[en] Organisms with different exposure routes should be used to simultaneously assess risks of metals in soils. - Application of 5% (w:w) novel metal immobilizing agent reduced the water soluble, the calcium chloride extracted as well as the pore water concentration of zinc in soils from Maatheide, a metal contaminated site in the northeast of Belgium. Addition of the metal immobilizing agents also eliminated acute toxicity to the potworm Enchytraeus albidus and the earthworm Eisenia fetida and chronic toxicity to the springtail Folsomia candida. Cocoon production by E. fetida, however, was still adversely affected. These differences may be explained by the species dependent routes of metal uptake: F. candida is probably mainly exposed via pore water while in E. fetida dietary exposure is probably also important. From these results it is clear that organisms with different exposure routes should be used simultaneously to assess the environmental risk of metal contaminated soils

[en] Currently, soil quality criteria or soil risk assessments of metals are based on laboratory toxicity tests which are carried out in soils freshly spiked with metal salts. With these data, species sensitivity distributions are fitted, from which hazardous concentrations and predicted no effect concentrations are derived. However, due to long-term processes, called ageing, soil metal availability decreases with time. Here we show that pH is the most important parameter determining the effect of ageing on zinc partitioning in soils, with the effect of ageing becoming more important with increasing pH. Furthermore, zinc bioavailability, expressed as the internal zinc concentrations in red clover (Trifolium pratense) is closely related to pore water zinc concentration. In addition, there is a clear dose-response relationship between the survival of the earthworm Eisenia fetida and the calcium chloride-extracted zinc fraction. These results indicate that zinc partitioning can be used to predict zinc bioavailability to terrestrial organisms. However, the use of spiked soils in toxicity assays can result in an over-estimation of the effects of zinc, especially at a high pH. - Zn ageing is affected by pH, while Zn partitioning can be used to predict its bioavailability

[en] Highlights: • Chronic toxicity of Pb varied 4-fold among three algae species. • The use of an organic P avoided Pb precipitation in the experiments. • pH and Dissolved Organic Carbon strongly affect Pb toxicity, Ca and Mg do not. • A bioavailability model was developed that accurately predicts toxicity. • Algae may become the most sensitive species to Pb above pH 7.4. - Abstract: 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 PO_4"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

[en] Pollution induced community tolerance (PICT) is based on the phenomenon that toxic effects reduce survival of the most sensitive organisms, thus increasing community tolerance. Community tolerance for a contaminant is thus a strong indicator for the presence of that contaminant at the level of adverse concentrations. Here we assessed PICT in 11 soils contaminated with zinc runoff from galvanised electricity pylons and 11 reference soils sampled at 10 m distance from these pylons. Using PICT, the influence of background concentration and bioavailability of zinc on zinc sensitivity and functional diversity of microbial communities was assessed. Zinc sensitivity of microbial communities decreased significantly with increasing zinc concentrations in pore water and calcium chloride extracted fraction while no significant relationship was found with total zinc concentration in the soil. It was also found that functional diversity of microbial communities decreased with increasing zinc concentrations, indicating that increased tolerance is indeed an undesirable phenomenon when environmental quality is considered. The hypothesis that zinc sensitivity of microbial communities is related to background zinc concentration in pore water could not be confirmed. - Zinc sensitivity of microbial communities and functional diversity decrease with increasing zinc concentration in the pore water

[en] An extensive data set describing effects of the herbicide linuron on macrophyte-dominated microcosms was analysed with a food web model to assess effects on ecosystem functioning. We showed that sensitive phytoplankton and periphyton groups in the diets of heterotrophs were gradually replaced by more tolerant phytoplankton species as linuron concentrations increased. This diet shift - showing redundancy among phytoplankton species - allowed heterotrophs to maintain their functions in the contaminated microcosms. On an ecosystem level, total gross primary production was up to hundred times lower in the treated microcosms but the uptake of dissolved organic carbon by bacteria and mixotrophs was less sensitive. Food web efficiency was not consistently lower in the treated microcosms. We conclude that linuron predominantly affected the macrophytes but did not alter the overall functioning of the surrounding planktonic food web. Therefore, a risk assessment that protects macrophyte growth also protects the functioning of macrophyte-dominated microcosms. - Highlights: → Food web modelling reveals the functional response of species and ecosystem to linuron. → Primary production was more sensitive to linuron than bacterial production. → Linuron replaced sensitive phytoplankton by tolerant phytoplankton in heterotrophs' diets. → Linuron did not change the functioning of heterotrophs. - Food web modelling reveals functional redundancy of the planktonic community in microcosms treated with linuron.

