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The primary goal of the present study is to provide a broad view of best practices for evaluating bioavailability models for metals for use in the protection of aquatic life. We describe the state of the science regarding 1) the evaluation and selection of ecotoxicity data, 2) the selection of bioavailability models for use in normalization, and 3) subsequent application of bioavailability models. Although many examples of normalization steps exist worldwide, a scheme is proposed to evaluate and select a model that takes account of its representativeness (water chemistry and taxonomic coverage of the ecotoxicity data set) and validation performance. Important considerations for a suitable model are the quantity of inputs needed, accuracy, and ease of use, all of which are needed to set protective values for aquatic life and to use these values to evaluate potential risks to organisms in receiving waters. Although the end results of different model application approaches may be broadly similar, the differences in these application frameworks ultimately come down to a series of trade-offs between who needs to collect the data and use the bioavailability model, the different requirements of spatial scales involved (e.g., regional vs site-specific values), and model predictiveness and protectiveness. Ultimately, understanding the limits and consequences of these trade-offs allows for selection of the most appropriate model and application framework to best provide the intended levels of aquatic life protection. Environ Toxicol Chem 2019;39:118-130. © 2019 SETAC.

There is concern over whether regulatory criteria for copper (Cu) are protective against chemosensory and behavioral impairment in aquatic organisms. We compiled Cu toxicity data for these and other sublethal endpoints in 35 tests with saltwater organisms and compared the Cu toxicity thresholds with biotic ligand model (BLM)-based estimated chronic limits (ECL values, which are 20% effect concentrations [EC20s] for the embryo-larval life stage of the blue mussel [Mytilus edulis], a saltwater species sensitive to Cu that has historically been used to derive saltwater Cu criteria). Only 8 of the 35 tests had sufficient toxicity and chemistry data to support unequivocal conclusions (i.e., a Cu EC20 or no-observed-effect concentration could be derived, and Cu and dissolved organic carbon [DOC] concentrations were measured [or DOC concentrations could be inferred from the test-water source]). The BLM-based ECL values would have been protective (i.e., the ECL was lower than the toxicity threshold) in 7 of those 8 tests. In the remaining 27 tests, this meta-analysis was limited by several factors, including 1) the Cu toxicity threshold was a "less than" value in 19 tests because only a lowest-observed-effect concentration could be calculated and 2) Cu and/or DOC concentrations often were not measured. In 2 of those 27 tests, the ECL would not have been protective if based only on a conservatively high upper-bound DOC estimate. To facilitate future evaluations of the protectiveness of aquatic life criteria for metals, we urge researchers to measure and report exposure-water chemistry and test-metal concentrations that bracket regulatory criteria. Environ Toxicol Chem 2018;37:1515-1522. © 2018 SETAC.

Copper (Cu) can impair olfaction in juvenile Pacific salmon (as well as other fishes), thus potentially inhibiting the ability of juveniles to avoid predators or to find food. Because Cu is commonly elevated in stormwater runoff in urban environments, storm events may result in elevated Cu concentrations in salmon-bearing streams. Accordingly, there is concern that existing Cu criteria, which were not derived using data for olfactory-related endpoints, may not be adequately protective of juvenile salmon. However, a modification of the US Environmental Protection Agency (USEPA) biotic ligand model (BLM) for deriving site-specific Cu criteria was recently proposed, which accounted for the sensitivity of olfactory endpoints. The modification was based on olfactory inhibition in juvenile coho salmon (Oncorhynchus kisutch) exposed to Cu in various combinations of pH, hardness, alkalinity, and dissolved organic carbon (DOC) concentrations. We used that olfactory-based BLM to derive 20% inhibition concentrations (IC20) values for Cu for 133 stream locations in the western United States. The olfactory BLM-based IC20 values were compared to the existing hardness-based Cu criteria and the USEPA's BLM-based Cu criteria for these representative natural waters of the western United States. Of the 133 sampling locations, mean hardness-dependent acute and chronic Cu criteria were below the mean olfactory-based BLM IC20 value in 122 (92%) and 129 (97%) of the waters, respectively (i.e.

