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Short-term (60 min) europium (Eu) biouptake fluxes by the freshwater green alga Chlamydomonas reinhardtii were investigated in the presence and absence of ligands (e.g., malic acid and citric acid) and a second rare earth metal, samarium (Sm). Data were interpreted in the context of the biotic ligand model, which uses experimentally determined stability constants to take into account the competition and complexation of the metal of interest. In the absence of ligands or competitors, Eu biouptake was well described by a Michaelis-Menten equation with the maximal uptake flux ( Jmax) and Michaelis-Menten constant ( Km) of Jmax = 1.7 × 10−14 mol cm−2 s−1 and Km = 10−7.0 M (corresponding to an affinity constant of 107.0 M−1). Biouptake of Eu (or Sm) decreased as the concentration of a competing rare earth element (i.e., Sm or Eu) increased, as predicted by the biotic ligand model. On the other hand, when hydrophilic complexes were formed with citric and malic acid, Eu biouptake was much greater than predicted on the basis of free ion concentrations alone. Overall, the results showed that for C. reinhardtii the rare earth elements were likely to share a common biouptake pathway; biouptake of one rare earth element was reduced when another was present, and rare earth element complexes were bioavailable. Environ Toxicol Chem 2014;33:2609-2615. © 2014 SETAC [ABSTRACT FROM AUTHOR]

Soil tests have been widely developed to predict trace metal uptake by plants. The prediction of metal toxicity, however, has rarely been tested. The present study was set up to compare 8 established soil tests for diagnosing phytotoxicity in contaminated soils. Nine soils contaminated with Zn or Cu by metal mining, smelting, or processing were collected. Uncontaminated reference soils with similar soil properties were sampled, and series of increasing contamination were created by mixing each with the corresponding soil. In addition, each reference soil was spiked with either ZnCl2 or CuCl2 at several concentrations. Total metal toxicity to barley seedling growth in the field-contaminated soils was up to 30 times lower than that in corresponding spiked soils. Total metal (aqua regia-soluble) toxicity thresholds of 50% effective concentrations (EC50) varied by factors up to 260 (Zn) or 6 (Cu) among soils. For Zn, variations in EC50 thresholds decreased as aqua regia > 0.43 M HNO3 > 0.05 M ethylenediamine tetraacetic acid (EDTA) > 1 M NH4NO3 > cobaltihexamine > diffusive gradients in thin films (DGT) > 0.001 M CaCl2, suggesting that the last extraction is the most robust phytotoxicity index for Zn. The EDTA extraction was the most robust for Cu-contaminated soils. The isotopically exchangeable fraction of the total soil metal in the field-contaminated soils markedly explained the lower toxicity compared with spiked soils. The isotope exchange method can be used to translate soil metal limits derived from soils spiked with metal salts to site-specific soil metal limits. Environ Toxicol Chem 2014;33:2479-2487. © 2014 SETAC [ABSTRACT FROM AUTHOR]

Scientifically sound risk assessment and derivation of environmental quality standards for lead (Pb) in the freshwater environment are hampered by insufficient data on chronic toxicity and bioavailability to unicellular green algae. Here, we first performed comparative chronic (72-h) toxicity tests with three algal species in medium at pH 6, containing 4 mg fulvic acid (FA)/L and containing organic phosphorous (P), i.e. glycerol-2-phosphate, instead of PO43- to prevent lead-phosphate mineral precipitation. Pseudokirchneriella subcapitata was 4-fold more sensitive to Pb than Chlorella kesslerii, with Chlamydomonas reinhardtii in the middle. The influence of medium physico-chemistry was therefore investigated in detail with P. subcapitata. In synthetic test media, higher concentrations of fulvic acid or lower pH protected against toxicity of (filtered) Pb to P. subcapitata, while effects of increased Ca or Mg on Pb toxicity were less clear. When toxicity was expressed on a free Pb2+ ion activity basis, a log-linear, 260-fold increase of toxicity was observed between pH 6.0 and 7.6. Effects of fulvic acid were calculated to be much more limited (1.9-fold) and were probably even non-existent (depending on the affinity constant for Pb binding to fulvic acid that was used for calculating speciation). A relatively simple bioavailability model, consisting of a log-linear pH effect on Pb2+ ion toxicity linked to the geochemical speciation model Visual Minteq (with the default NICA-Donnan description of metal and proton binding to fulvic acid), provided relatively accurate toxicity predictions. While toxicity of (filtered) Pb varied 13.7-fold across 14 different test media (including four Pb-spiked natural waters) with widely varying physico-chemistry (72h-EC50s between 26.6 and 364 µg/L), this bioavailability model displayed mean and maximum prediction errors of only 1.4 and 2.2-fold, respectively, thus indicating the potential usefulness of this bioavailability model to reduce uncertainty in site-specific risk assessment. A model-based comparison with other species indicated that the sensitivity difference between P. subcapitata and two of the most chronically Pb-sensitive aquatic invertebrates (the crustacean Ceriodaphnia dubia and the snail Lymnaea stagnalis) is strongly pH dependent, with P. subcapitata becoming the most sensitive of the three at pH > 7.4. This indicates that inter-species differences in Pb bioavailability relationships should be accounted for in risk assessment and in the derivation of water quality criteria or environmental quality standards for Pb. The chronic toxicity data with three algae species and the bioavailability model presented here will help to provide a stronger scientific basis for evaluating ecological effects of Pb in the freshwater environment. [ABSTRACT FROM AUTHOR]

