bodies were taken, chemically characterized, and used in the acute Cu BLM to predict the 21-d chronic Cu toxicity for D. magna. The half-maximal effective concentration (EC50) values, determined using the Organisation for Economic Co-operation and Development (OECD) 21-d reproduction test (OECD Method 211), were compared with the BLM simulated EC50 values. The same EC50 comparison was performed with the results of 19 chronic tests in synthetic media, with a wide range of hardness and alkalinity and a fixed 2 mg/L dissolved organic carbon (DOC) concentration. The acute BLM was modified only by adjustment of the accumulation associated with 50% of an effect value (EA50). The modified BLM model was able to predict, within a factor of two, 95% of the 21-d EC50 and 89% of the 21-d half-maximal lethal concentrations (LC50) in natural waters, and 100% of the 21-d EC50 and 21-d LC50 in synthetic waters. The regulatory implications of using a slightly modified version of an acute BLM to predict chronic effects are discussed.     

Ecological hazard assessment of major veterinary benzimidazoles: acute and chronic toxicities to aquatic microbes and invertebrates

Aquatic toxicities of six benzimidazole-based anthelmintics-namely, albendazole, thiabendazole, flubendazole, febantel, fenbendazole, and oxfendazole-were evaluated with a marine bacterium, Vibrio fischeri, and a freshwater invertebrate, Daphnia magna. Delayed and chronic toxicity tests using D. magna also were conducted for benzimidazoles with high acute toxicity. Vibrio fischeri was greater than 10-fold less sensitive to most of the benzimidazoles tested compared to daphnids. For D. magna, the most acutely toxic anthelmintic compound tested was fenbendazole (48-h median effective concentration [EC50s], 16.5 microg/L), followed by flubendazole (48-h EC50, 66.5 micro/L), albendazole (48-h EC50, 67.9 microg/L), febantel (48-h EC50, 216.5 microg/L), thiabendazole (48-h EC50, 843.6 microg/L), and oxfendazole (48-h EC50, 1,168.4 microg/L). The lipophilicity parameter, log Kow, explained the observed acute D. magna toxicity of the individual benzimidazoles (r = -0.91, p < 0.01). Delayed expression of toxicity observed for 21 d after 96-h exposure to fenbendazole and flubendazole was not notable, which might result from the relatively high elimination constants for the chemicals. With chronic exposure to fenbendazole, D. magna survival, reproduction, and growth were significantly impacted at 1.25 to 4.1 microg/L (p < 0.05). Hazard quotients estimated for fenbendazole, albendazole, flubendazole, and febantel were 2,770, 9.7, 4, and 1.2, respectively, suggesting a need for further investigation and a potential for environmental concerns, particularly with fenbendazole.     

Determination of short-term copper toxicity in a multispecies microalgal population using flow cytometry

This study was conducted to determine the role of algal-algal interactions in a multispecies microalgal population on their sensitivities to copper based on an enzyme inhibition assay using flow cytometric measures. Autofluorescence (chlorophyll a and phycocyanin) was used to identify species and count algal signals. The effect of multispecies population on copper toxicity of Microcystis aeruginousa was detected (1) at the same initial cell density, (2) at the same surface area, and (3) in the presence and absence of Chlorella pyrenoidosa and Scenedesmus obliquus. As copper concentrations increased, esterase activity of M. aeruginosa changed in a concentration-dependent manner. The 24 h EC(50) value of M. aeruginosa in the multispecies population was significantly (P < 0.05) higher than those in the single-species population. Compared with S. obliquus, the effect of C. pyrenoidosa on M. aeruginosa was more marked (the 24 h EC(50) value of copper on fluorescin diacetate fluorescence of M. aeruginosa was 11 microg/L). At 48 h copper exposure (6 microg/L) analysis of intracellular reactive oxygen species levels also showed similar algal-algal interactions in multispecies microalgal populations. The pigment assay suggested that these algal-algal interactions occurred only at low concentrations (< 13 microg/L, 24 and 48 h copper exposure). This study demonstrates the importance of using multispecies populations to estimate metal toxicity in natural waters.     

