Ambient Water Quality Criteria Research Articles

English

The National Tunnel is a part of the Central City / Idaho Springs Superfund site. Because passive treatment is an important possibility for removal of contaminants from the water, the USEPA and the Colorado Division of Public Health and Environment (CDPHE) have been sponsoring a bench-scale study of different organic substrates for sulfate-reducing bioreactors (SRBRs). The substrates being tested include ethanol, woodchips and hay, woodchips and corn stover, and crab-shell chitin. After 6-18 months of operation, all of the reactors are showing significant amounts of sulfate reduction. In all of the reactors, Cu and Zn are removed to below their respective ambient water quality criteria of 0.010 and 0.100 mg/L. As is commonly observed in SRBRs, Mn removal is significantly less, with the exception of the chitin reactors. The reason for chitin's superior Mn removal may be the dissolution of calcite from the crab shell. In the chitin reactors, Ca has increased from 210 to 870 mg/L and alkalinity has increased from zero to up to 5,000 mg CaCO3 / L. Furthermore, the pH of the effluent leaving the chitin systems averages 6.9. In most SRBRs, Mn is precipitated as MnCO3 and significant removal does not occur until the pH is raised to between 7 and 8. This is the case in the other types of SRBRs being tested at the National Tunnel, as their Mn removal efficiencies have only approached 50 % at pH values ranging from 6.5 to 7.5. However, in the chitin reactors, 86% of the influent Mn is being removed from 21.5 mg/L to an average of 3 mg/L. The high removal is very similar to the removal of Mn in pulsed limestone beds that are maximized for the dissolution of calcite. These chitin reactors have been operating for six months while the other substrate reactors have been operating for over one year.

Critical tissue copper residues for marine bivalve ( Mytilus galloprovincialis) and echinoderm ( Strongylocentrotus purpuratus) embryonic development: Conceptual, regulatory and environmental implications

Critical tissue copper (Cu) residues associated with adverse effects on embryo-larval development were determined for the Mediterranean mussel ( Mytilus galloprovincialis) and purple sea urchin ( Strongylocentrotus purpuratus) following laboratory exposure to Cu-spiked seawater collected from San Diego Bay, California, USA. Whole body no-observed-effect-residues (NOER) were similar, with means of 21 and 23 μg g −1 dw, for M. galloprovincialis and S. purpuratus, respectively. Mean whole body median effect residues (ER50) were 49 and 142 μg g −1 dw for M. galloprovincialis and S. purpuratus, respectively. The difference in ER50s between species was reduced to a factor of <2 when expressed as soft tissue residues. Coefficients of variation among whole body-ER50s were 3-fold lower than median waterborne effect concentrations (EC50) for both species exposed to samples varying in water quality characteristics. This suggests that tissue concentrations were a better predictor of toxicity than water concentrations. The CBRs described herein do not differentiate between the internal Cu concentrations that are metabolically available and those that are accumulated and then detoxified. They do appear, however, to be well enough related to the level of accumulation at the site of action of toxicity that they serve as useful surrogates for the copper concentration that affects embryonic development of the species tested. Results presented have potentially important implications for a variety of monitoring and assessment strategies. These include regulatory approaches for deriving saltwater ambient water quality criteria for Cu, contributions towards the development of a saltwater biotic ligand model, the conceptual approach of using CBRs, and ecological risk assessment.

An assessment of the application factor used to derive the saltwater acute ambient water quality copper criterion