The acute toxicity of cadmium, copper, and zinc to white sturgeon ( Acipenser transmontanus) and rainbow trout ( Oncorhynchus mykiss) were determined for 7 developmental life stages in flow-through water-only exposures. Metal toxicity varied by species and by life stage. Rainbow trout were more sensitive to cadmium than white sturgeon across all life stages, with median effect concentrations (hardness-normalized EC50s) ranging from 1.47 µg Cd/L to 2.62 µg Cd/L with sensitivity remaining consistent during later stages of development. Rainbow trout at 46 d posthatch (dph) ranked at the 2nd percentile of a compiled database for Cd species sensitivity distribution with an EC50 of 1.46 µg Cd/L and 72 dph sturgeon ranked at the 19th percentile (EC50 of 3.02 µg Cd/L). White sturgeon were more sensitive to copper than rainbow trout in 5 of the 7 life stages tested with biotic ligand model (BLM)-normalized EC50s ranging from 1.51 µg Cu/L to 21.9 µg Cu/L. In turn, rainbow trout at 74 dph and 95 dph were more sensitive to copper than white sturgeon at 72 dph and 89 dph, indicating sturgeon become more tolerant in older life stages, whereas older trout become more sensitive to copper exposure. White sturgeon at 2 dph, 16 dph, and 30 dph ranked in the lower percentiles of a compiled database for copper species sensitivity distribution, ranking at the 3rd (2 dph), 5th (16 dph), and 10th (30 dph) percentiles. White sturgeon were more sensitive to zinc than rainbow trout for 1 out of 7 life stages tested (2 dph with an biotic ligand model-normalized EC50 of 209 µg Zn/L) and ranked in the 1st percentile of a compiled database for zinc species sensitivity distribution. Environ Toxicol Chem 2014;33:2259-2272. © 2014. The Authors. This article is a US government work and, as such, is in the public domain in the United States of America. Environmental Toxicology and Chemistry published byWiley Periodicals, Inc. on behalf of SETAC. This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made. [ABSTRACT FROM AUTHOR]

Uptake and elimination kinetics of metals in soil invertebrates are a function of both soil and organism properties. This study critically reviewed metal toxicokinetics in soil invertebrates and its potential use for assessing bioavailability. Uptake and elimination rate constants of different metals are summarized. Invertebrates have different strategies for essential and non-essential metals. As a consequence, different types of models must be applied to describe metal uptake and elimination kinetics. We discuss model parameters for each metal separately and show how they are influenced by exposure concentrations and by physiological properties of the organisms. Soil pH, cation exchange capacity, clay and organic matter content significantly affect uptake rates of non-essential metals in soil invertebrates. For essential metals, kinetics is hardly influenced by soil properties, but rather prone to physiological regulation mechanisms of the organisms. Our analysis illustrates that toxicokinetics can be a valuable measurement to assess bioavailability of soil-bound metals. [ABSTRACT FROM AUTHOR]

Studies were conducted to assess the feasibility of a primary FIsh Gill Cell culture system (FIGCS) for both laboratory and field based environmental monitoring of rivers known to be affected by metal contamination. FIGCS were exposed in the laboratory and in the field to water from the River Hayle, a metal-contaminated system in Cornwall, United Kingdom. Water chemistry, including transition metal concentrations, changes in transepithelial electrical resistance (TEER), cell viability and the expression of metal responsive genes, metallothionein A and B were measured. FIGCS tolerated river water in the laboratory showing no loss in TEER or cell viability following 24h exposure. The cells also tolerated transport to the field (~1000km and 30h) and exposure to unfiltered and filtered river water. Metallothionein A and B, a measure of intracellular biologically active metals, expression was induced in the laboratory and field on exposure to water from sites with elevated metal concentrations compared to those sites where metal levels were below water metal Environmental Quality Standards. This demonstrates that FIGCS detects bioreactive metals in river waters on exposure in the laboratory or field and can be used for on-site environmental monitoring as well as investigations into bioavailability and toxicity of contaminant mixtures in natural waters. [ABSTRACT FROM AUTHOR]

The bioavailability and toxicity of copper (Cu) in Shelter Island Yacht Basin (SIYB), San Diego, CA, USA, was assessed with simultaneous toxicological, chemical, and modeling approaches. Toxicological measurements included laboratory toxicity testing with Mytilus galloprovincialis (Mediterranean mussel) embryos added to both site water (ambient) and site water spiked with multiple Cu concentrations. Chemical assessment of ambient samples included total and dissolved Cu concentrations, and Cu complexation capacity measurements. Modeling was based on chemical speciation and predictions of bioavailability and toxicity using a marine Biotic Ligand Model (BLM). Cumulatively, these methods assessed the natural buffering capacity of Cu in SIYB during singular wet and dry season sampling events. Overall, the three approaches suggested negligible bioavailability, and isolated observed or predicted toxicity, despite an observed gradient of increasing Cu concentration, both horizontally and vertically within the water body, exceeding current water quality criteria for saltwater. [ABSTRACT FROM AUTHOR]

The water effect ratio (WER) procedure developed by the US Environmental Protection Agency is commonly used to derive site-specific criteria for point-source metal discharges into perennial waters. However, experience is limited with this method in the ephemeral and intermittent systems typical of arid climates. The present study presents a regression model to develop WER-based site-specific criteria for a network of ephemeral and intermittent streams influenced by nonpoint sources of Cu in the southwestern United States. Acute (48-h) Cu toxicity tests were performed concurrently with Daphnia magna in site water samples and hardness-matched laboratory waters. Median effect concentrations (EC50s) for Cu in site water samples ( n = 17) varied by more than 12-fold, and the range of calculated WER values was similar. Statistically significant (α = 0.05) univariate predictors of site-specific Cu toxicity included (in sequence of decreasing significance) dissolved organic carbon (DOC), hardness/alkalinity ratio, alkalinity, K, and total dissolved solids. A multiple-regression model developed from a combination of DOC and alkalinity explained 85% of the toxicity variability in site water samples, providing a strong predictive tool that can be used in the WER framework when site-specific criteria values are derived. The biotic ligand model (BLM) underpredicted toxicity in site waters by more than 2-fold. Adjustments to the default BLM parameters improved the model's performance but did not provide a better predictive tool compared with the regression model developed from DOC and alkalinity. Environ Toxicol Chem 2014;33:1865-1873. © 2014 SETAC [ABSTRACT FROM AUTHOR]

