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.     

Development and field validation of a biotic ligand model predicting chronic copper toxicity to Daphnia magna

In this study, we developed a toxicity model predicting the long-term effects of copper on the reproduction of the cladoceran Daphnia magna that is based on previously reported toxicity tests in 35 exposure media with different water chemistries. First, it was demonstrated that the acute copper biotic ligand model (BLM) for D. magna could not serve as a reliable basis for predicting chronic copper toxicity. Consequently, BLM constants for chronic exposures were derived by multiple regression analysis of 21-d median effective concentrations (EC50s; expressed as Cu2+ activity) versus physicochemistry from a large toxicity dataset and the results of an additional experiment in which the individual effect of sodium on copper toxicity was investigated. The effect of sodium on chronic toxicity (log K NaBL = 2.91) seemed to be similar to its effect on acute toxicity (log K NaBL = 3.19). However, in contrast to the acute BLM, no significant calcium, magnesium, or combined competition effect was observed, and an increase in proton competition and bioavailability of CuOH+ and CuCO3 complexes was noted. Some indirect evidence was also found for some limited toxicity of complexes of copper with two of three tested types of dissolved organic matter. Because the latter was only a minor effect, this factor was not included in the chronic Cu BLM. The newly developed model performed well in predicting 21-d EC50s and no-observed-effect concentrations in natural water samples: 79% of the toxicity threshold values were predicted within a factor of two of the observed values. It is clear, however, that more research is needed to provide information on the exact mechanisms that have resulted in different BLM constants for chronic exposures (as opposed to acute exposures). It is suggested that the developed model can contribute to the improvement of risk assessment procedures of copper by incorporating bioavailability of copper in these regulatory exercises.     

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.     

Biotic ligand model of the acute toxicity of metals. 2. Application to acute copper toxicity in freshwater fish and Daphnia

The biotic ligand model (BLM) was developed to explain and predict the effects of water chemistry on the acute toxicity of metals to aquatic organisms. The biotic ligand is defined as a specific receptor within an organism where metal complexation leads to acute toxicity. The BLM is designed to predict metal interactions at the biotic ligand within the context of aqueous metal speciation and competitive binding of protective cations such as calcium. Toxicity is defined as accumulation of metal at the biotic ligand at or above a critical threshold concentration. This modeling framework provides mechanistic explanations for the observed effects of aqueous ligands, such as natural organic matter, and water hardness on metal toxicity. In this paper, the development of a copper version of the BLM is described. The calibrated model is then used to calculate LC50 (the lethal concentration for 50% of test organisms) and is evaluated by comparison with published toxicity data sets for freshwater fish (fathead minnow, Pimephales promelas) and Daphnia.     

Development of a chronic zinc biotic ligand model for Daphnia magna

The individual effects of the cations Ca(2+), Mg(2+), Na(+), and H(+) on the chronic toxicity of Zn to the waterflea Daphnia magna were investigated in different series of univariate experiments, resulting in the development of a chronic Zn biotic ligand model (BLM) for this species. Using the mathematical approach based on a linear relationship between cation activity and metal activity at the EC(x) level, the following stability constants for binding of competing cations to the biotic ligand (BL) were derived: logK(CaBL) = 3.22, logK(MgBL) = 2.69, logK(NaBL) = 1.90, and logK(HBL) = 5.77. With the derived constants and a logK(ZnBL) of 5.31, two different BLMs that predict chronic zinc toxicity (EC(50), no observed effect concentration (NOEC)) for D. magna as a function of water characteristics were developed. Fractions of binding sites occupied by Zn at the considered effect levels EC(50) and NOEC were 0.127 and 0.084, respectively. The NOEC-based model predicts the Zn toxicity within a factor of 2, while the chronic EC(50) could be predicted within a factor of 1.5. In the future, these chronic Zn BLMs for D. magna can improve the ecological relevancy of zinc risk assessments by decreasing the bioavailability-related uncertainty of zinc toxicity.     

Biotic ligand model prediction of copper toxicity to daphnids in a range of natural waters in Chile

The objective of this study was to assess the predictive capacity of the biotic ligand model (BLM) for acute copper toxicity to daphnids as applied to a number of freshwaters from Chile and to synthetic laboratory-prepared waters. Thirty-seven freshwater bodies were sampled, chemically characterized, and used to determine the copper concentration associated with the 50% of mortality (LC50) for Daphnia magna, Daphnia pulex, and Daphnia obtusa (native to Chile). The data were then used to run three versions of the acute copper BLM, and the predicted LC50s were compared to the observed ones. The same was done with synthetic assay media at various hardness and dissolved organic carbon (DOC) levels. The BLM versions differed in the affinity constants for some biotic ligand-ion pairs, stability constants for inorganic Cu complexes, and assumptions regarding Cu binding to DOC. All three versions showed a high degree of predictive performance, mostly within a twofold range of observed toxicity values. The D. obtusa data set was used to compare water quality criteria (WQC) derived from the observed toxicity values with those derived from either the BLM or the U.S. Environmental Protection Agency (U.S. EPA) procedure. For most low DOC waters, the three procedures generated similar WQCs. For the high-DOC waters, the EPA-derived criteria were significantly lower, that is, greatly overprotective. The results are also discussed in terms of the validation of the BLM for regulatory use.     