The basis for all US Environmental Protection Agency (USEPA) acute ambient water quality criteria is the chemical specific final acute value (FAV; an estimate of the concentration of the chemical corresponding to a cumulative probability of 0.05 of acute toxicity values for all genera with which acceptable acute tests have been conducted). The acute criterion for all chemicals is equal to the chemical's FAV divided by an application factor of 2. The intention of dividing the FAV by a factor of 2 is to convert the acute toxicity value to an incipient acute toxicity value, resulting in an acute criterion concentration that will protect against toxic effects to aquatic organisms. In the case of copper (Cu) in saltwater, the FAV is reduced from the normal 0.05 probability to equal to the genus mean acute value (GMAV; the geometric mean of copper effect concentration 50% [EC50] values) of the economically important marine bivalves of the genus Mytilus. Analyses to determine an application factor specific to Mytilus and copper were performed to assess the adequacy of the application factor of 2. An estimate of a dissolved copper application factor that is specific to and protective of Mytilus was determined using the results of sixty-four 48-h embryo survival and shell development copper toxicity tests of natural water samples collected from sites around the United States. A variety of point-estimate effects concentrations (EC1, EC5, EC10, EC20, and chronic values [ChV]) and statistical toxic-effect endpoints (no observed effect concentration [NOEC] and lowest observed effect concentration [LOEC]) were derived from the test results and compared. The most similar toxic effect endpoint estimates were EC1 approximately equal to NOEC, EC10 approximately equal to ChV, and EC20 approximately equal to LOEC. Probabilistic methods were used to determine a specific application factor with a high probability of providing protection. This analysis suggests that an application factor of 1.5 (rather than 2) is adequate to provide a high degree of protection against acute effects of dissolved copper to Mytilus. In context, this translates to an acute saltwater dissolved copper criterion of 6.4 microg Cu/L compared to the current acute criterion of 4.8 microg Cu/L.

An evaluation of freshwater mussel toxicity data in the derivation of water quality guidance and standards for copper

The state of Oklahoma has designated several areas as freshwater mussel sanctuaries in an attempt to provide freshwater mussel species a degree of protection and to facilitate their reproduction. We evaluated the protection afforded freshwater mussels by the U.S. Environmental Protection Agency (U.S. EPA) hardness-based 1996 ambient copper water quality criteria, the 2007 U.S. EPA water quality criteria based on the biotic ligand model and the 2005 state of Oklahoma copper water quality standards. Both the criterion maximum concentration and criterion continuous concentration were evaluated. Published acute and chronic copper toxicity data that met American Society for Testing and Materials guidance for test acceptability were obtained for exposures conducted with glochidia or juvenile freshwater mussels. We tabulated toxicity data for glochidia and juveniles to calculate 20 species mean acute values for freshwater mussels. Generally, freshwater mussel species mean acute values were similar to those of the more sensitive species included in the U.S. EPA water quality derivation database. When added to the database of genus mean acute values used in deriving 1996 copper water quality criteria, 14 freshwater mussel genus mean acute values included 10 of the lowest 15 genus mean acute values, with three mussel species having the lowest values. Chronic exposure and sublethal effects freshwater mussel data available for four species and acute to chronic ratios were used to evaluate the criterion continuous concentration. On the basis of the freshwater mussel toxicity data used in this assessment, the hardness-based 1996 U.S. EPA water quality criteria, the 2005 Oklahoma water quality standards, and the 2007 U.S. EPA water quality criteria based on the biotic ligand model might need to be revised to afford protection to freshwater mussels.

Trend Analysis of Nutrient Concentrations and Loads in Selected Canals of the Southern Indian River Lagoon, Florida

Long-term nutrient concentration trends and load variations at six monitoring stations on four canals in the Southern Indian River Lagoon (Florida, USA) were evaluated using the Estimate Trend (Estrend) and Load Estimator (Loadest) programs. The results of trend analysis on nutrient concentrations suggested that the nutrient trend patterns were spatially variable. Increasing trends were most often observed in orthophosphate and/or total phosphorus at five stations. Significantly increased annual loads were observed for orthophosphate at four stations from 1979 through 2004. The median concentrations of ammonia (0.05 to 0.10 mg l−1) were greater than the State of Florida surface water quality criteria of class III freshwater body for ammonia. The median concentrations of total phosphorus (138 to 376 μg l−1) were greater than the USEPA ambient water quality criteria recommendation for the study area (Nutrient Ecoregion XIII). Nutrient (phosphorus and nitrogen) loads observed in this study are likely to impair the water quality in the Southern Indian River Lagoon.

