Implementation of the CREED approach for environmental assessments.

Environmental exposure data are a key component of chemical and ecological assessments, supporting and guiding environmental management decisions and regulations. Measures taken to protect the environment based on exposure data can have social and economic implications. Flawed information may lead to measures being taken in the wrong place or to important action not being taken. Although the advantages of harmonizing evaluation methods have been demonstrated for hazard information, no comparable approach is established for exposure data evaluation. The goal of Criteria for Reporting and Evaluating Exposure Datasets (CREED) is to improve the transparency and consistency with which exposure data are evaluated regarding usability in environmental assessments. Here, we describe the synthesis of the CREED process, and propose methods and tools to summarize and interpret the outcomes of the data usability evaluation in support of decision-making and communication. The CREED outcome includes a summary that reports any key gaps or shortcomings in the reliability (data quality) and relevance (fitness for purpose) of the data being considered. The approach has been implemented in a workbook template (provided as Supporting Information), for assessors to readily follow the workflow and create a report card for any given dataset. The report card communicates the outcome of the CREED evaluation and summarizes important dataset attributes, providing a concise reference pertaining to the dataset usability for a specified purpose and documenting data limitations that may restrict data use or increase environmental assessment uncertainty. The application of CREED is demonstrated through three case studies, which also were used during beta testing of the methodology. As experience with the CREED approach application develops, further improvements may be identified and incorporated into the framework. Such development is to be encouraged in the interest of better science and decision-making, and to make environmental monitoring and assessment more cost-effective. Integr Environ Assess Manag 2024;20:1019-1034. © 2024 SETAC.

Development and Validation of Multiple Linear Regression Models for Predicting Chronic Zinc Toxicity to Freshwater Microalgae.

Multiple linear regression (MLR) models were developed for predicting chronic zinc toxicity to a freshwater microalga, Chlorella sp., using three toxicity-modifying factors (TMFs): pH, hardness, and dissolved organic carbon (DOC). The interactive effects between pH and hardness and between pH and DOC were also included. Models were developed at three different effect concentration (EC) levels: EC10, EC20, and EC50. Models were independently validated using six different zinc-spiked Australian natural waters with a range of water chemistries. Stepwise regression found hardness to be an influential TMF in model scenarios and was retained in all final models, while pH, DOC, and interactive terms had variable influence and were only retained in some models. Autovalidation and residual analysis of all models indicated that models generally predicted toxicity and that there was little bias based on individual TMFs. The MLR models, at all effect levels, performed poorly when predicting toxicity in the zinc-spiked natural waters during independent validation, with models consistently overpredicting toxicity. This overprediction may be from another unaccounted for TMF that may be present across all natural waters. Alternatively, this consistent overprediction questions the underlying assumption that models developed from synthetic laboratory test waters can be directly applied to natural water samples. Further research into the suitability of applying synthetic laboratory water-based models to a greater range of natural waters is needed. Environ Toxicol Chem 2023;42:2630-2641. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Natural organic matter source, concentration, and pH influences the toxicity of zinc to a freshwater microalga.

Zinc is a contaminant of concern in aquatic environments and is a known toxicant to many aquatic organisms. Dissolved organic matter (DOM) is a toxicity modifying factor for zinc and is an important water chemistry parameter. This study investigated the influence of DOM concentration, source, and water pH on the chronic toxicity of zinc to a freshwater microalga, Chlorella sp. The influence of DOM on zinc toxicity was dependent on both concentration and source. In the absence of DOM, the 72-h EC50 was 112 µg Zn.L-1. In the presence of a DOM high in fulvic-like components, zinc toxicity was either slightly decreased (<4-fold increase in EC10s across 15 mg C.L-1 range) or unchanged (minimal difference in EC50s). In the presence of a DOM high in humic-like (aromatic and high molecular weight) components, zinc toxicity was slightly decreased at the EC10 level and strongly increased at the EC50 level. The influence of pH on zinc toxicity was dependent on the source of DOM present in the water. In the presence of DOM high in humic-like components pH did not influence toxicity. In the presence of DOM high in fulvic-like components, pH had a significant effect on EC50 values. Labile zinc (measured by diffusive gradients in thin-films) followed linear relationships with dissolved zinc but could not explain the changes in observed toxicity, with similar DGT-labile zinc relationships shown for the two DOMs despite each DOM influencing toxicity differently. This indicates changes in toxicity may be unrelated to changes in zinc lability. The results suggest that increased toxicity of zinc in the presence of DOM may be due to direct uptake of Zn-DOM complexes. This study highlights the importance of considering DOM source and characteristics when incorporating DOM into water quality guidelines through bioavailability models.