Populations of white sturgeon ( Acipenser transmontanus) are in decline in North America. This is attributed, primarily, to poor recruitment, and white sturgeon are listed as threatened or endangered in several parts of British Columbia, Canada, and the United States. In the Columbia River, effects of metals have been hypothesized as possible contributing factors. Previous work has demonstrated that early life stage white sturgeon are particularly sensitive to certain metals, and concerns over the level of protectiveness of water quality standards are justified. Here we report results from acute (96-h) toxicity tests for copper (Cu), cadmium (Cd), zinc (Zn), and lead (Pb) from parallel studies that were conducted in laboratory water and in the field with Columbia River water. Water effect ratios (WERs) and sensitivity parameters (i.e., median lethal accumulations, or LA50s) were calculated to assess relative bioavailability of these metals in Columbia River water compared to laboratory water, and to elucidate possible differences in sensitivity of early life stage white sturgeon to the same concentrations of metals when tested in the different water sources. For Cu and Pb, white sturgeon toxicity tests were initiated at two life stages, 8 and 40 days post-hatch (dph), and median lethal concentrations (LC50s) ranged between 9-25 μg Cu/L and 177-1,556 μg Pb/L. LC50s for 8 dph white sturgeon exposed to Cd in laboratory water and river water were 14.5 and 72 μg/L, respectively. Exposure of 8 dph white sturgeon to Zn in laboratory and river water resulted in LC50s of 150 and 625 μg/L, respectively. Threshold concentrations were consistently less in laboratory water compared with river water, and as a result, WERs were greater than 1 in all cases. In addition, LA50s were consistently greater in river water exposures compared with laboratory exposures in all paired tests. These results, in combination with results from the biotic ligand model, suggest that the observed differences in toxicity between river water exposures and laboratory water exposures were not entirely due to differences in water quality and metal bioavailability but rather in combination with differences in fish sensitivity. It is hypothesized that differences in concentrations of calcium in the different water sources might have resulted in differences in acquired sensitivity of sturgeon to metals. Canadian water quality guidelines, US national criteria for the protection of aquatic life, and water quality criteria for the state of Washington were less than LC50 values for all metals and life stages tested in laboratory and Columbia River water. With the exception, however, that 40 dph white sturgeon exposed to Cu in laboratory water resulted in threshold values that bordered US national criteria and criteria for the state of Washington. [ABSTRACT FROM AUTHOR]

Highlights: [•] Na+ uptake and ammonia excretion shift from skin to gills over post-hatch development. [•] Waterborne Cu inhibits Na+ uptake by the skin only in early development (3dph). [•] By late development (25dph), Cu inhibits both gill Na+ uptake and ammonia excretion. [•] The skin is the likely site of Cu toxicity immediately following hatch. [•] This shift in site and possible mechanism of toxicity has implications for the BLM. [Copyright &y& Elsevier]

Protons and other cations may inhibit metal uptake and alleviate metal toxicity in aquatic organisms, but less is known about these interactions in soil organisms. The present study investigated the influence of solution chemistry on uptake and toxicity of Ni in Enchytraeus crypticus after 14 days exposure. Ca2+, Mg2+ and Na+ were found to exert significant effects on both uptake and toxicity of Ni. An extended Langmuir model, which incorporated cation competition effects, well predicted Ni uptake. The LC50{Ni2+} predicted by a developed Biotic Ligand Model matched well with observed values. These suggest that cation competition needs to be taken into account when modelling uptake and effects. The binding constants of Ni2+, Mg2+ and Na+ on the uptake and toxic action sites were similar, but for Ca2+ they differed. This indicates that the effect of Ca2+ on Ni2+ toxicity cannot simply be explained by the competition for entry into organism. [Copyright &y& Elsevier]

Biotic ligand models (BLM) explicitly accounting for hypothetical interactions with biotic ligands and bioavailability as dictated by water chemistry have been developed for various metals and different organisms. It is only recently that BLMs for plants have received increasing attention. Lettuce is one of the most important vegetable crops in the world. This study investigated the impacts of Ca, Mg, K, Na and pH, on acute toxicity of Ni and Cd to butter-head lettuce seedlings ( Lactuca sativa L.). 4-day assays with the root elongation inhibition ( REI) as the endpoint were performed in hydroponic solutions. Magnesium was found to be the sole cation significantly enhancing the median inhibition concentration (IC50) of Ni with increasing concentration. By incorporating the competitive effects of Mg, the Ni-toxicity prediction was improved significantly as compared to the total metal model (TMM) and the free ion activity model (FIAM). The conditional stability constants derived from the Ni-BLM were log K = 2.86, log K = 5.1, and f = 0.57. A slight downtrend was observed in the 4-d IC50 of Cd at increasing H concentrations, but this tendency was not consistent and statistically significant ( p = 0.07) over the whole range. The overall variations of Cd-toxicity within the tested Na, K, Ca and Mg concentration ranges were relatively small and not statistically significant. 80 % of lettuce REI by Cd could be explained using both TMM and FIAM instead of BLM in the present study. Thus, the mechanistically underpinned models for soil quality guidelines should be developed on a metal-specific basis across different exposure conditions. [ABSTRACT FROM AUTHOR]