Reprint of “Chronic toxicity of silver nitrate to Ceriodaphnia dubia and Daphnia magna, and potential mitigating factors”

We investigated the chronic toxicity of Ag, as silver nitrate, using two freshwater aquatic cladoceran species, Ceriodaphnia dubia and Daphnia magna, to generate data for the development of a chronic ambient water quality criterion for Ag. Preliminary studies with C. dubia showed variable results which were related to the equilibration time between food and silver. Follow-up testing was conducted using a 3 h equilibration time, which stabilized dissolved Ag concentrations and the toxicity of Ag +. Results with C. dubia conducted individually (1 per cup, n = 10) and in mass (30 per chamber, n = 2) gave similar results once similar standardized equilibration times were used. The maximum acceptable toxicant concentration (MATC) of Ag to C. dubia and D. magna was 9.61 and 3.00 μg dissolved Ag/L, respectively. The chronic toxicity of Ag + to C. dubia was also evaluated in the presence of: (1) dissolved organic carbon (DOC) and (2) sulfide. The addition of DOC (0.4 mg/L) resulted in a ∼50% decrease in toxicity while the addition of sulfide (75.4 nM) deceased toxicity by 42%. Whole-body Ag concentration in D. magna was positively correlated with increased levels of Ag exposure, however; we observed a non-statistical decrease in whole-body Na levels, an estimator of sodium homeostasis.

Chronic toxicity of silver nitrate to Ceriodaphnia dubia and Daphnia magna, and potential mitigating factors

We investigated the chronic toxicity of Ag, as silver nitrate, using two freshwater aquatic cladoceran species, Ceriodaphnia dubia and Daphnia magna, to generate data for the development of a chronic ambient water quality criterion for Ag. Preliminary studies with C. dubia showed variable results which were related to the equilibration time between food and silver. Follow-up testing was conducted using a 3 h equilibration time, which stabilized dissolved Ag concentrations and the toxicity of Ag +. Results with C. dubia conducted individually (1 per cup, n = 10) and in mass (30 per chamber, n = 2) gave similar results once similar standardized equilibration times were used. The maximum acceptable toxicant concentration (MATC) of Ag to C. dubia and D. magna was 9.61 and 3.00 μg dissolved Ag/L, respectively. The chronic toxicity of Ag + to C. dubia was also evaluated in the presence of: (1) dissolved organic carbon (DOC) and (2) sulfide. The addition of DOC (0.4 mg/L) resulted in a ∼50% decrease in toxicity while the addition of sulfide (75.4 nM) deceased toxicity by 42%. Whole-body Ag concentration in D. magna was positively correlated with increased levels of Ag exposure, however; we observed a non-statistical decrease in whole-body Na levels, an estimator of sodium homeostasis.

Predicting Pb bioavailability to freshwater microalgae in the presence of fulvic acid: Algal cell density as a variable

In order to better understand the relationship between lead speciation and its bioavailability in natural waters, the interactions between Pb(II), fulvic acid and the freshwater alga, Chlorella kesslerii were studied at various algal cell densities. An increase in cellular lead or fulvic acid adsorbed to algae was observed with decrease of the cell density from ca. 10 7 to 10 5 cells ml −1. In the presence of fulvic acid, cellular Pb was greater than that expected for the same free lead ion concentrations in the absence of fulvic acid in agreement to our previous study. This effect was found to be more pronounced at lower cell density, in accordance with increased fulvic acid adsorption to algae. Good fit between experimental observations and model predictions of cellular Pb at various cell densities, was observed by assuming that fulvic acid adsorbed to algae give rise to additional binding sites for Pb(II). The findings of this study indicate that a further extension of the biotic ligand model which includes the formation of a ternary complex and cell density (or concentration) as an input parameter is needed to improve its site-specific predictive capacity, especially in the case of dissolved organic matter-rich surface waters. This extension of predictive capacity would allow to reduce the deviations from the BLM model predictions for microalgae in the presence of dissolved organic matter and hence will serve as a mechanistic tool for establishing ambient site-specific water quality criteria.

