Charlotte Nys

Toxicity of lead (Pb) to freshwater green algae: Development and validation of a bioavailability model and inter-species sensitivity comparison

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 PO4(3-) 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 Pb(2+) 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 Pb(2+) 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.

The derivation of effects threshold concentrations of lead for European freshwater ecosystems

The main objective of the present study was to derive ecologically relevant effect threshold concentrations of (dissolved) Pb for selected European Union (EU) freshwater rivers, using the 2008 EU Voluntary Risk Assessment Report as a starting point and more advanced methodologies than those used in the Voluntary Risk Assessment Report. This included 1) implementing more robust quality criteria for selecting chronic toxicity data; 2) the conversion of total to dissolved Pb concentrations using a combination of an empirical equation relating inorganic Pb solubility and geochemical speciation modeling to account for effects of dissolved organic matter; 3) the use of bioavailability models for chronic toxicity for species belonging to 3 different trophic levels; and 4) the use of robust methods for large data set handling (such as species sensitivity distribution [SSD] analysis). The authors used published bioavailability models for an algal species (Pseudokirchneriella subcapitata) and a daphnid (Ceriodaphnia dubia) and developed a new model for the fathead minnow (Pimephales promelas). The research has shown that these models are also useful for, and reasonably accurate in, predicting chronic toxicity to other species, including a snail, a rotifer, midge larvae, and an aquatic plant (read-across). A comprehensive chronic toxicity data set for Pb was compiled, comprising 159 individual high-quality toxicity data for 25 different species. By applying the total dissolved conversion and the bioavailability models, normalized toxicity values were obtained, which were then entered into a SSD analysis. Based on the parametric best-fitting SSDs, the authors calculated that ecological threshold concentrations of Pb protecting 95% of freshwater species for 7 selected European freshwater scenarios were between 6.3 μg dissolved Pb/L and 31.1 μg dissolved Pb/L.

Reproductive toxicity of binary and ternary mixture combinations of nickel, zinc, and lead to Ceriodaphnia dubia is best predicted with the independent action model

Metals occur as mixtures in the environment. Risk assessment procedures for metals currently lack a framework to incorporate chronic metal mixture toxicity. In the present study, the toxicity of binary and ternary mixture combinations of Ni, Zn, and Pb was investigated in 3 large-scale experiments using the standard chronic (7-d) Ceriodaphnia dubia reproductive toxicity test. These metals were selected because of anticipated differences in mode of action. The toxicity of the metals in most mixtures, expressed as either free metal ion activities or as dissolved metal concentrations, were antagonistic relative to the concentration addition model, whereas no significant (p < 0.05) interactive effects were observed relative to the independent action model. The only exception was the binary Pb-Zn mixture, for which mixture effects were noninteractive based on the dissolved concentrations, but antagonistic based on free ion activities all relative to the independent action model. Overall, the independent action model fitted the observed toxicity better than the concentration addition model, which is consistent with the different modes of action of these metals. The concentration addition model mostly overestimated toxicity. Finally, the present study warns against extrapolation of the type of interactive effects between species, even when they are closely related. Environ Toxicol Chem 2016;35:1796-1805.

Comparison of chronic mixture toxicity of Ni‐Zn‐Cu and Ni‐Zn‐Cu‐Cd mixtures between Ceriodaphnia dubia and Pseudokirchneriella subcapitata

Although aquatic organisms in the environment are exposed to mixtures of metals, risk assessment for metals is most commonly performed on a metal-by-metal basis. To increase the knowledge about chronic mixture effects, the authors investigated whether metal mixture effects are dependent on the biological species, mixture composition, and metal concentration ratio. The authors evaluated the effects of quaternary Ni-Zn-Cu-Cd and ternary Ni-Zn-Cu mixtures on 48-h algal growth rate (Pseudokirchneriella subcapitata) and 7-d daphnid reproduction (Ceriodaphnia dubia) using a ray design. Single metals were 3-fold to 42-fold more toxic for C. dubia than for P. subcapitata, based on the 50% effective concentration expressed as free metal activity, the range representing different metals. Statistical analysis of mixture effects showed that the ternary and quaternary mixture effects were antagonistic on algal growth relative to the concentration addition (CA) model, when the analysis was based on dissolved concentrations and on free metal ion activities. Using the independent action (IA) model, mixture effects in both rays were statistically noninteractive for algal growth when the analysis was based on dissolved concentrations; however, the interactions shifted toward antagonism when based on free ion activities. The ternary Ni-Zn-Cu mixture acted antagonistically on daphnid reproduction relative to both reference models, either expressed as free ion activities or dissolved concentrations. When Cd was added to the mixture, however, the mixture effects shifted toward noninteractivity for daphnids. The metal concentration ratio did not significantly influence the magnitude of observed antagonistic effects. Regardless of statistical interactions observed, based on the present study, CA and in most instances also IA can serve as a protective model for ternary Ni-Zn-Cu and quaternary Ni-Zn-Cu-Cd toxicity to both species. Environ Toxicol Chem 2017;36:1056-1066.

The effect of pH on chronic aquatic nickel toxicity is dependent on the pH itself: Extending the chronic nickel bioavailability models

The environmental quality standard for Ni in the European Commissions Water Framework Directive is bioavailability based. Although some of the available chronic Ni bioavailability models are validated only for pH ≤ 8.2, a considerable fraction of European surface waters has a pH > 8.2. Therefore, the authors investigated the effect of a change in pH from 8.2 to 8.7 on chronic Ni toxicity in 3 invertebrate (Daphnia magna, Lymnaea stagnalis, and Brachionus calyciflorus) and 2 plant species (Pseudokirchneriella subcapitata and Lemna minor). Nickel toxicity was almost always significantly higher at pH 8.7 than at pH 8.2. To test whether the existing chronic Ni bioavailability models developed for pH ≤ 8.2 can be used at higher pH levels, Ni toxicity at pH 8.7 was predicted based on Ni toxicity observed at pH 8.2. This resulted in a consistent underestimation of toxicity. The results suggest that the effect of pH on Ni(2+) toxicity is dependent on the pH itself: the slope of the pH effect is steeper above than below pH 8.2 for species for which a species-specific bioavailability model exists. Therefore, the existing chronic Ni bioavailability models were modified to allow predictions of chronic Ni toxicity to invertebrates and plants in the pH range of 8.2 to 8.7 by applying a pH slope (SpH ) dependent on the pH of the target water. These modified Ni bioavailability models resulted in more accurate predictions of Ni toxicity to all 5 species (within 2-fold error), without the bias observed using the bioavailability models developed for pH ≤ 8.2. The results of the present study can decrease the uncertainty in implementing the bioavailability-based environmental quality standard under the Water Framework Directive for high-pH regions in Europe.

Chapter 7 – Environmental Toxicity Assessment of Complex Inorganic Materials

Abstract The management of the risks posed by complex inorganic materials for the environment requires an appropriate identification of their possible hazards and exposure. Most chemical management systems outline how to identify and characterise environmental hazards; however data on complex inorganic materials allowing to fulfil the information requirements are usually scarce. The assessment is therefore frequently based on the constituents of the complex inorganic material. However this approach poses the scientific challenges to address the consideration of the combined environmental effects of the contained metal/metal compounds. The default assessment can be refined by applying approaches quantifying the solubility and bioavailability of the metals included in the material and specific techniques that were developed for hazard and risk assessments of single inorganic compounds, notably, metals. This chapter outlines the issues and options for tiered approaches for refinement, and illustrates them with some practical examples.