Effects of chronic dietary copper exposure on growth and reproduction of Daphnia magna

A matter of current, intense debate with regard to the effects of metals on biological systems is the potential toxicity of metals associated with food particles. Recently developed biotic ligand models (BLM), which predict the toxicity of waterborne metals, may not be valid if the dietary exposure route contributes to metal toxicity. The present study is, to our knowledge, the first that investigates the potential toxicity of dietary copper to a freshwater invertebrate (i.e., Daphnia magna) feeding on a live diet (i.e., the green alga Pseudokircheneriella subcapitata). Algae were exposed for 3 d to different copper concentrations, resulting in algal copper burdens between approximately 6.2 X 10(-16) and 250 x 10(-16) g cell(-1). These algae were then used as food in chronic, 21-d D. magna toxicity tests in which growth, reproduction, and copper accumulation were assessed. Three exposure scenarios were tested: A waterborne exposure, a dietary exposure, and a combined waterborne and dietary exposure. Although exposure to dietary copper resulted in an increased copper body burden of the adult daphnids, it did not contribute to toxicity and did not affect the 21-d effect concentrations expressed as waterborne copper, indicating that the previously established good predictive capacity of the chronic D. magna BLM is not affected. On the contrary, exposure to the highest dietary copper levels resulted in an increase of as much as 75% in growth and reproduction. To our knowledge, this is the first evidence that dietary copper exposure of a freshwater invertebrate feeding on a live diet resulted in a beneficial effect.     

Predicting acute zinc toxicity for Daphnia magna as a function of key water chemistry characteristics: development and validation of a biotic ligand model

The individual effect of different major cations (Ca2+, Mg2+, Na+, K+, and H+) on the acute toxicity of zinc to the waterflea Daphnia magna was investigated. The 48-h median effective concentration (EC50) in the baseline test medium (i.e., a standard medium with very low ion concentrations) was about 6 microM (Zn2+). An increase of Ca2+ (from 0.25 mM to 3 mM), Mg2+ (from 0.25 mM to 2 mM), and Na+ activity (from 0.077 mM to 13 mM) reduced zinc toxicity by a factor of 6.3, 2.1, and 3.1, respectively. No further toxicity reduction was observed when Ca2+ and Mg2+ activities exceeded 3.0 and 2.0 mM, respectively. Both K+ and H+ did not significantly alter zinc toxicity (expressed as Zn2+ activity). From these data, conditional stability constants for Ca2+ (log K = 3.24), Mg2+ (log K = 2.97), Na+ (log K = 2.16), and Zn2+ (log K = 5.31) were derived and incorporated into a biotic ligand model (BLM) predicting acute zinc toxicity to D. magna in surface waters with different water quality characteristics. Validation of the developed BLM using 17 media with different pH, hardness, and dissolved organic carbon (DOC) content resulted in a significant correlation coefficient (R2 = 0.76) between predicted and observed 48-h EC50. Eighty-eight percent of the predictions were within a factor of 1.3 of the observed 48-h EC50.     

Dissolved fraction of standard laboratory cladoceran food alters toxicity of waterborne silver to Ceriodaphnia dubia