The goal of this study was to evaluate the reliability of the Biotic Ligand Model to predict Cu toxicity in very hard surface water (>200 mg/L as CaCO3), relative to current copper criteria methodologies (hardness-based equation and the water-effect ratio; WER). To test these methods, we conducted acute Cu toxicity tests with three aquatic test species (Ceriodaphnia dubia, Daphnia pulex and Pimephales promelas) in seven surface waters. The sites were representative of effluent-dependent or effluent-dominated streams common to the arid western United States of America (arid West) and a wide range of water quality variables were tested. In addition, concurrent Cu toxicity tests were conducted in laboratory waters that were matched to hardness and alkalinity of the sites to facilitate calculation of WER values. Results were used to characterize empirical relationships between water quality characteristics and Cu toxicity, and to compare measured Cu toxicity with Biotic Ligand Model (BLM) predictions. Acute toxicity tests were also conducted with C. dubia and P. promelas in a range of Ca or Mg-dominated hardness concentrations to determine the independent effects of Ca or Mg on Cu toxicity at high hardness levels. Conclusions from this study suggest that the BLM generates appropriate criteria for the waters tested in this study when compared to the hardness-based equation or WER approach. Although the historical site-specific methods are useful for surface waters with hardness ≤250 mg/L as CaCO3, the unique conditions of arid West streams require site-specific methods that account for the influences of critical water quality variables (i.e., pH, dissolved organic carbon, alkalinity, Ca, Mg and Na). Therefore, the BLM offers an improved alternative to the hardness-based and WER approaches, particularly for situations where the current methods would be under-protective of sensitive aquatic life.

Worldwide transfer and introduction of non-indigenous species in ballast water causes significant environmental and economic impact. One way to address this problem is to remove or inactivate organisms that are found in ballast water. In this study, 3 experiments were conducted in Puget Sound, Washington, USA, using a prototype ozone treatment system installed on a commercial oil tanker, the S/T Tonsina. Treatment consisted of ozone gas diffused into a ballast tank for 5 and 10 h. Treatment and control tanks were sampled during the ozonation period for chemistry, cultur- able bacteria, phytoplankton and zooplankton. Selected fish and invertebrates were placed in cages deployed in the treatment and control tanks. Ozone introduced into seawater rapidly converts bro- mide (Br - ) to bromines (HOBr/OBr - ), compounds that are disinfectants. These were measured as total residual oxidant (TRO). Ozone treatment inactivated large portions of culturable bacteria, phyto- plankton and zooplankton. The highest reductions observed were 99.99% for the culturable bacteria, >99% for dinoflagellates and 96% for zooplankton. Caged animal results varied among taxa and locations in the ballast tank. Sheepshead minnows and mysid shrimp were most susceptible, shore crabs and amphipods the least. Distribution of ozone in the treatment tank was not homogenous during experiments, as suggested by the observed TRO concentrations and lower efficacies for inactivating the different taxa in selected ballast tank locations. Low concentrations of bromoform, a disinfection byproduct, were found in treated ballast water.

The influence of a commercial humic acid (Aldrich; AHA) on the development of anthracene photoinduced toxicity to the duckweed Lemna gibba was examined using both room- and low-temperature (77°K) chlorophyll fluorescence assays. Plants were exposed to 2 mg liter -1 anthracene both with and without 6.2 mg liter -1 of AHA and grown under either visible light or simulated solar radiation that mimics the natural abundance of UV radiation. Exposure periods ranged from 1 to 48 h to examine temporal changes in chlorophyll degradation and chlorophyll a fluorescence induction in response to these light and HA treatments. The onset of anthracene photoinduced toxicity followed a definite sequence; chlorophyll a fluorescence induction parameters (F v /F m , and t 1 /2) responded earliest to anthracene exposure, with observable chlorophyll degradation requiring up to 24 to 48 h. Of these, t 1 /2 was the most sensitive, with significant inhibition apparent within I h of exposure. Throughout the entire 48-h exposure, 6.2 mg liter 1 AHA ameliorated the photoinduced toxicity of anthracene, in terms of both chlorophyll degradation and F v / F m inhibition. In contrast, AHA delayed the complete inhibition of t 1 /2 by only I to 24 h rather than permanently protecting the plants from anthracene damage to PS2. This suggests that AHA may slow, but not prevent, the entrance of either intact anthracene or its photooxidized byproducts under these exposure conditions.