Comparison of Multiple Linear Regression and Biotic Ligand Models for Predicting Acute and Chronic Zinc Toxicity to Freshwater Organisms.

Multiple linear regression (MLR) models for predicting zinc (Zn) toxicity to freshwater organisms were developed based on three toxicity-modifying factors: dissolved organic carbon (DOC), hardness, and pH. Species-specific, stepwise MLR models were developed to predict acute Zn toxicity to four invertebrates and two fish, and chronic toxicity to three invertebrates, a fish, and a green alga. Stepwise regression analyses found that hardness had the most consistent influence on Zn toxicity among species, whereas DOC and pH had a variable influence. Pooled acute and chronic MLR models were also developed, and a k-fold cross-validation was used to evaluate the fit and predictive ability of the pooled MLR models. The pooled MLR models and an updated Zn biotic ligand model (BLM) performed similarly based on (1) R2 , (2) the percentage of effect concentration (ECx) predictions within a factor of 2.0 of observed ECx, and (3) residuals of observed/predicted ECx versus observed ECx, DOC, hardness, and pH. Although fit of the pooled models to species-specific toxicity data differed among species, species-specific differences were consistent between the BLM and MLR models. Consistency in the performance of the two models across species indicates that additional terms, beyond DOC, hardness, and pH, included in the BLM do not help explain the differences among species. The pooled acute and chronic MLR models and BLM both performed better than the US Environmental Protection Agency's existing hardness-based model. We therefore conclude that both MLR models and the BLM provide an improvement over the existing hardness-only models and that either could be used for deriving ambient water quality criteria. Environ Toxicol Chem 2023;42:393-413. © 2022 SETAC.

The influence of hardness at varying pH on zinc toxicity and lability to a freshwater microalga, Chlorella sp.

Zinc is an essential element for aquatic organisms, however, activities such as mining and refining, as well as zinc's ubiquitous role in modern society can contribute to elevated environmental concentrations of zinc. Water hardness is widely accepted as an important toxicity modifying factor for metals in aquatic systems, though other factors such as pH are also important. This study investigated the influence of increasing water hardness, at three different pH values (6.7, 7.6 and 8.3), on the chronic toxicity of zinc to the growth rate of a microalgae, Chlorella sp. Zinc toxicity decreased with increasing hardness from 5 to 93 mg CaCO3 L-1 at all three pH values tested. The 72 h growth rate inhibition EC50 values ranged from 6.2 µg Zn L-1 (at 5 mg CaCO3 L-1, pH 8.3) to 184 µg Zn L-1 (at 92 mg CaCO3 L-1, pH 6.7). Increases in hardness from 93 to 402 mg CaCO3 L-1 generally resulted in no significant (p > 0.05) reduction in zinc toxicity. DGT-labile zinc measurements did not correspond with the observed changes in zinc toxicity as hardness was varied within a pH treatment. This suggests that cationic competition from increased hardness is decreasing zinc toxicity, rather than changes in metal lability. This study highlighted that current hardness algorithms used in water quality guidelines may not be sufficiently protective of sensitive species, such as Chlorella sp., in high hardness waters.

Modeling the Bioavailability of Nickel and Zinc to Ceriodaphnia dubia and Neocloeon triangulifer in Toxicity Tests with Natural Waters.

We studied biotic ligand model (BLM) predictions of the toxicity of nickel (Ni) and zinc (Zn) in natural waters from Illinois and Minnesota, USA, which had combinations of pH, hardness, and dissolved organic carbon (DOC) more extreme than 99.7% of waters in a nationwide database. We conducted 7-day chronic tests with Ceriodaphnia dubia and 96-hour acute and 14-day chronic tests with Neocloeon triangulifer and estimated median lethal concentrations and 20% effect concentrations for both species. Toxicity of Ni and Zn to both species differed among test waters by factors from 8 (Zn tests with C. dubia) to 35 (Zn tests with N. triangulifer). For both species and metals, tests with Minnesota waters (low pH and hardness, high DOC) showed lower toxicity than Illinois waters (high pH and high hardness, low DOC). Recalibration of the Ni BLM to be more responsive to pH-related changes improved predictions of Ni toxicity, especially for C. dubia. For the Zn BLM, we compared several input data scenarios, which generally had minor effects on model performance scores (MPS). A scenario that included inputs of modeled dissolved inorganic carbon and measured Al and Fe(III) produced the highest MPS values for tests with both C. dubia and N. triangulifer. Overall, the BLM framework successfully modeled variation in toxicity for both Zn and Ni across wide ranges of water chemistry in tests with both standard and novel test organisms. Environ Toxicol Chem 2021;40:3049-3062. © 2021 SETAC. This article has been contributed to by US Government employees and their work is in the public domain in the USA.