The biotic ligand model (BLM) for the acute toxicity of cationic metals to aquatic organisms incorporates the toxicity-modifying effects of dissolved organic matter (DOM), but the default parameterization (i.e., assuming 10% of DOM is humic acid) does not differentiate DOM from different sources. We exposed a cladoceran (Ceriodaphnia dubia) to Ag in the presence of DOM from filtered YCT (standard yeast-Cerophyll(R)-trout chow food recommended by the U.S. Environmental Protection Agency [EPA] for cladocerans), from the Suwannee River (GA, USA; relatively little anthropogenic input), and from the Desjardins Canal in Hamilton (ON, Canada; receives treated municipal wastewater effluent). In all three treatments, the dissolved organic carbon (DOC) concentration was 2 mg/L (the concentration following addition of YCT slurry at the U.S. EPA-recommended volume ratio). The average 48-h median effects concentration (EC50) ratios for dissolved Ag in the presence and absence of DOM [i.e., (EC50 with DOM)/(EC50 without DOM)] were as follows: Suwannee River, 1.6; Desjardins Canal, 2.2; and YCT filtrate, 26.8. Therefore, YCT filtrate provided much more protection against Ag toxicity than that provided by DOM from the surface waters. The major spectral characteristic that differentiated YCT filtrate from the other two types of DOM was a strong tryptophan peak in the excitation- emission matrix for YCT. These results have important implications for interpreting Ag toxicity tests in which organisms are fed YCT, and they suggest BLM-calculated toxicity predictions might be improved by incorporating specific chemical constituents or surrogate indices of DOM. Another component of the protective effect against Ag toxicity, however, might be that the dissolved fraction of YCT served as an energy and/or nutrient source for C. dubia.     

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.     

An evaluation of biotic ligand models predicting acute copper toxicity to Daphnia magna in wastewater effluent

The toxicity of Cu to Daphnia magna was investigated in a series of 48-h immobilization assays in effluents from four wastewater treatment works. The assay results were compared with median effective concentration (EC50) forecasts produced by the HydroQual biotic ligand model (BLM), the refined D. magna BLM, and a modified BLM that was constructed by integrating the refined D. magna biotic ligand characterization with the Windermere humic aqueous model (WHAM) VI geochemical speciation model, which also accommodated additional effluent characteristics as model inputs. The results demonstrated that all the BLMs were capable of predicting toxicity by within a factor of two, and that the modified BLM produced the most accurate toxicity forecasts. The refined D. magna BLM offered the most robust assessment of toxicity in that it was not reliant on the inclusion of effluent characteristics or optimization of the dissolved organic carbon active fraction to produce forecasts that were accurate by within a factor of two. The results also suggested that the biotic ligand stability constant for Na may be a poor approximation of the mechanisms governing the influence of Na where concentrations exceed the range within which the biotic ligand stability constant value had been determined. These findings support the use of BLMs for the establishment of site-specific water quality standards in waters that contain a substantial amount of wastewater effluent, but reinforces the need for regulators to scrutinize the composition of models, their thermodynamic and biotic ligand parameters, and the limitations of those parameters.     

Ecotoxicity of a polycyclic aromatic hydrocarbon (PAH)-contaminated soil

Soil samples from a former cokery site polluted with polycyclic aromatic hydrocarbons (PAHs) were assessed for their toxicity to terrestrial and aquatic organisms and for their mutagenicity. The total concentration of the 16 PAHs listed as priority pollutants by the US Environmental Protection Agency (US-EPA) was 2634+/-241 mg/kgdw in soil samples. The toxicity of water-extractable pollutants from the contaminated soil samples was evaluated using acute (Vibrio fischeri; Microtox test, Daphnia magna) and chronic (Pseudokirchneriella subcapitata, Ceriodaphnia dubia) bioassays and the EC values were expressed as percentage water extract in the test media (v/v). Algal growth (EC50-3d=2.4+/-0.2% of the water extracts) and reproduction of C. dubia (EC50-7d=4.3+/-0.6%) were the most severely affected, compared to bacterial luminescence (EC50-30 min=12+/-3%) and daphnid viability (EC50-48 h=30+/-3%). The Ames and Mutatox tests indicated mutagenicity of water extracts, while no response was found with the umu test. The toxicity of the soil samples was assessed on the survival and reproduction of earthworms (Eisenia fetida) and collembolae (Folsomia candida), and on the germination and growth of higher plants (Lactuca sativa L.: lettuce and Brassica chinensis J.: Chinese cabbage). The EC50 values were expressed as percentage contaminated soil in ISO soil test medium (weight per weight-w/w) and indicated severe effects on reproduction of the collembola F. candida (EC50-28 d=5.7%) and the earthworm E. fetida (EC50-28 d=18% and EC50-56 d=8%, based on cocoon and juvenile production, respectively). Survival of collembolae was already affected at a low concentration of the contaminated soil (EC50-28 d=11%). The viability of juvenile earthworms was inhibited at much lower concentrations of the cokery soil (EC50-14 d=28%) than the viability of adults (EC50-14 d=74%). Only plant growth was inhibited (EC50-17d=26%) while germination was not. Chemical analyses of water extracts allowed us to identify inorganic water-extractable pollutants as responsible for toxicity on aquatic species, especially copper for effects on D. magna and C. dubia. The soil toxicity on collembolae and earthworms could be explained by 4 PAH congeners-fluorene, phenanthrene, pyrene, and fluoranthene. Yet, toxicity of the cokery soil as a whole was much lower than toxicity that could be deduced from the concentration of each congener in spiked soils, indicating that pollutants in the soil became less bioavailable with ageing.     