The use of the free ion approach to quantify the toxic effects of Cd and Ni to the earthworms Lumbricus rubellus and Aporrectodea longa exposed in soils of different types was explored. Median lethal concentration (LC50) of Cd (expressed as the total concentration in soil) varied by approximately 11-fold and 28-fold for L. rubellus and A. longa, respectively. For Ni, these values were 50-fold and 38-fold, respectively. For the 2 earthworm species, no significant influence of cations (H+, Ca2+, Mg2+, K+, and Na+) on Cd2+ toxicity was observed, while Mg2+ was found to significantly alleviate Ni2+ toxicity. The free ion activity model, which is a special case of the free ion approach with no impact of cations, sufficiently described the variability in Cd2+ toxicity across soils but failed in predicting Ni2+ toxicity. The free ion approach, in which the protective effects of Mg2+ were included, explained 89% and 84% of the variations in LC50{Ni2+} (expressed as free ion activity) for L. rubellus (log LC50{Ni2+} = 1.18log{Mg2+}−0.52) and A. longa (log LC50{Ni2+} = 0.51log{Mg2+}−2.16), respectively. Prediction error was within a factor of 2 for both Cd2+ and Ni2+ toxicity, indicating the applicability of the free ion approach for predicting toxicity of these 2 metals. Although extrapolation of the free ion approach across metals still needs more research efforts, this approach, as an alternative to the biotic ligand model, provides a feasible framework for site-specific risk assessment. Environ Toxicol Chem 2014;33:438-446. © 2013 SETAC [ABSTRACT FROM AUTHOR]

While it is increasingly being recognized that biotic ligand models (BLMs) are valuable in the risk assessment of metals in aquatic systems, the development of chronic BLMs has been less advanced for lead than for other metals. The authors investigated the univariate effects of Ca and pH on the chronic reproductive toxicity of Pb to Ceriodaphnia dubia at 4 levels. Calcium influenced chronic Pb toxicity to C. dubia only to a relatively small extent, whereas a high pH (8.2) provided strong protection against Pb toxicity (compared with lower pH levels). Based on this data set, a chronic Pb BLM for C. dubia was developed. The effect of pH was modeled as a single biotic ligand site competition by H+ with a log stability constant for binding of H+ to the biotic ligand ( KHBL) of 7.6, while no other competitive constants were needed. The developed BLM was shown, in an independent validation with 3 other data sets, to be capable of predicting chronic Pb toxicity to different clones of C. dubia by an error of less than a factor of 2 in most synthetic and natural waters considered. The results add to the growing evidence that BLM-based risk assessment or water-quality criteria for Pb are likely to be more appropriate relative to hardness-based assessments or criteria. Environ Toxicol Chem 2014;33:394-403. © 2013 SETAC [ABSTRACT FROM AUTHOR]

Abstract: The toxicity of single and multiple metal (Cd, Cu, Pb, and Zn) solutions to trout is predicted using an approach that combines calculations of: (1) solution speciation; (2) competition and accumulation of cations (H, Ca, Mg, Na, Cd, Cu, Pb, and Zn) on low abundance, high affinity and high abundance, low affinity biotic ligand sites; (3) a toxicity function that accounts for accumulation and potency of individual toxicants; and (4) biological response. The approach is evaluated by examining water composition from single metal toxicity tests of trout at 50% mortality, results of theoretical calculations of metal accumulation on fish gills and associated mortality for single, binary, ternary, and quaternary metal solutions, and predictions for a field site impacted by acid rock drainage. These evaluations indicate that toxicity of metal mixtures depends on the relative affinity and potency of toxicants for a given aquatic organism, suites of metals in the mixture, dissolved metal concentrations and ratios, and background solution composition (temperature, pH, and concentrations of major ions and dissolved organic carbon). A composite function that incorporates solution composition, affinity and competition of cations for two types of biotic ligand sites, and potencies of hydrogen and individual metals is proposed as a tool to evaluate potential toxicity of environmental solutions to trout. [Copyright &y& Elsevier]

Recent years have seen considerable improvement in water quality standards (QS) for metals by taking account of the effect of local water chemistry conditions on their bioavailability. We describe preliminary efforts to further refine water quality standards, by taking account of the composition of the local ecological community (the ultimate protection objective) in addition to bioavailability. Relevance of QS to the local ecological community is critical as it is important to minimise instances where quality classification using QS does not reconcile with a quality classification based on an assessment of the composition of the local ecology (e.g. using benthic macroinvertebrate quality assessment metrics such as River InVertebrate Prediction and Classification System (RIVPACS)), particularly where ecology is assessed to be at good or better status, whilst chemical quality is determined to be failing relevant standards. The alternative approach outlined here describes a method to derive a site-specific species sensitivity distribution (SSD) based on the ecological community which is expected to be present at the site in the absence of anthropogenic pressures (reference conditions). The method combines a conventional laboratory ecotoxicity dataset normalised for bioavailability with field measurements of the response of benthic macroinvertebrate abundance to chemical exposure. Site-specific QS are then derived from the 5%ile of this SSD. Using this method, site QS have been derived for zinc in an area impacted by historic mining activities. Application of QS can result in greater agreement between chemical and ecological metrics of environmental quality compared with the use of either conventional (QS) or bioavailability-based QS (QS). In addition to zinc, the approach is likely to be applicable to other metals and possibly other types of chemical stressors (e.g. pesticides). However, the methodology for deriving site-specific targets requires additional development and validation before they can be robustly applied during surface water classification. [ABSTRACT FROM AUTHOR]