The growth rates of two diatoms, acidophilic Asterionella ralfsii and circumneutral A. formosa, were differentially affected by varying pH, Al, and EDTA in chemically defined media. Free Al ion concentration increased as pH and EDTA concentration decreased. Free trace metal ion concentration decreased as EDTA levels increased but increased by orders of magnitude upon addition of Al. pH had an overriding species specific effect on growth rate; at low pH A. ralfsii had higher growth rates than A. formosa and vice versa at high pH. For both species higher EDTA levels depressed growth rates. Moderate additions of Al generally resulted in growth stimulation. The growth rate stimulations, especially at 200 and 400 μg L−1 Al additions, correlate to increases in free trace metal ion concentrations. The EDTA-AI interaction effects on growth rate were both pH and concentration dependent: at pH 7 both species were stimulated by addition of Al at all EDTA levels (except A. ralfsii at 5.0 mM EDTA and A. formosa at 0.5 mNM EDTA); at pH 6 Al addition either stimulated or had no effect on the growth rates of both species (except at low EDTA and high Al levels); at pH 5 A. formosa did not grow and additions of 200 μg L−1 Al stimulated growth of A. ralfsii. It is likely that the effect of pH, Al, and EDTA on speciation of essential or toxic trace metals affects growth rates of these diatoms in a species specific manner.

The effects of pH and Al on the acidophilic diatom Asterionella ra[fsii var. americana K6m. were examined in axenic batch cultures. Experiments were performed under conditions of both high (pH 5) and low (pH 6) Al solubility over a range of concentrations from 0 to 30 firno liter-’ total Al. Growth rates were analyzed with respect to analytically determined Al concentrations and to predicted changes in dissolved metal ion speciation in response to Al additions. Growth rates of A. rufiii were significantly reduced above 15 pmol liter-’ total Al at both pH 5 and 6. Al additions increased estimated free ion activities of Al 3+, Fe3+, and Cu*+ through indirect chelator interactions at pH 5 and 6; therefore, all three were significantly correlated with growth rate reductions, Independent manipulations of total Fe and Cu, however, suggested that Al was not indirectly increasing either Fe’+ or Cu2+ free ion activities to toxic levels. Relationships of growth rates to both inorganic monomeric Al (A13 and to estimates of pA1 were strongly pHdependent with toxicity being greater per unit of dissolved Al concentration at pH 6 than at pH 5. These results are consistent qualitatively with predictions that H.’ ions can ameliorate dissolved metal toxicity by competitively excluding AP+ ions from binding to cell-surface ligands. The impact of Al on natural phytoplankton populations therefore is likely to depend on a combination of pHdependent Al solubility, the protonation of cell-surface ligands, and chelator-mediated metal speciation.

Changes in cell size and silica content were examined in response to aluminum additions in cultures of the acidophilic diatom Asterionella ralfsii var. americana Korn at pH 6.0. The effect of Al were examined over a range of steady-state growth rates using silica-limited semicontinuous cultures (Si:P=8.0). Addittions of ≥2.8 μmol.L -1 total Al decreased mean cell length, total surface area, and biovolume up to 40-50%. The effets of Al were dependent on growth rate with the magnitude of size reduction increasing at higher growth rates. The effects of Al were dependent on growth rate with the magnitude of size reduction increasing at higher growth rates. The proportion of small (approximately 15-20 μm) cell length classes increased relative to large (approximately 50 μm length) cell length classes when total Al exceeded 2.8 μmol.L -1 , particularly at higher growth rates (...)

The ability of a commercial (Aldrich Chemical Co.) humic acid (AHA) to ameliorate the photo-induced toxicity of polycyclic aromatic hydrocarbons (PAHs) was examined using Lemna gibba L. (G3). Plants were exposed to anthracene and benzo(a)pyrene both with and without AHA and grown under visible light as well as lighting that simulates relative abundances of UV-A and UV-B in natural sunlight (SSR). Modest additions of 1.6 mg.L-1 AHA were sufficient to ameliorate the photo-induced toxicity of 2 mg.L-1 anthracene by improving growth rates to nearly 50% of controls and inducing minor recovery from complete chlorosis in the most highly affected plants. Benzo(a)pyrene induced minor, but significant, chlorosis under SSR, and AHA additions always increased growth rate and chlorophyll content, although to less of a degree than anthracene toxicity under SSR. The protective effects of AHA on anthracene toxicity increased linearly with increases in AHA concentrations up to 6.2 mg.L-1. Slopes of these relationships changed in the presence of UV light relative to visible light treatments; thus UV changed the extent to which AHA mediates PAH toxicity. However, the net effect was still for AHA to ameliorate PAH photo-induced toxicity even though UV has the potential to photooxidize AHA and enhance the production of potentially toxic reactive oxygen species from AHA photosensitization.