Application of Biotic Ligand Model in Predicting Copper Acute Toxicity to Carp (<Emphasis Type="Italic">Cyprinidae</Emphasis>)

Three representative species of Cyprinidae fishes (Aristichthys nobilis, Ctenopharyngodon idellus, and Cyprinus carpio), which are abundant in Chinese surface waters, were studied to determine their sensitivity to copper (Cu) in acute exposures. We first performed acute toxicity tests to determine the Cu LC₅₀ value for each species in water with varying characteristics. The biotic ligand model (BLM) was then calibrated using the toxicity data for these species together with binding properties specific to Cu. The BLM calibration involved the calculation of the level of Cu accumulation in the gills that resulted in 50% lethality (i.e., LA₅₀). The LA₅₀ values for A. nobilis, C. idellus and C. carpio were 5.16, 11.60 and 9.00 nmol g^?1. The model calibrated to these data was improved by adjusting the Cu-proton exchange constant (pK _CuHA-A) and dissolved organic carbon (DOC) to values of 1.84 and 4.67E-3 mol g^?1, respectively. The calibrated Cu-BLM was validated for these three common fish species by comparing predicted and observed LC₅₀ values, which were in agreement to within a factor of 2. The results of this study provide an important contribution to ecological risk assessment and establishment of water quality criteria for Cu in China.     

Influence of calcium, magnesium, sodium, potassium and pH on copper toxicity to barley (Hordeum vulgare)

The extent to which Ca(2+), Mg(2+), Na(+), K(+) ions and pH independently influence copper toxicity to barley (Hordeum vulgare) was assessed by measuring root growth in nutrient solutions. Increased Ca(2+) activity resulted in a sixfold decrease in [EC50(cu2+)] values, while a positive relationship between the cation activity and the EC50 was expected. Increased Mg(2+) activity resulted in a twofold increase in [EC50(cu2+)] values. Na(+), K(+) and H(+) activities did not significantly affect Cu(2+) toxicity. The obtained results indicated that competition for binding sites between Cu(2+) and cations such as Ca(2+), Mg(2+), Na(+), K(+) and H(+) is not an important factor in determining Cu(2+) toxicity to H. vulgare. However, the EC50s could, with one exception, be predicted within a factor three based on the free Cu(2+) activity, indicating that the free Cu(2+) activity cannot only be used to predict metal toxicity to aquatic, but also to terrestrial organisms.     

Effects of temperature on the sensitivity of sludge worm Tubifex tubifex Müller to selected heavy metals

The present study evaluates the effect of temperature on the sensitivity of the freshwater tubificid sludge worm Tubifex tubifex Müller to 10 heavy metal ions. Metals used in this study were cadmium, chromium, cobalt, copper, iron, lead, manganese, mercury, nickel, and zinc. The acute toxicity of these heavy metals was studied at 15, 20, 25, and 30 degrees C. The percentage mortality, relative toxicity, and EC50 values and their 95% confidence limits from 24 to 96 h were determined at varying temperatures. The EC50 values (mg/liter) of metal ions at 15 degrees C were Hg2+, 0.034; Cu2+, 0.340; Cr6+, 1.846; Zn2+, 10.99; Ni2+, 25.10; Cd2+, 56; Fe3+, 86.09; Co2+, 239.39; Pb2+, 456.76; and Mn2+, 164.55. At 30 degrees C the values were Hg2+, 0.014; Cu2+, 0.031; Cr6+, 0.872; Zn2+, 3.37; Ni2+, 18; Cd2+, 28.55; Fe3+, 71.26; Co2+, 95.35; Pb2+, 165.22; and Mn2+, 239.39. The results indicate that the acute toxicity of cadmium, chromium, cobalt, copper, lead, mercury, nickel, and zinc increases with temperature increase. The toxicity of manganese was not influenced by temperature, and temperature had little effect on iron toxicity. The rank order of toxicity of metal ions at 15, 20, 25, and 30 degrees C is presented and discussed. It is concluded that temperature is an important factor in short-term acute toxicity tests. The study indicates that seasonal temperature changes are an important variable in determining the amount of heavy metals that may be safely released from metal industries and other similar sources into the aquatic environment. Influence of temperature on the short- and long-term toxicity of chemicals should be considered for establishing appropriate water-quality criteria and standards to protect aquatic flora and fauna and human health.     

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.     