Highlights: [•] Copper uptake and effects in Folsomia candida were studied upon solution exposure. [•] The effect of copper on F. candida survival showed a hormetic-type response. [•] A biotic ligand model approach was used to assess Ca and pH effects on Cu toxicity. [•] Calcium and pH to a certain extent explained copper toxicity and uptake. [•] BLM predicted survival showed good correlation with measured values. [ABSTRACT FROM AUTHOR]

Abstract: Dissolved organic matter (DOM) exerts direct and indirect influences on aquatic organisms. In order to better understand how DOM causes these effects, potentiometric titration was carried out for a wide range of autochthonous and terrigenous freshwater DOM isolates. The isolates were previously characterized by absorbance and fluorescence spectroscopy. Proton binding constants (pK a) were grouped into three classes: acidic (pK a ≤5), intermediate (58.5). Generally, the proton site densities (L T) showed maximum peaks at the acidic and basic ends around pK a values of 3.5 and 10, respectively. More variably positioned peaks occurred in the intermediate pK a range. The acid–base titrations revealed the dominance of carboxylic and phenolic ligands with a trend for more autochthonous sources to have higher total L T. A summary parameter, referred to as the Proton Binding Index (PBI), was introduced to summarize chemical reactivity of DOMs based on the data of pK a and L T. Then, the already published spectroscopic data were explored and the specific absorbance coefficient at 340nm (i.e. SAC340), an index of DOM aromaticity, was found to exhibit a strong correlation with PBI. Thus, the tendencies observed in the literature that darker organic matter is more protective against metal toxicity and more effective in altering physiological processes in aquatic organisms can now be rationalized on a basis of chemical reactivity to protons. [Copyright &y& Elsevier]

The present study sought to quantify the components of a biotic ligand model (BLM) for the effects of Cd on Folsomia candida (Collembola). Assuming that soil porewater is the main route of exposure and to exclude the effects of soil particles on metal availability, animals were exposed for 7 d to different Cd concentrations between 0.1 mM and 100 mM in simplified soil solutions at different Ca concentrations (0.2 mM, 0.8 mM, 3.2 mM, and 12.8 mM) or at different pH (5.0, 6.0, and 7.0). Higher Ca concentrations decreased the toxicity of Cd (adult survival) in test solutions, whereas toxicity was slightly lower at pH 7 and 6 than at pH 5, suggesting a mitigating effect of Ca and to a lesser extent pH on Cd toxicity to F. candida. Internal Cd concentrations in the animals increased with increasing exposure level but were significantly reduced by increasing Ca concentrations and were not significantly affected by pH. By using Langmuir isotherms, binding constants for Cd, Ca, and protons and the fraction of binding sites occupied by Cd were calculated and used to predict effects of Cd on survival. Predicted toxicity showed a good agreement with measured responses when Ca and pH were used as separate factors or combined together. The present study shows indications of protective effects of Ca but less of protons on the toxicity and uptake of Cd in F. candida on exposure to simplified soil solutions, which can be described using the principles of a biotic ligand model. Environ Toxicol Chem 2013;32:1759-1767. © 2013 SETAC [ABSTRACT FROM AUTHOR]

Abstract: The toxicity of many metals is impacted by environmental pH, through both competition and complexation by hydroxide and carbonate ions. To establish safe environmental regulation it is important to properly define the relationship between pH and metal toxicity, a process that involves manipulating the pH of test water in the lab. The current study compares the effects of the three most common pH manipulation methods (carbon dioxide, acid–base addition, and chemical buffers) on acute Pb toxicity of a model fish species, Pimephales promelas. Acidification of test water revealed that the Pb and Pb2+ LC50 values were impacted by the pH manipulation method, with the following order of effects: HCl

The effect of major cation activity (Ca2+, Mg2+, Na+, K+) on Ni toxicity, with dose expressed as exposure (total dissolved Ni concentration NiTot) or free Ni ion activity (in solution Ni2+), or as tissue residue (Ni concentration in plant tissue NiTiss) to the aquatic plant Lemna minor L. was examined. In addition, Ni accumulation kinetics was explored to provide mechanistic insight into current approaches of toxicity modeling, such as the tissue residue approach and the biotic ligand model (BLM), and the implications for plant Ni risk assessment. Major cations did not inhibit Ni accumulation via competitive inhibition as expected by the BLM framework. For example, Ca2+ and Mg2+ (sulfate as counter-anion) had an anticompetitive effect on Ni accumulation, suggesting that Ca or Mg forms a ternary complex with Ni-biotic ligand. The counter-anion of the added Ca (sulfate, chloride, or nitrate) affected plant response (percentage of root growth inhibition) to Ni. Generally, sulfate and chloride influenced plant response while nitrate did not, even when compared within the same range of Ca2+, which suggests that the anion dominated the observed plant response. Overall, although an effect of major cations on Ni toxicity to L. minor L. was observed at a physiological level, Ni2+ or NiTot alone modeled plant response, generally within a span of twofold, over a wide range of water chemistry. Thus, consideration of major cation competition for improving Ni toxicity predictions in risk assessment for aquatic plants may not be necessary. Environ. Toxicol. Chem. 2013;32:810-821. © 2013 SETAC [ABSTRACT FROM AUTHOR]