Release of copper from sintered tungsten–bronze shot under different pH conditions and its potential toxicity to aquatic organisms

Sintered tungsten-bronze is a new substitute for lead shot, and is about to be deposited in and around the wetlands of North America. This material contains copper in the alloyed form of bronze. This in vitro study was performed according to U.S. Fish and Wildlife Service criteria to determine the dissolution rate of copper from the shot, and to assess the toxic risk that it may present to aquatic organisms. The dissolution of copper from tungsten-bronze shot, pure copper shot, and glass beads was measured in a buffered, moderately hard, synthetic water of pH 5.5, 6.6, and 7.8 over a 28-day period. The dissolution of copper from both the control copper shot and the tungsten-bronze shot was affected significantly by the pH of the water and the duration of dissolution (all p values<0.000). The rate of copper release from tungsten bronze shot was 30 to 50 times lower than that from the copper shot, depending on pH (p<0.0000). The observed expected environmental concentration of copper released from tungsten-bronze shot after 28 days was 0.02 microg/L at pH 7.8, and 0.4 microg/L at pH 5.6, using a loading and exposure scenario specific in a U.S. Fish and Wildlife Service protocol. Ratio Quotient values derived from the highest EEC observed in this study (0.4 microg/L), and the copper toxic effect levels for all aquatic species listed in the U.S. Environmental Protection Agency ambient water quality criteria database, were all far less than the 0.1 criterion value. Given the conditions stipulated by the U.S. Fish and Wildlife Service and the U.S. Environmental Protection Agency, heavy loading from discharged tungsten-bronze shot would not pose a toxic risk to potable water, or to soil. Consequently, it would appear that no toxic risks to aquatic organisms will attend the use of tungsten-bronze shot of the approved composition. Given the likelihood that sintered tungsten-bronze of the same formula will be used for fishing weights, bullets, and wheel balance weights, it is expected that the use of this new material in these applications will not be associated with toxic risks to aquatic life.

RISK ASSESSMENT OF WATER QUALITY IN THREE NORTH CAROLINA, USA, STREAMS SUPPORTING FEDERALLY ENDANGERED FRESHWATER MUSSELS (UNIONIDAE)

Water quality data were collected from three drainages supporting the endangered Carolina heelsplitter (Lasmigona decorata) and dwarf wedgemussel (Alasmidonta heterodon) to determine the potential for impaired water quality to limit the recovery of these freshwater mussels in North Carolina, USA. Total recoverable copper, total residual chlorine, and total ammonia nitrogen were measured every two months for approximately a year at sites bracketing wastewater sources and mussel habitat. These data and state monitoring datasets were compared with ecological screening values, including estimates of chemical concentrations likely to be protective of mussels, and federal ambient water quality criteria to assess site risks following a hazard quotient approach. In one drainage, the site-specific ammonia ecological screening value for acute exposures was exceeded in 6% of the samples, and 15% of samples exceeded the chronic ecological screening value; however, ammonia concentrations were generally below levels of concern in other drainages. In all drainages, copper concentrations were higher than ecological screening values most frequently (exceeding the ecological screening values for acute exposures in 65-94% of the samples). Chlorine concentrations exceeding the acute water quality criterion were observed in 14 and 35% of samples in two of three drainages. The ecological screening values were exceeded most frequently in Goose Creek and the Upper Tar River drainages; concentrations rarely exceeded ecological screening values in the Swift Creek drainage except for copper. The site-specific risk assessment approach provides valuable information (including site-specific risk estimates and ecological screening values for protection) that can be applied through regulatory and nonregulatory means to improve water quality for mussels where risks are indicated and pollutant threats persist.