Speciation, behavior, and bioavailability of copper downstream of a mine-impacted lake

A combination of Cu speciation analysis and toxicity testwork was conducted to assess the behavior, speciation, and bioavailability of Cu in a stream system rich in dissolved organic carbon (DOC) downstream of a mine-impacted lake (East Lake, ON, Canada). Elevated levels (approximately 50 microg/L) of Cu exist in the lake due to the release of dissolved Cu to the water column from underlying sediments. Most of the Cu present in East Lake and downstream is present as filterable species that represent 74 to 100% of the total. Measurements of labile Cu as measured by diffusive gradients in thin films (DGT) suggest that most of the Cu is unavailable to aquatic biota. The DGT results indicate that 9 to 24% of Cu within the receiving environment is biologically available. Decreases in the labile Cu fraction with distance downstream of East Lake correlate well with increases in the concentration of DOC (r(2) = 0.79-0.95), presumably due to the progressive importance of Cu-organic complexes. The relationship between filterable Cu and SO(4)(2-) downstream of East Lake was linear (r(2) = 0.99) for all sampling periods, suggesting that decreases in filterable Cu concentration downstream of East Lake could be attributed solely to dilution (i.e., conservative behavior). Variations in the filterable Cu concentration resulting in 50% mortality (LC50 = 96-203 microg/L) and the concentration resulting in an inhibition of reproduction by 25% (IC25 = 75-156 microg/L) with respect to Ceriodaphnia dubia (7-d incubation) in Cu-spiked solutions could be explained by differences in labile-Cu concentrations as determined by DGT. The considerable complexation capacity afforded by lake and stream waters can be attributed to complexation of Cu with abundant DOC (7-17 mg/L). The relevance of the toxicity data to water-effect ratio testwork, and the associated development of site-specific water quality objectives, are discussed.     

Copper-containing, framed intrauterine devices for contraception: a systematic review of randomized controlled trials

BACKGROUND: Intrauterine devices (IUDs) are safe and effective methods of long-term reversible contraception. The design and copper content as well as placement of the copper on IUDs could affect their effectiveness and side effect profile. We compared different copper IUDs for their effectiveness and side effects. STUDY DESIGN: We searched multiple electronic databases with appropriate keywords and names of the IUDs known to be on the market. We searched the reference lists of papers identified and contacted authors when possible. There was no language restriction. Randomized controlled trials comparing different IUDs that reported on clinical outcomes were considered for inclusion. Two reviewers independently extracted data on outcomes and trial characteristics. We combined the trial results in meta-analyses and expressed results as rate difference (RD) using a fixed-effects model with 95% confidence interval (CI). In the presence of significant heterogeneity, a random-effects model was applied. RESULTS: We included 35 trials, resulting in 18 comparisons of 10 different IUDs in approximately 48,000 women. TCu380A was more effective in preventing pregnancy than MLCu375 (RD 1.70%, 95% CI 0.07-2.95% after 4 years of use). TCu380A was also more effective than MLCu250, TCu220 and TCu200. There tended to be fewer pregnancies with TCu380S compared to TCu380A after the first year of use, a difference which was statistically significant in the fourth year (RD -1.62%, 95% CI -3.00% to -0.24%). This occurred despite more expulsions with TCu380S (RD 3.50%, 95% CI 0.36-6.63% at 4 years). MLCu375 was no more effective than TCu220 at 1 year of use, or MLCu250 and NovaT up to 3 years. Compared to TCu380A or TCu380S, none of the IUDs showed any benefits in terms of bleeding or pain or any of the other reasons for early discontinuation. None of the trials that reported events at insertion found one IUD easier to insert than another or caused less pain at insertion. There is no evidence that uterine perforation rates vary by type of device. There are minimal randomized data on IUD use in nulliparous women. CONCLUSIONS: TCu380A and TCu380S appear to be more effective than other IUDs. No IUD showed consistently lower removal rates for bleeding and pain in comparison to other IUDs. There is no evidence that any particular framed copper device is better suited to women who have not had children.