The Influence of pH on Zinc Lability and Toxicity to a Tropical Freshwater Microalga.

Increased focus on the development and application of bioavailability-based metal water quality guideline values requires increased understanding of the influence of water chemistry on metal bioavailability and toxicity. Development of empirical models, such as multiple linear regression models, requires the assessment of the influence of individual water quality parameters as toxicity-modifying factors. The present study investigated the effect of pH on the lability and toxicity of zinc (Zn) to a tropical green microalga (Chlorella sp.). Zinc speciation and lability were explored using the Windermere Humic Aqueous Model (WHAM7), ultrafiltration, and diffusive gradients in thin films (DGT). Zinc toxicity increased significantly with increasing pH from 6.7 to 8.3, with 50% growth inhibition effect concentrations decreasing from 185 to 53 µg l-1 across the pH range. Linear relationships between DGT-labile Zn and dissolved Zn did not vary across the tested pH range, nor did the linear relationship between dissolved (<0.45 µm) and ultrafiltered (<3 kDa) Zn. Our findings show that Zn toxicity to this freshwater alga is altered as a function of pH across environmentally realistic pH ranges and that these toxicity changes could not be explained by Zn speciation and lability as measured by DGT and WHAM7. Environ Toxicol Chem 2021;40:2836-2845. © 2021 SETAC.

A Review of Water Quality Factors that Affect Nickel Bioavailability to Aquatic Organisms: Refinement of the Biotic Ligand Model for Nickel in Acute and Chronic Exposures.

A review of nickel (Ni) toxicity to aquatic organisms was conducted to determine the primary water quality factors that affect Ni toxicity and to provide information for the development and testing of a biotic ligand model (BLM) for Ni. Acute and chronic data for 66 aquatic species were compiled for the present review. The present review found that dissolved organic carbon (DOC) and hardness act as toxicity-modifying factors (TMFs) because they reduced Ni toxicity to fish and aquatic invertebrates, and these effects were consistent in acute and chronic exposures. The effects of pH on Ni toxicity were inconsistent, and for most organisms there was either no effect of pH or, in some cases, a reduction in toxicity at low pH. There appears to be a unique pH effect on Ceriodaphnia dubia that results in increased toxicity at pHs above 8, but otherwise the effects of TMFs were consistent enough across all organisms and endpoints that a single set of parameters in the Ni BLM worked well with all acute and chronic toxicity data for fish, amphibians, aquatic invertebrates, and aquatic plants and algae. The unique effects of pH on C. dubia may be due to mixture toxicity involving both Ni and bicarbonate. The implications of this mixture effect on BLM modeling and a proposed set of BLM parameters for C. dubia are addressed in the review. Other than this exception, the Ni BLM with a single set of parameters could successfully predict toxicity to all acute and chronic data compiled in the present review. Environ Toxicol Chem 2021;40:2121-2134. © 2021 SETAC.

Comparison of Multiple Linear Regression and Biotic Ligand Models to Predict the Toxicity of Nickel to Aquatic Freshwater Organisms.

Toxicity-modifying factors can be modeled either empirically with linear regression models or mechanistically, such as with the biotic ligand model (BLM). The primary factors affecting the toxicity of nickel to aquatic organisms are hardness, dissolved organic carbon (DOC), and pH. Interactions between these terms were also considered. The present study develops multiple linear regressions (MLRs) with stepwise regression for 5 organisms in acute exposures, 4 organisms in chronic exposures, and pooled models for acute, chronic, and all data and compares the performance of the Pooled All MLR model to the performance of the BLM. Independent validation data were used for evaluating model performance, which for pooled models included data for organisms and endpoints not present in the calibration data set. Hardness and DOC were most often selected as the explanatory variables in the MLR models. An attempt was also made at evaluating the uncertainty of the predictions for each model; predictions that showed the most error tended to show the highest levels of uncertainty as well. The performances of the 2 models were largely equal, with differences becoming more apparent when looking at the performance within subsets of the data. Environ Toxicol Chem 2021;40:2189-2205. © 2021 SETAC.