Arsenic Bioaccumulation in Freshwater Fishes

ABSTRACT The arsenic ambient water quality criterion (AWQC) for protection of human health via ingestion of aquatic organisms is currently 0.14 μ g/L. This AWQC is derived using a bioconcentration factor (BCF) of 44, which is a consumption-weighted average based on two data points for oysters and fish that was proposed by the U.S. Environmental Protection Agency in 1980 for broad application to freshwater and marine environments. This BCF is based on the assumption that bioaccumulation is a simple linear function of the exposure concentration. In the nearly quarter of a century since this BCF was promulgated, there have been additions to the arsenic bioaccumulation database and a broader scientific understanding of bioaccumulation mechanisms and how they can be applied to estimating tissue concentrations in aquatic organisms. From this database, we identified 12 studies of arsenic bioaccumulation in freshwater fishes in order to explore differences in laboratory-generated BCFs and field-generated bioaccumulation factors (BAFs) and to assess their relationship to arsenic concentrations in water. Our analysis indicates that arsenic concentrations in tissue and arsenic BAFs may be power functions of arsenic concentration in water. A power function indicates that the highest BCF values may occur at low background levels and may decrease as environmental concentrations increase above the ambient range.

The Potential for Chromium to Affect the Fertilization Process of Chinook Salmon (Oncorhynchus tshawytscha) in the Hanford Reach of the Columbia River, Washington, USA

The Hanford Nuclear Reservation in south central Washington was claimed by the federal government as a site for the production of plutonium. During the course of production and operation of the facilities at Hanford, radionuclides and chromium were discharged directly into the river and also contaminated the groundwater. This study was designed to assess the effects of chromium (Cr) on Chinook salmon (Oncorhynchus tshawytscha) fertilization under exposure conditions similar to those of the Hanford Reach of the Columbia River. Chinook salmon gametes were exposed to aqueous Cr concentrations ranging from 0 to 266 microg Cr l(-1). The current ambient water-quality criteria (AWQC) established for the protection of aquatic life (United States Environmental Protection Agency [USEPA] 1986) is 11 microg Cr l(-1). Cr has been measured in pore water from bottom sediments of the Columbia River at concentrations >600 microg Cr l(-1). Under exposure conditions designed to closely mimic events that occur in the river, the fertilization of Chinook salmon eggs was not affected by concentrations of Cr ranging from 11 to 266 microg Cr l(-1). Data suggest that the instantaneous nature of fertilization likely limits the potential effects of Cr on fertilization success. As a result, the current AWQC of 11 mug Cr l(-1) is most likely protective of Chinook salmon fertilization.

Reassessment of Cyanide Ambient Water Quality Criteria: An Integrated Approach to Protection of the Aquatic Environment

The U.S. Environmental Protection Agency’s (USEPA) current ambient water quality criteria (AWQC) for cyanide were developed in 1984. Since this time, additional research on cyanide toxicity and analytical chemistry has suggested that cyanide AWQC values need to be updated to reflect the current state-of-the-science and to ensure that the methods for implementing the cyanide AWQC reflect the bioavailable and toxic forms of cyanide. Therefore, the Water Environment Research Foundation (WERF) sponsored a reassessment of the AWQC for cyanide by initiating a thorough review of the current scientific literature on cyanide and conducting additional laboratory studies to further understand cyanide chemistry and toxicity. Consistent with the USEPA’s draft strategy for developing AWQC, this evaluation also considered whether the cyanide AWQC are protective of benthos, threatened and endangered (T&E) species, and aquatic-dependent wildlife. This reassessment of AWQC for cyanide resulted in proposed freshwater acute and chronic criteria of 23 and 4.8 µg CN/L, respectively, which are comparable to the current freshwater acute and chronic criteria of 22 and 5.2 µg CN/L (free cyanide). For saltwater organisms, the reassessment resulted in proposed acute and chronic criteria of 20 and 4.1 µg CN/L (free cyanide), respectively, compared to the current saltwater acute and chronic criteria which are both 1.0 µg CN/L. The difference in the current and proposed saltwater criteria values is attributed to recent cyanide toxicity testing with several crab species in the genus Cancer and the copepod Acartia tonsa, which suggests this genus is not as sensitive to cyanide as previous cyanide toxicity testing indicated. A sediment-based cyanide criterion does not appear warranted if it is assumed that benthic organisms are not inordinately more sensitive to cyanide than the water column organisms that drive the basis for the proposed freshwater and saltwater criteria (the available cyanide toxicity data do not suggest that they would be), and given that bioavailable forms of cyanide are not expected to accumulate appreciably in sediment. Cyanide should thus be effectively regulated based on water column-based criteria and concentrations. Based on a combination of available empirical and estimated cyanide toxicity values for T&E species, the proposed freshwater criteria appear to be protective