[en] In aquatic ecosystems, mixtures of chemical and natural stressors can occur which may significantly complicate risk assessment approaches. Here, we show that effects of binary combinations of four different insecticides and Microcystis aeruginosa, a toxic cyanobacteria, on Daphnia pulex exhibited distinct interaction patterns. Combinations with chlorpyrifos and tetradifon caused non-interactive effects, tebufenpyrad caused an antagonistic interaction and fenoyxcarb yielded patterns that depended on the reference model used (i.e. synergistic with independent action, additive with concentration addition). Our results demonstrate that interactive effects cannot be generalised across different insecticides, not even for those targeting the same biological pathway (i.e. tebufenpyrad and tetradifon both target oxidative phosphorylation). Also, the concentration addition reference model provided conservative predictions of effects in all investigated combinations for risk assessment. These predictions could, in absence of a full mechanistic understanding, provide a meaningful solution for managing water quality in systems impacted by both insecticides and cyanobacterial blooms. - Highlights:: • 2 of 4 insecticide-Microcystis combinations showed no interactive effect on Daphnia. • One insecticide showed antagonistic deviation patterns. • For one other insecticide the results depended on the reference model used. • Interactive effects between insecticides and Microcystis cannot be generalized. • The concentration addition model provides conservative estimates of mixture effects. - Interactive effects between insecticides and cyanobacterial stressors cannot be generalized, not even for insecticides with closely related known modes of action

[en] The European Union regulation on Registration, Evaluation, Authorization and Restriction of Chemical substances (REACH) (EC, 2006) requires the characterization of the chronic toxicity of many chemicals in the aquatic environment, including molybdate (MoO₄^2-). Our literature review on the ecotoxicity of molybdate revealed that a limited amount of reliable chronic no observed effect concentrations (NOECs) for the derivation of a predicted no-effect concentration (PNEC) existed. This paper presents the results of additional ecotoxicity experiments that were conducted in order to fulfill the requirements for the derivation of a PNEC by means of the scientifically most robust species sensitivity distribution (SSD) approach (also called the statistical extrapolation approach). Ten test species were chronically exposed to molybdate (added as sodium molybdate dihydrate, Na₂MoO₄.2H₂O) according to internationally accepted standard testing guidelines or equivalent. The 10% effective concentrations (EC10, expressed as measured dissolved molybdenum) for the most sensitive endpoint per species were 62.8-105.6 (mg Mo)/L for Daphnia magna (21 day-reproduction), 78.2 (mg Mo)/L for Ceriodaphnia dubia (7 day-reproduction), 61.2-366.2 (mg Mo)/L for the green alga Pseudokirchneriella subcapitata (72 h-growth rate), 193.6 (mg Mo)/L for the rotifer Brachionus calyciflorus (48 h-population growth rate), 121.4 (mg Mo)/L for the midge Chironomus riparius (14 day-growth), 211.3 (mg Mo)/L for the snail Lymnaea stagnalis (28 day-growth rate), 115.9 (mg Mo)/L for the frog Xenopus laevis (4 day-larval development), 241.5 (mg Mo)/L for the higher plant Lemna minor (7 day-growth rate), 39.3 (mg Mo)/L for the fathead minnow Pimephales promelas (34 day-dry weight/biomass), and 43.2 (mg Mo)/L for the rainbow trout Oncorhynchus mykiss (78 day-biomass). These effect concentrations are in line with the few reliable data currently available in the open literature. The data presented in this study can serve as a basis for the derivation of a PNEC_aquatic that can be used for national and international regulatory purposes and for setting water quality criteria. Using all reliable data that are currently available, a HC_5,50% (median hazardous concentration affecting 5% of the species) of 38.2 (mg Mo)/L was derived with the statistical extrapolation approach.

[en] In the context of the European Water Framework Directive, controlled flooding of lowlands is considered as a potential water management strategy to minimise the risk of flooding of inhabited areas. However, due to historical pollution and overbank sedimentation, metal levels are elevated in most wetlands, which can cause adverse effects on the ecosystem's dynamics. Additionally, salinity affects the bioavailability of metals present or imported into these systems. The effect of different flooding regimes and salinity exposure scenarios (fresh- and brackish water conditions) on Cu and Zn accumulation in the oligochaete Tubifex tubifex (Mueller, 1774) was examined. Metal mobility was closely linked to redox potential, which is directly related to the prevalent hydrological regime. Flooded, and thus more reduced, conditions minimized the availability of metals, while oxidation of the substrates during a drier period was associated with a rapid increase of metal availability and accumulation in the oligochaetes. - Metal bioavailability in wetlands.

[en] A Biotic Ligand Model was developed predicting the effect of cobalt on root growth of barley (Hordeum vulgare) in nutrient solutions. The extent to which Ca²⁺, Mg²⁺, Na⁺, K⁺ ions and pH independently affect cobalt toxicity to barley was studied. With increasing activities of Mg²⁺, and to a lesser extent also K⁺, the 4-d EC50_Co2+ increased linearly, while Ca²⁺, Na⁺ and H⁺ activities did not affect Co²⁺ toxicity. Stability constants for the binding of Co²⁺, Mg²⁺ and K⁺ to the biotic ligand were obtained: log K _CoBL = 5.14, log K _MgBL = 3.86 and log K _KBL = 2.50. Limited validation of the model with one standard artificial soil and one standard field soil showed that the 4-d EC50_Co2+ could only be predicted within a factor of four from the observed values, indicating further refinement of the BLM is needed. - Biotic Ligand Models are not only a useful tool to assess metal toxicity in aquatic systems but can also be used for terrestrial plants