Evaluation of Acute and Chronic Toxicity of Nickel and Zinc to 2 Sensitive Freshwater Benthic Invertebrates Using Refined Testing Methods.

The US Environmental Protection Agency (USEPA) is reviewing the protectiveness of the national ambient water quality criteria (WQC) for nickel (Ni) and zinc (Zn) and compiling toxicity databases to update the WQC. An amphipod (Hyalella azteca) and a unionid mussel (Lampsilis siliquoidea) have shown high sensitivity to Ni and Zn in previous studies. However, there remained uncertainties regarding the influence of test duration (48 vs 96 h) and the presence and absence of food in acute exposures with the amphipod, and there were also concerns about poor control of amphipod growth and reproduction and mussel growth in chronic exposures. We conducted acute 48- and 96-h water-only toxicity tests to evaluate the influence of feeding and test durations on the toxicity of dissolved Ni and Zn to the amphipod; we also used recently refined test methods to conduct chronic Ni and Zn toxicity tests to evaluate the sensitivity of the amphipod (6-wk exposure) and the mussel (4- and 12-wk exposures). The 96-h 50% effect concentrations (EC50s) of 916 µg Ni/L and 99 µg Zn/L from acute amphipod tests without feeding decreased from the 48-h EC50s by 62 and 33%, respectively, whereas the 96-h EC50s of 2732 µg Ni/L and 194 µg Zn/L from the tests with feeding decreased from the 48-h EC50s by 10 and 26%, indicating that the presence or absence of food had apparent implications for the 96-h EC50. Our chronic 6-wk EC20s for the amphipod (4.5 µg Ni/L and 35 µg Zn/L) were 50 to 67% lower than the 6-wk EC20s from previous amphipod tests, and our chronic 4-wk EC20s for the mussel (41 µg Ni/L and 66 µg Zn/L) were similar to or up to 42% lower than the 4-wk EC20s from previous mussel tests. The lower EC20s from the present study likely reflect more accurate estimates of inherent sensitivity to Ni and Zn due to the refined test conditions. Finally, increasing the chronic test duration from 4 to 12 wk substantially increased the toxicity of Zn to the mussel, whereas the 4- and 12-wk Ni effect needs to be re-evaluated to understand the large degree of variation in organism responses observed in the present study. Environ Toxicol Chem 2020;39:2256-2268. © 2020 SETAC.

Validation of Bioavailability-Based Toxicity Models for Metals.

Regulatory jurisdictions worldwide are increasingly incorporating bioavailability-based toxicity models into development of protective values (PVALs) for freshwater and saltwater aquatic life (e.g., water quality criteria, standards, and/or guidelines) for metals. Use of such models for regulatory purposes should be contingent on their ability to meet performance criteria as specified through a model-validation process. Model validation generally involves an assessment of a model's appropriateness, relevance, and accuracy. We review existing guidance for validation of bioavailability-based toxicity models, recommend questions that should be addressed in model-validation studies, discuss model study type and design considerations, present several new ways to evaluate model performance in validation studies, and suggest a framework for use of model validation in PVAL development. We conclude that model validation should be rigorous but flexible enough to fit the user's purpose. Although a model can never be fully validated to a level of zero uncertainty, it can be sufficiently validated to fit a specific purpose. Therefore, support (or lack of support) for a model should be presented in such a way that users can choose their own level of acceptability. We recommend that models be validated using experimental designs and endpoints consistent with the data sets that were used to parameterize and calibrate the model and validated across a broad range of geographically and ecologically relevant water types. Environ Toxicol Chem 2019;39:101-117. © 2019 SETAC.

Total Recoverable Aluminum: Not Totally Relevant for Water Quality Standards.