Survey of methodologies for developing media screening values for ecological risk assessment

This review evaluates the methodologies of 13 screening value (SV) compilations that have been commonly used in ecological risk assessment (ERA), including compilations from state and U.S. federal agencies, the Oak Ridge National Laboratory (ORNL), Canada, The Netherlands, and Australia. The majority of surfacewater SVs were primarily derived for the protection of aquatic organisms using 2 approaches: (1) a statistical assessment of toxicity values by species groupings, such as "ambient water quality criteria," or (2) extrapolation of a lowest observed adverse effect level determined from limited toxicity data using an uncertainty factor. Sediment SVs were primarily derived for the protection of benthic invertebrates using 2 approaches: (1) statistical interpretations of databases on the incidence of biological effects and chemical concentrations in sediment, or (2) values derived from equilibrium partitioning based on a surfacewater SV. Soil SVs were derived using a diversity of approaches and were usually based on the lowest value determined from soil toxicity to terrestrial plants or invertebrates and, less frequently, from modeled, incidental soil ingestion or chemical accumulation in terrestrial organisms. The various SV compilations and methodologies had varying levels of conservatism and were not consistent in the pathways and receptors considered in the SV derivation. Many SVs were derived from other compilations and were based on outdated values, or they relied on only older toxicity data. Risk assessors involved in ERA should carefully evaluate the technical basis of SVs and consider the uncertainty in any value used to determine the presence or absence of risk and the need for further assessment.

Use of laboratory toxicity tests with bivalve and echinoderm embryos to evaluate the bioavailability of copper in San Diego Bay, California, USA

Copper concentrations in parts of San Diego Bay (CA, USA) exceed ambient water quality criteria (WQC; currently 3.1 microg/L dissolved, U.S. Environmental Protection Agency [U.S. EPA]). In order to better understand the bioavailability of copper to water-column organisms in the bay, toxicity tests were performed with copper added to surface water collected from various sites in the estuary over a three-year period. The species and endpoints used, bivalve and echinoderm embryo-larval development, are among the most sensitive in the U.S. EPA's national toxicity dataset, which is used to derive WQC. No toxicity was observed in ambient bay water samples, as indicated by high proportions of normally developed larvae in control treatments, averaging 93+/-5% across all sites and all sampling events. Median effects concentrations (EC50), obtained by copper spiking of ambient water samples, ranged from 1.7 to 3.4 times lower at sites located near the mouth compared to sites near the back of the bay. These data indicate a gradient in complexation capacity increasing from the mouth to the back of the bay, which is consistent with similar trends in dissolved organic carbon and total suspended solids. For the bay as a whole, estimates for total recoverable and dissolved water-effect ratios (WER) ranged from 2.07 to 2.27 and 1.54 to 1.67, respectively. Water-effect ratios of this magnitude suggest that adoption of a somewhat higher site-specific WQC for San Diego Bay still would achieve the level of protection that is intended by the WQC guidelines.

Survey of Methodologies for Developing Media Screening Values for Ecological Risk Assessment