Copper (Cu) is a contaminant of potential concern for a uranium mine whose receiving waters are in the World Heritage-listed Kakadu National Park in northern Australia. The physicochemical characteristics of the freshwaters in this region enhance metal bioavailability and toxicity. Seven tropical species were used to assess the chronic toxicity of Cu in extremely soft freshwater from a creek upstream of the mine. Sensitivity to Cu was as follows: Moinodaphnia macleayi > Chlorella sp. > Velesunio sp. > Hydra viridissima > Amerianna cumingi > Lemna aequinoctialis > Mogurnda mogurnda. The 10% effect concentrations (EC10s) ranged from 1.0 µg/L Cu for the cladoceran Moinodaphnia macleayi to 9.6 µg/L for the fish M. mogurnda. The EC50s ranged from 6.6 µg/L Cu for the mussel Velesunio sp. to 22.5 µg/L Cu for M. mogurnda. Geochemical modeling predicted Cu to be strongly bound to fulvic acid (80%-99%) and of low bioavailability (0.02%-11.5%) under these conditions. Protective concentrations (PCs) were derived from a species sensitivity distribution for the local biota. The 99% PC (PC99), PC95, PC90, and PC80 values were 0.5, 0.8, 1.0, and 1.5 µg/L Cu, respectively. These threshold values suggest that the current Australian and New Zealand default national 99% protection guideline value for Cu (1.0 µg/L) would not provide adequate protection in freshwaters of low hardness, particularly for this area of high conservation value. The continuous criterion concentration predicted by the Cu biotic ligand model for conditions of low pH (6.1), low dissolved organic carbon (2.5 mg/L), low hardness (3.3 mg/L), and 27 °C was 0.48 µg/L Cu, comparable with the PC99. Consideration of the natural water quality conditions of a site is paramount for protective water quality guidelines. Environ Toxicol Chem 2022;41:2808-2821. © 2022 Commonwealth of Australia. Environmental Toxicology and Chemistry © 2022 SETAC., (© 2022 Commonwealth of Australia. Environmental Toxicology and Chemistry © 2022 SETAC.)

In the present study, we assessed the use of existing user-friendly bioavailability tools to predict metal bioavailability and the risk of toxicity in a typical Nigerian surface water. The effect of prevailing water chemistry on toxicity of metals was also assessed in laboratory studies. Surface water samples were collected at four locations downstream in the Ogun River in Lagos State, and water chemistry analysis was carried out using standard methods. Relevant parameters were inputted into the Bio-Met software and Metal Bioavailability Assessment Tool (M-Bat), which are run on a Microsoft Excel spreadsheet, to obtain the site-specific hazardous concentrations affecting 5% of the population (HC5)/predicted-no-effect concentrations (PNECs) for selected metals and risk characterization ratios (RCRs) at locations downstream in the river. Assessments using the bioavailability tools showed that two locations, Owode-Onirin and Kara, were more sensitive to Zn and Pb inputs compared to the other locations. The RCRs for Cu, Zn, and Pb, respectively, were >1 at all locations, indicating a potential risk of toxicity to aquatic life. Results from laboratory studies conformed with predictions from the bioavailability tools because Zn and Pb were more toxic to aquatic organisms in surface water collected from Owode-Onirin and Kara locations, respectively, compared to toxicity in surface water from other locations. The issue of bioavailability in metal pollution control is widely accepted and has been incorporated into water quality guidelines (WQGs) in the United States, the United Kingdom, and Europe. In the absence of regulations incorporating bioavailability in developing countries including Nigeria, it is essential to assess the applicability of existing methods incorporating bioavailability to surface waters in this region. Findings from such studies will facilitate the development of region-specific WQGs for metals which will be protective of locally relevant aquatic life. Environ Toxicol Chem 2022;41:2537-2547. © 2022 SETAC., (© 2022 SETAC.)

The equilibrium partitioning sediment benchmarks (ESBs) derived by the US Environmental Protection Agency (USEPA) in 2005 provide a mechanistic framework for understanding metal bioavailability in sediments by considering equilibrium partitioning (EqP) theory, which predicts that metal bioavailability in sediments is determined largely by partitioning to sediment particles. Factors that favor the partitioning of metals to sediment particles, such as the presence of acid volatile sulfide (AVS) and sediment organic matter, reduce metal bioavailability to benthic organisms. Because ESBs link metal bioavailability to partitioning to particles, they also predict that measuring metals in porewater can lead to a more accurate assessment of bioavailability and toxicity to benthic organisms. At the time of their development, sediment ESBs based on the analysis of porewater metal concentrations were limited to comparison with hardness-dependent metals criteria for the calculation of interstitial water benchmark units (IWBUs). However, the multimetal biotic ligand model (mBLM) provides a more comprehensive assessment of porewater metal concentrations, because it considers factors in addition to hardness, such as pH and dissolved organic carbon, and allows for interactions between metals. To evaluate the utility of the various sediment and porewater ESBs, four Hyalella azteca bioassay studies were identified that included sediment and porewater measurements of metals and porewater bioavailability parameters. Evaluations of excess simultaneously extracted metals, IWBUs, and mBLM toxic units (TUs) were compared among the bioassay studies. For porewater, IWBUs and mBLM TUs were calculated using porewater metal concentrations from samples collected using centrifugation and peepers. The percentage of correct predictions of toxicity was calculated for each benchmark comparison. The mBLM-based assessment using peeper data provided the most accurate predictions for the greatest number of samples among the evaluation methods considered. This evaluation demonstrates the value of porewater-based evaluations in conjunction with sediment chemistry in understanding toxicity observed in bioassay studies. Integr Environ Assess Manag 2022;18:1335-1347. © 2021 SETAC., (© 2021 SETAC.)