Variable toxicity of ionic liquid-forming chemicals to Lemna minor and the influence of dissolved organic matter

Ionic liquids (ILs) are nonvolatile organic salts that remain liquid over a wide range of temperatures. Ionic liquids are promoted as environmentally friendly alternatives to the volatile organic solvents that are currently in widespread industrial usage. Although ILs are unlikely to contribute to air pollution, their potential effects on aquatic ecosystems are largely unknown. Furthermore, information is lacking on how ILs will interact with common features of aquatic environments, such as dissolved organic matter (DOM). We assessed the effect of five IL-forming chemicals on the growth of duckweed, Lemna minor, a common aquatic vascular plant. In general, 1-alkyl-3-methylimidazolium chemicals with longer alkyl chains were more toxic to L. minor than those with short alkyl chain lengths. The concentration that produced a 50% reduction (the EC50) in root growth was 8.56 ppm when a butyl chain was present but was 0.25 ppm (i.e., much more toxic) when an octyl chain was substituted. Butyl-substituted 3-methylpyridinium (root growth EC50 of 7.49 ppm) and 3-methylimidazolium cations had similar toxicity, whereas a tetrabutyl ammonium cation was considerably less toxic (root growth EC50 of 32.71 ppm). When we tested whether DOM reduced the toxicity of these cations, we saw no effect of a low-molecular-weight organic acid or commercial humic matter. In contrast, natural DOM reduced the toxicity of imidazolium, but only at low concentrations. Design and use of ILs and other new chemicals should incorporate not only standard toxicity tests but also information on how such chemicals will interact with other components of aquatic ecosystems.     

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 on Acute Toxicity of Zinc to Larval Fathead Minnows (Pimephales promelas)

We conducted laboratory toxicity tests in support of the development of a biotic ligand model (BLM) to predict acute toxicity of zinc (Zn) to fathead minnows (Pimephales promelas). To test the effect of dissolved organic matter (DOM) on Zn toxicity, we exposed larval fathead minnows to Zn in water containing elevated concentrations of dissolved organic carbon (DOC) in 96-h static-renewal toxicity tests. We tested DOM isolated from four surface waters: Cypress Swamp, Delaware; Edisto River, South Carolina; Suwannee River, Georgia; and Wilmington, Delaware, wastewater treatment effluent. The DOM isolates from the Edisto River and Wilmington wastewater treatment effluent contained elevated concentrations of NaCl (20–110× control NaCl) due to the use of a Na⁺-exchange resin to remove Ca²⁺ and Mg²⁺ during the DOM isolation process. Therefore, we also performed Zn toxicity tests in which we added up to 20 mM NaCl to exposure solutions containing Cypress Swamp and Suwannee River DOM. A threshold concentration of 11 mg DOC/L was needed to decrease Zn toxicity, after which the 96 h Zn LC50 was positively correlated with DOC concentration. Elevated NaCl concentrations did not alter Zn toxicity in the presence of DOM. In conjunction with data from other studies with fish and invertebrates, results of this study were used to calibrate Version 2.1.1 of the Zn BLM. BLM-predicted LC50s for our exposure waters containing elevated DOM concentrations were within the range of acceptable deviation relative to the observed LC50s (i.e., 0.5–2× observed LC50s); however, BLM-predicted LC50s for our exposure waters containing < 1 mg DOC/L were 2–3× lower than the observed LC50s (i.e., the BLM over-predicted the toxicity). Therefore, the current composite-species BLM for Zn could be improved for fathead minnows if that species were modeled separately from the other species used to calibrate Version 2.1.1.     

Cross-phylum comparison of a chronic biotic ligand model to predict chronic toxicity of copper to a freshwater rotifer, Brachionus calyciflorus (Pallas)

Short chronic 48-h toxicity tests with the freshwater rotifer Brachionus calyciflorus (Pallas) were conducted to assess the modifying effects of pH and natural dissolved organic carbon (DOC) concentration on reproductive toxicity of Cu. Toxicity tests were carried out in four test waters according to a 2 x 2 design, in which pH (6 and 7.8) and DOC (5 and 15 mg C/L) were the test variables. Concentrations of dissolved Cu with no observed effect at 48 h (NOEC) varied 12-fold between 8.2 and 103 microg/L. Higher DOC and higher pH resulted in a reduction of toxicity, which is in line with the concepts of the biotic ligand model (BLM). A chronic Cu-BLM, originally developed for the cladoceran Daphnia magna, was calibrated to the rotifer dataset and was found to be able to predict all rotifer NOECs with an error factor of less than 1.6. This finding may be of great interest for risk assessment and the establishment of water quality criteria, as it suggests that chronic Cu-BLMs are comparable across phyla (i.e., arthropoda to rotifera).