This review evaluates the methodologies of 13 screening value (SV) compilations that have been commonly used in ecological risk assessment (ERA), including compilations from state and U.S. federal agencies, the Oak Ridge National Laboratory (ORNL), Canada, The Netherlands, and Australia. The majority of surfacewater SVs were primarily derived for the protection of aquatic organisms using 2 approaches: (1) a statistical assessment of toxicity values by species groupings, such as “ambient water quality criteria,” or (2) extrapolation of a lowest observed adverse effect level determined from limited toxicity data using an uncertainty factor. Sediment SVs were primarily derived for the protection of benthic invertebrates using 2 approaches: (1) statistical interpretations of databases on the incidence of biological effects and chemical concentrations in sediment, or (2) values derived from equilibrium partitioning based on a surfacewater SV. Soil SVs were derived using a diversity of approaches and were usually based on the lowest value determined from soil toxicity to terrestrial plants or invertebrates and, less frequently, from modeled, incidental soil ingestion or chemical accumulation in terrestrial organisms. The various SV compilations and methodologies had varying levels of conservatism and were not consistent in the pathways and receptors considered in the SV derivation. Many SVs were derived from other compilations and were based on outdated values, or they relied on only older toxicity data. Risk assessors involved in ERA should carefully evaluate the technical basis of SVs and consider the uncertainty in any value used to determine the presence or absence of risk and the need for further assessment.

Population models of farmed abalone Haliotis diversicolor supertexta exposed to waterborne zinc

A stage-classified demographic method was performed to investigate the effects of increased waterborne zinc (Zn) concentrations on the population dynamics of abalone Haliotis diversicolor supertexta. We reanalyzed the results of a 7-day acute and a 28-day chronic toxicity bioassays to examine the survival and growth performances when exposing abalone to different levels of zinc stresses. An energy-based biological approach was adopted to model the effects of zinc on fecundity. These data provided stage-specific schedules of vital rates that were used to parameterize a projection matrix model for abalone. Simulations were carried out to produce temporal population abundance changes under seven exposure scenarios including a control group and six treated cohorts ranged from 0.03 to 1 mg l −1 Zn. Model manipulations indicated that a reduction of individual growth rate was observed at an exposed Zn concentration greater than 0.12 mg l −1, whereas the significant influence of survivorship was occurred until the Zn concentration reached 0.25 mg l −1. For all treatments, Zn induced a slight decrease in fecundity. The asymptotic population growth rate decreased from λ=1.00 for the control group to λ=0.9968 for abalone population exposed to 1 mg l −1 Zn, indicating a potential risk of population intrinsic growth rates for abalone exposed to higher levels of waterborne Zn. These findings provide a pivotal effort for setting of the ambient water quality criterion for protecting the aquacultural species.

Biotic Ligand Model, a Flexible Tool for Developing Site-Specific Water Quality Guidelines for Metals

The biotic ligand model (BLM) is a mechanistic approach that greatly improves our ability to generate site-specific ambient water quality criteria (AWQC)for metals in the natural environment relative to conventional relationships based only on hardness. The model is flexible; all aspects of water chemistry that affect toxicity can be included, so the BLM integrates the concept of bioavailability into AWQC--in essence the computational equivalent of water effect ratio (WER) testing. The theory of the BLM evolved from the gill surface interaction model (GSIM) and the free ion activity model (FIAM). Using an equilibrium geochemical modeling framework, the BLM incorporates the competition of the free metal ion with other naturally occurring cations (e.g., Ca2+, Na+, Mg2-, H+), togetherwith complexation by abiotic ligands [e.g., DOM (dissolved organic matter), chloride, carbonates, sulfide] for binding with the biotic ligand, the site of toxic action on the organism. On the basis of fish gill research, the biotic ligands appear to be active ion uptake pathways (e.g., Na+ transporters for copper and silver, Ca2+ transporters for zinc, cadmium, lead, and cobalt), whose geochemical characteristics (affinity = log K, capacity = Bmax) can be quantified in short-term (3-24 h) in vivo gill binding tests. In general, the greater the toxicity of a particular metal, the higher the log K. The BLM quantitatively relates short-term binding to acute toxicity, with the LA50 (lethal accumulation) being predictive of the LC50 (generally 96 h for fish, 48 h for daphnids). We critically evaluate currently available BLMs for copper, silver, zinc, and nickel and gill binding approaches for cadmium, lead, and cobalt on which BLMs could be based. Most BLMs originate from tests with fish and have been recalibrated for more sensitive daphnids by adjustment of LA50 so as to fit the results of toxicity testing. Issues of concern include the arbitrary nature of LA50 adjustments; possible mechanistic differences between daphnids and fish that may alter log K values, particularly for hardness cations (Ca2+, Mg2+); assumption of fixed biotic ligand characteristics in the face of evidence that they may change in response to acclimation and diet; difficulties in dealing with DOM and incorporating its heterogeneity into the modeling framework; and the paucity of validation exercises on natural water data sets. Important needs include characterization of biotic ligand properties at the molecular level; development of in vitro BLMs, extension of the BLM approach to a wider range of organisms, to the estuarine and marine environment, and to deal with metal mixtures; and further development of BLM frameworks to predict chronic toxicity and thereby generate chronic AWQC.