Biotic ligand models (BLMs) have been broadly accepted and used in ecological risk assessment of heavy metals for toxicity normalization with respect to water chemistry. However, the importance of assessing bioavailability by using BLMs has not been widely recognized among Japanese stakeholders. Failing to consider bioavailability may result in less effective risk management than would be possible if currently available state-of-the-art methods were used to relate bioavailable concentrations to toxic effects. In this study, an ecological risk assessment was conducted using BLMs for 6 rivers in Tokyo to stimulate discussion about bioavailability of heavy metals and the use of BLMs in ecological risk management in Japan. In the risk analysis, a Bayesian approach was used to take advantage of information from previous analyses and to calculate uncertainties in the estimation of risk. Risks were judged to be a concern if the predicted environmental concentration exceeded the 5th percentile concentration (HC5) of the species sensitivity distribution. Based on this criterion, risks to stream biota from exposure to Cu were judged not to be very severe, but it would be desirable to conduct further monitoring and field surveys to determine whether temporary exposure to concentrations exceeding the HC5 causes any irreversible effects on the river ecosystem. The risk of exposure to Ni was a concern at only 1 of the 6 sites. BLM corrections affected these conclusions in the case of Cu but were moot in the case of Ni. The use of BLMs in risk assessment calculations for Japanese rivers requires water quality information that is, unfortunately, not always available. Integr Environ Assess Manag 2013; 9: 63-69. © 2012 SETAC [ABSTRACT FROM AUTHOR]

Copper (Cu) is a widespread soil contaminant that is known to be highly toxic to soil biota. Limited information is available on the response of wild endemic species to Cu in the literature, which hinders ecological risk assessments and revegetation. In the present study, the phytotoxicity of Cu in nutrient solution was studied in five Australian endemic plant species (Acacia decurrens, Austrodanthonia richardsonii (Wallaby Grass), Bothriochloa macra (Redgrass), Eucalyptus camaldulensis var. camaldulensis (River Red-Gum) and Dichanthium sericeum (Bluegrass) and two vegetable plants species (Lactuca sativa L. ‘Great lakes’ and Raphanus sativa L.). Vegetable species were grown in a more concentrated nutrient solution. The response of B. macra was also compared between the two nutrient solutions (dilute and concentrated nutrient solution). In the first experiment, D. sericeum and E. camaldulensis were found to be highly sensitive to Cu exposure in nutrient culture. Critical exogenous Cu concentrations (50 percent reduction in roots) for E. camaldulensis, D. sericeum, A. richardsonii, B. macra (dilute), L. sativa, B. macra (concentrated), R. sativa and A. decurrens were, respectively, (μg/L) 16, 35, 83, 88, 97, 105, 128 and 186. Copper tolerance in B. macra was observed to be higher in the more concentrated nutrient solution despite the estimated Cu2+ concentration being very similar in treatment solutions. Additional short-term rhizo-accumulation studies showed that neither Ca2+ not K+ was responsible for reduced uptake at the roots. However, the estimated maximum shoot Cu was reduced from 41 to 24mg/kg in the more concentrated solution. [Copyright &y& Elsevier]

Abstract: Metal gill binding and toxicity can be modeled using the concentration addition model, in which the toxic unit (TU) concept is used to determine if constituent metals are acting in a strictly additive, less than, or greater than additive fashion. To test this hypothesis, rainbow trout (Oncorhynchus mykiss) were exposed to a matrix of Pb plus Cd mixtures (nominal concentrations=0.75, 1.5, 2.25, 3.0μmolL−1), in the presence or absence of mainly terrigenous (allochthonous; 10mg CL−1) natural organic matter (NOM), and metal–gill binding, and toxicity was quantified. Based on its greater affinity for metal–gill binding sites, Cd–gill binding was expected to exceed Pb–gill binding during metal mixture exposure, but this only occurred at the lowest metal concentrations (0.75μmolL−1); at higher concentrations Pb–gill binding was greater than Cd–gill binding. These unexpected observations were because Pb and Cd likely bind to different populations of high affinity, low capacity binding sites on the gill, which was borne out in subsequent attempts to mathematically model metal–gill interactions during metal-mixture exposure. The presence of an additional low affinity, high capacity population of Pb–gill binding sites also contributed to higher Pb–gill accumulation. Metal–gill interactions were complicated by NOM, which exacerbated toxicity during Cd-only exposure despite lowering Cd–gill accumulation. NOM also promoted Cd–gill binding in the presence of low-moderate concentrations of Pb (0.75 and 1.50μmolL−1). We suggest that direct interactions of Cd–NOM complexes with the gill, and increases in Cd bioavailability due to Pb outcompeting Cd for NOM–metal binding sites due to its greater affinity for such ligands, accounted for greater Cd–gill binding and toxicity. We conclude that interactions of Pb and Cd with the gill cannot be predicted using the concentration addition model, and that NOM is not universally protective against metal–gill binding and toxicity when fish are exposed to metal mixtures. [Copyright &y& Elsevier]

Cyanide can be toxic to aquatic organisms, and the U.S. Environmental Protection Agency has developed ambient water-quality criteria to protect aquatic life. Recent work suggests that considering free, rather than total, cyanide provides a more accurate measure of the biological effects of cyanides and provides a basis for water-quality criteria. Aquatic organisms are sensitive to free cyanide, although certain metals can form stable complexes and reduce the amount of free cyanide. As a result, total cyanide is less toxic when complexing metals are present. Cyanide is often present in complex effluents, which requires understanding how other components within these complex effluents can affect cyanide speciation and bioavailability. The authors have developed a model to predict the aqueous speciation of cyanide and have shown that this model can predict the toxicity of metal-cyanide complexes in terms of free cyanide in solutions with varying water chemistry. Toxicity endpoints based on total cyanide ranged over several orders of magnitude for various metal-cyanide mixtures. However, predicted free cyanide concentrations among these same tests described the observed toxicity data to within a factor of 2. Aquatic toxicity can be well-described using free cyanide, and under certain conditions the toxicity was jointly described by free cyanide and elevated levels of bioavailable metals. Environ. Toxicol. Chem. 2012; 31: 1774-1780. © 2012 SETAC [ABSTRACT FROM AUTHOR]