A large water quality data set, representing more than 100 surface-water locations sampled from 2007 to 2017 in the Los Alamos area of New Mexico, USA's Pajarito Plateau, was assembled to evaluate Al concentrations in unfiltered and filtered samples. Aluminum concentrations often exceeded United States Environmental Protection Agency (USEPA) and New Mexico ambient water quality criteria (AWQC), regardless of filter size and sample location. However, AWQC are based on laboratory toxicity studies using soluble Al salts and do not reflect natural conditions in Pajarito Plateau surface waters. The plateau is predominately covered by glassy and recrystallized volcanic ashes (e.g., Bandelier Tuff) containing colloidal to sand-sized aluminosilicates. Samples from natural background drainages and areas downstream of developed regions exhibited similar Al concentrations, suggesting that AWQC exceedances are caused by naturally elevated Al concentrations. Solubility calculations indicated that most samples were oversaturated with respect to amorphous Al(OH)3 (s). Therefore, AWQC exceedances are likely artifacts of the "total recoverable" sample preparation, which includes acidification and partial digestion, thereby liberating nonbioavailable Al from aluminosilicates. Accordingly, Al concentrations were strongly associated with suspended sediment concentrations (SSCs), implying that aluminosilicates in suspended sediment contributed to AWQC exceedances and Al oversaturation. Solid-phase particle characterization, using X-ray diffraction (XRD) and scanning electron microscopy with electron dispersive spectroscopy (SEM/EDS) did not identify potentially bioavailable amorphous Al(OH)3 (s) in any sample tested. Thus, current sample collection and analysis protocols should not be used to evaluate attainment of Al AWQC on the Pajarito Plateau or locations where aluminosilicates are substantial contributors to total recoverable Al. A sample preparation method (e.g., pH 4 extraction) capable of differentiating nonbioavailable and bioavailable forms of Al is recommended. Otherwise, current New Mexico and USEPA sample preparation approaches will continue to generate artifactual AWQC exceedances in surface waters that contain aluminosilicates. Integr Environ Assess Manag 2019;00:1-14. © 2019 SETAC.

Evaluating the effects of pH, hardness, and dissolved organic carbon on the toxicity of aluminum to freshwater aquatic organisms under circumneutral conditions.

Although it is well known that increasing water hardness and dissolved organic carbon (DOC) concentrations mitigate the toxicity of aluminum (Al) to freshwater organisms in acidic water (i.e., pH < 6), these effects are less well characterized in natural waters at circumneutral pHs for which most aquatic life regulatory protection criteria apply (i.e., pH 6-8). The evaluation of Al toxicity under varying pH conditions may also be confounded by the presence of Al hydroxides and freshly precipitated Al in newly prepared test solutions. Aging and filtration of test solutions were found to greatly reduce toxicity, suggesting that toxicity from transient forms of Al could be minimized and that precipitated Al hydroxides contribute significantly to Al toxicity under circumneutral conditions, rather than dissolved or monomeric forms. Increasing pH, hardness, and DOC were found to have a protective effect against Al toxicity for fish (Pimephales promelas) and invertebrates (Ceriodaphnia dubia, Daphnia magna). For algae (Pseudokirchneriella subcapitata), the protective effects of increased hardness were only apparent at pH 6, less so at pH 7, and at pH 8, increased hardness appeared to increase the sensitivity of algae to Al. The results support the need for water quality-based aquatic life protection criteria for Al, rather than fixed value criteria, as being a more accurate predictor of Al toxicity in natural waters. Environ Toxicol Chem 2018;37:49-60. © 2017 SETAC.

Development and application of a biotic ligand model for predicting the chronic toxicity of dissolved and precipitated aluminum to aquatic organisms.

Aluminum (Al) toxicity to aquatic organisms is strongly affected by water chemistry. Toxicity-modifying factors such as pH, dissolved organic carbon (DOC), hardness, and temperature have a large impact on the bioavailability and toxicity of Al to aquatic organisms. The importance of water chemistry on the bioavailability and toxicity of Al suggests that interactions between Al and chemical constituents in exposures to aquatic organisms can affect the form and reactivity of Al, thereby altering the extent to which it interacts with biological membranes. These types of interactions have previously been observed in the toxicity data for other metals, which have been well described by the biotic ligand model (BLM) framework. In BLM applications to other metals (including cadmium, cobalt, copper, lead, nickel, silver, and zinc), these interactions have focused on dissolved metal. A review of Al toxicity data shows that concentrations of Al that cause toxicity are frequently in excess of solubility limitations. Aluminum solubility is strongly pH dependent, with a solubility minimum near pH 6 and increasing at both lower and higher pH values. For the Al BLM, the mechanistic framework has been extended to consider toxicity resulting from a combination of dissolved and precipitated Al to recognize the solubility limitation. The resulting model can effectively predict toxicity to fish, invertebrates, and algae over a wide range of conditions. Environ Toxicol Chem 2018;37:70-79. © 2017 SETAC.