Derivation of an ambient water quality criterion for mercury: taking account of site-specific conditions.

Mercury is considered to be a serious risk to wildlife. As a result, the Great Lakes Water Quality Initiative and others have developed ambient water quality criteria (AWQC) for the protection of wildlife. These AWQC have been controversial, however, because the AWQC were single values that did not account for site-specific conditions, derivation of the AWQC relied on a single no-observed-adverse-effect level, and the AWQC had an unknown level of conservatism because of reliance on both average and conservative assumptions and uncertainty factors. Rather than develop a single-value AWQC for total mercury, we derived an AWQC model that explicitly incorporates factors controlling bioavailability, methylation rates, and bioaccumulation in the aquatic environment (e.g., pH, dissolved organic carbon). To derive our AWQC model, field data were collected from 31 lakes in Ontario and an additional 10 lakes in Nova Scotia (North America). In the field study, levels of total and methylmercury in water and fish as well as levels of key water quality variables were determined. We conducted multiple-regression analysis to derive a model that estimates mercury levels in prey of mink. Mink are very sensitive to mercury exposure. An independent dataset consisting of 51 water bodies in the United States was then used to confirm the validity and robustness of the AWQC model. Next, we combined the results of chronic-feeding studies with similar protocols and endpoints in a meta-analysis to derive a dose-response curve for mink exposed to mercury in the diet. In the final step, we used a probabilistic risk model to estimate the concentrations of methylmercury in water that would lead to levels in fish sufficient for a 10% probability of exceeding the lethal dose affecting 5% of the mink population. The result is an AWQC equation for mercury for the protection of wildlife that can be used with a variety of site-specific conditions.

Effects of Chronic Waterborne and Dietary Metal Exposures on Gill Metal-Binding: Implications for the Biotic Ligand Model

The biotic ligand modeling (BLM) approach has gained recent widespread interest among the scientific and regulatory communities because of its potential for developing ambient water quality criteria (AWQC), which are site-specific, and in performing aquatic risk assessment for metals. Currently, BLMs are used for predicting acute toxicity (96 h LC50 for fish) in any defined water chemistry. The conceptual framework of the BLM has a strong physiological basis because it considers that toxicity of metals occurs due to the binding of free metal ions at the physiologically active sites of action (biotic ligand, e.g., fish gill) on the aquatic organism, which can be characterized by conditional binding constants (log K) and densities (Bmax). At present, these models assume that only water chemistry variables such as competing cations (e.g., Na+, Ca2+, Mg2+, and H+), inorganic ligands (e.g., hydroxides, chlorides, carbonates), and organic ligands (dissolved organic matter) can influence the bioavailability of free metal ions and thereby the acute toxicity of metals. Current BLMs do not consider the effects of chronic history of the fish in modifying gill-metal binding characteristics and acute toxicity. Here, for Cu, Cd, and Zn, we review a number of recent studies on the rainbow trout that describe significant modifying effects of chronic acclimation to waterborne factors (hardness and chronic metal exposure) and dietary composition (metal and essential ion content) on gill metalbinding characteristics (on both log K and Bmax) and on acute toxicity. We conclude that the properties of gill-metal interaction and toxicological sensitivity appear to be dynamic rather than fixed, with important implications for further development of both acute and chronic BLMs. Now that the initial framework of the BLM has been established, future research needs a more integrative approach with additional emphasis on the dynamic properties of the biotic ligand to make it a successful tool for ecological risk assessment of metals in the natural environment.