Within the biotic ligand model (BLM) construct, major cations are considered to be simple competitors for metal binding to uptake sites and may offer some protection against metal-induced toxicity, but the influence of essential trace elements and cell preconditioning to different micronutrient concentrations on metal uptake and toxicity is considered negligible. To test these underlying assumptions, we monitored Cd uptake and toxicity in a green alga ( Chlamydomonas reinhardtii) after long-term exposures (60 h) to a range of environmentally realistic free Zn2+, Co2+, Fe3+, Mn2+, Ca2+, and Cu2+ concentrations buffered with nitrilotriacetic acid. A 200-fold increase in free [Mn2+] as well as a 100-fold increase in free [Fe3+] did not affect Cd uptake or toxicity, whereas a 50-fold increase in free [Ca2+] effectively offered some protection, as predicted by the BLM. However, a 10-fold increase in free [Cu2+] significantly enhanced Cd toxicity by a factor of approximately 2, whereas a 100-fold increase in free [Zn2+] and [Co2+] from 10−11 to 10−9 M significantly decreased Cd uptake and toxicity by more than twofold. These effects did not change with prior algal acclimation to different essential micronutrient concentrations. Low essential trace metal concentrations may strongly affect the uptake and toxicity of Cd in freshwater algae and should be taken into consideration in future developments of the BLM. Environ. Toxicol. Chem. 2012; 31: 1445-1452. © 2012 SETAC [ABSTRACT FROM AUTHOR]

The United States Environmental Protection Agency's (U.S. EPA) current ambient water quality criteria (AWQC) for zinc in freshwater are hardness-based and were last updated in 1995. The acute and chronic freshwater toxicity databases have since expanded substantially and the U.S. EPA's minimum phylogenetic diversity requirements for chronic zinc toxicity are now met (an acute:chronic ratio was previously required). Additionally, several acute and chronic biotic ligand models (BLMs) for zinc have since been developed and validated for freshwater organisms. Using the expanded toxicity database and existing BLMs, we developed a unified zinc BLM that could efficiently predict both acute and chronic toxicity over a wide range of zinc bioavailabilities. The unified BLM, developed by objectively averaging the biotic ligand binding constants for zinc (Zn2+) and competing cations (Ca2+, Mg2+, Na+, H+) from existing BLMs, performed better in predicting toxicity to a diverse set of organisms than any individual existing BLM. Performance of the unified BLM was further improved by optimizing the biotic ligand binding constant for the ZnOH+ species. The updated freshwater zinc toxicity database and unified BLM were then used to estimate the fifth percentiles of the acute and chronic species sensitivity distributions following the U.S. EPA guidelines for AWQC development. Environ. Toxicol. Chem. 2012;31:1264-1272. © 2012 SETAC [ABSTRACT FROM AUTHOR]

Abstract: Evaluating water quality and the health of aquatic organisms is challenging in systems with systematic diel (24h) or less predictable runoff-induced changes in water composition. To advance our understanding of how to evaluate environmental health in these dynamic systems, field studies of diel cycling were conducted in two streams (Silver Bow Creek and High Ore Creek) affected by historical mining activities in southwestern Montana. A combination of sampling and modeling tools was used to assess the toxicity of metals in these systems. Diffusive Gradients in Thin Films (DGT) samplers were deployed at multiple time intervals during diel sampling to confirm that DGT integrates time-varying concentrations of dissolved metals. Site specific water compositions, including time-integrated dissolved metal concentrations determined from DGT, a competitive, multiple-toxicant biotic ligand model, and the Windemere Humic Aqueous Model Version 6.0 (WHAM VI) were used to determine the equilibrium speciation of dissolved metals and biotic ligands. The model results were combined with previously collected toxicity data on cutthroat trout to derive a relationship that predicts the relative survivability of these fish at a given site. This integrative approach may prove useful for assessing water quality and toxicity of metals to aquatic organisms in dynamic systems and evaluating whether potential changes in environmental health of aquatic systems are due to anthropogenic activities or natural variability. [Copyright &y& Elsevier]

Various quality predictors of seven different natural dissolved organic matter (DOM) and humic substances were evaluated for their influence on protection of Daphnia magna neonates against copper (Cu) toxicity. Protection was examined at 3 and 6 mg l of dissolved organic carbon (DOC) of each DOM isolate added to moderately hard, dechlorinated water. Other water chemistry parameters (pH, concentrations of DOC, calcium, magnesium and sodium) were kept relatively constant. Predictors included absorbance ratios Abs (index of molecular weight) and Abs-octanol/Abs-water (index of lipophilicity), specific absorption coefficient (SAC; index of aromaticity), and fluorescence index (FI; index of source). In addition, the fluorescent components (humic-like, fulvic-like, tryptophan-like, and tyrosine-like) of the isolates were quantified by parallel factor analysis (PARAFAC). Up to 4-fold source-dependent differences in protection were observed amongst the different DOMs. Significant correlations in toxicity amelioration were found with Abs, Abs-octanol/Abs-water, SAC, and with the humic-like fluorescent component. The relationships with FI were not significant and there were no relationships with the tryptophan-like or tyrosine-like fluorescent components at 3 mg C l, whereas a negative correlation was seen with the fulvic-like component. In general, the results indicate that larger, optically dark, more lipophilic, more aromatic DOMs of terrigenous origin, with higher humic-like content, are more protective against Cu toxicity. A method for incorporating SAC as a DOM quality indicator into the Biotic Ligand Model is presented; this may increase the accuracy for predicting Cu toxicity in natural waters. [ABSTRACT FROM AUTHOR]