Chronic toxicity of aluminum, at a pH of 6, to freshwater organisms: Empirical data for the development of international regulatory standards/criteria.

The chemistry, bioavailability, and toxicity of aluminum (Al) in the aquatic environment are complex and affected by a wide range of water quality characteristics (including pH, hardness, and dissolved organic carbon). Data gaps in Al ecotoxicology exist for pH ranges representative of natural surface waters (pH 6-8). To address these gaps, a series of chronic toxicity tests were performed at pH 6 with 8 freshwater species, including 2 fish (Pimephales promelas and Danio rerio), an oligochaete (Aeolosoma sp.), a rotifer (Brachionus calyciflorus), a snail (Lymnaea stagnalis), an amphipod (Hyalella azteca), a midge (Chironomus riparius), and an aquatic plant (Lemna minor). The 10% effect concentrations (EC10s) ranged from 98 µg total Al/L for D. rerio to 2175 µg total Al/L for L. minor. From these data and additional published data, species-sensitivity distributions (SSDs) were developed to derive concentrations protective of 95% of tested species (i.e., 50% lower confidence limit of a 5th percentile hazard concentration [HC5-50]). A generic HC5-50 (not adjusted for bioavailability) of 74.4 µg total Al/L was estimated using the SSD. An Al-specific biotic ligand model (BLM) was used to develop SSDs normalized for bioavailability based on site-specific water quality characteristics. Normalized HC5-50s ranged from 93.7 to 534 µg total Al/L for waters representing a range of European ecoregions, whereas a chronic HC5 calculated using US Environmental Protection Agency aquatic life criteria methods (i.e., a continuous criterion concentration [CCC]) was 125 µg total Al/L when normalized to Lake Superior water in the United States. The HC5-50 and CCC values for site-specific waters other than those in the present study can be obtained using the Al BLM. Environ Toxicol Chem 2018;37:36-48. © 2017 SETAC.

Development of biotic ligand model-based freshwater aquatic life criteria for lead following us environmental protection agency guidelines.

The US Environmental Protection Agency's (USEPA's) current ambient water quality criteria (AWQC) for lead (Pb) in freshwater were developed in 1984. The criteria are adjusted for hardness, but more recent studies have demonstrated that other parameters, especially dissolved organic carbon (DOC) and pH, have a much stronger influence on Pb bioavailability. These recent studies have been used to support development of a biotic ligand model (BLM) for Pb in freshwater, such that acute and chronic Pb toxicity can be predicted over a wide range of water chemistry conditions. Following USEPA guidelines for AWQC development and using a methodology consistent with that used by the USEPA in developing its recommended BLM-based criteria for copper in 2007, we propose acute and chronic BLM-based AWQC for Pb in freshwater. In addition to the application of the BLM approach that can better account for site-specific Pb bioavailability, the toxicity data sets presented are much more robust than in 1984, and there are now sufficient chronic Pb toxicity data available that use of an acute-to-chronic ratio is no longer necessary. Over a range of North American surface waters with representative water chemistry conditions, proposed acute BLM-based Pb criteria ranged from approximately 20 to 1000 µg/L and chronic BLM-based Pb criteria ranged from approximately 0.3 to 40 µg/L. The lowest criteria were for water with low DOC (1.2 mg/L), pH (6.7), and hardness (4.3 mg/L as CaCO3), whereas the highest criteria were for water with high DOC (9.8 mg/L), pH (8.2), and hardness (288 mg/L as CaCO3 ). Environ Toxicol Chem 2017;36:2965-2973. © 2017 SETAC.

Development and application of a multimetal multibiotic ligand model for assessing aquatic toxicity of metal mixtures.

A multimetal, multiple binding site version of the biotic ligand model (mBLM) has been developed for predicting and explaining the bioavailability and toxicity of mixtures of metals to aquatic organisms. The mBLM was constructed by combining information from single-metal BLMs to preserve compatibility between the single-metal and multiple-metal approaches. The toxicities from individual metals were predicted by assuming additivity of the individual responses. Mixture toxicity was predicted based on both dissolved metal and mBLM-normalized bioavailable metal. Comparison of the 2 prediction methods indicates that metal mixtures frequently appear to have greater toxicity than an additive estimation of individual effects on a dissolved metal basis. However, on an mBLM-normalized basis, mixtures of metals appear to be additive or less than additive. This difference results from interactions between metals and ligands in solutions including natural organic matter, processes that are accounted for in the mBLM. As part of the mBLM approach, a technique for considering variability was developed to calculate confidence bounds (called response envelopes) around the central concentration-response relationship. Predictions using the mBLM and response envelope were compared with observed toxicity for a number of invertebrate and fish species. The results show that the mBLM is a useful tool for considering bioavailability when assessing the toxicity of metal mixtures.

Metal mixture modeling evaluation project: 2. Comparison of four modeling approaches.

As part of the Metal Mixture Modeling Evaluation (MMME) project, models were developed by the National Institute of Advanced Industrial Science and Technology (Japan), the US Geological Survey (USA), HDR|HydroQual (USA), and the Centre for Ecology and Hydrology (United Kingdom) to address the effects of metal mixtures on biological responses of aquatic organisms. A comparison of the 4 models, as they were presented at the MMME workshop in Brussels, Belgium (May 2012), is provided in the present study. Overall, the models were found to be similar in structure (free ion activities computed by the Windermere humic aqueous model [WHAM]; specific or nonspecific binding of metals/cations in or on the organism; specification of metal potency factors or toxicity response functions to relate metal accumulation to biological response). Major differences in modeling approaches are attributed to various modeling assumptions (e.g., single vs multiple types of binding sites on the organism) and specific calibration strategies that affected the selection of model parameters. The models provided a reasonable description of additive (or nearly additive) toxicity for a number of individual toxicity test results. Less-than-additive toxicity was more difficult to describe with the available models. Because of limitations in the available datasets and the strong interrelationships among the model parameters (binding constants, potency factors, toxicity response parameters), further evaluation of specific model assumptions and calibration strategies is needed.

Impact of organic carbon on the stability and toxicity of fresh and stored silver nanoparticles.

Studies investigating the impact of particle size and capping agents on nanosilver toxicity in pristine laboratory conditions are becoming available. However, the relative importance of known environmental mitigating factors for dissolved silver remains poorly characterized for nanosilver in context with existing predictive toxicity models. This study investigated the implications of freshly prepared versus stored 20 and 100 nm nanosilver stocks to freshwater zooplankton (Ceriodaphnia dubia) in presence and absence of dissolved organic carbon (DOC). Results indicated that while the acute toxicity of nanosilver decreased significantly with larger size and higher DOC, storage resulted in significant increases in toxicity and ion release. The most dramatic decrease in toxicity due to DOC was observed for the 20 nm particle (2.5-6.7 fold decrease), with more modest toxicity reductions observed for the 100 nm particle (2.0-2.4 fold) and dissolved silver (2.7-3.1 fold). While a surface area dosimetry presented an improvement over mass when DOC was absent, the presence of DOC confounded its efficacy. The fraction of dissolved silver in the nanosilver suspensions was most predictive of acute toxicity regardless of system complexity. Biotic Ligand Model (BLM) predictions based on the dissolved fraction in nanosilver suspensions were comparable to observed toxicity.

Influences of water chemistry on the acute toxicity of lead to Pimephales promelas and Ceriodaphnia dubia.

The acute toxicity of lead (Pb) was examined for fathead minnows (Pimephales promelas; 96-h) and daphnids (Ceriodaphnia dubia; 48-h) in waters modified for hardness (as CaSO4), dissolved organic carbon (DOC; as Aldrich humic acid) and alkalinity (as NaHCO3) for parameterization of an acute freshwater biotic ligand model (BLM). Additionally, acute (96-h) and chronic (30-d) bioassays were performed for P. promelas to more clearly define the influence of pH (5.5-8.3) on Pb toxicity as modified by addition of HCl or NaOH using an automated titration system. Results indicate that Ca(2+) is protective against acute Pb toxicity to P. promelas but not C. dubia. Strong protection was afforded by DOC and NaHCO(3) against acute Pb toxicity to P. promelas, whereas milder protection was observed for C. dubia with both parameters. Dissolved Pb LC50s from the P. promelas pH bioassays revealed a complex effect of pH on Pb toxicity, likely explained in part by Pb speciation and the competitive interaction of H(+) with ionic Pb(2+). Chronic pH bioassays also demonstrated that 30-d growth is not impaired in fathead minnows at relevant Pb concentrations. The findings reported herein suggest that development of separate BLMs for P. promelas and C. dubia should be considered.