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Protecting the structure and functioning of soil ecosystems is one of the central aims of current regulations of chemicals. This is, for instance, shown by the emphasis on the protection of key drivers and ecosystem services as proposed in the protection goal options for soil organisms by the European Food Safety Authority (EFSA). Such targets require insight into soil biodiversity, its role in the functioning of ecosystems, and the way it responds to stress. Also required are tools and methodologies for properly assessing biodiversity. To address these issues, the Society of Environmental Toxicology and Chemistry (SETAC) Europe 14 th Special Science Symposium (SESSS14) was held 19 to 20 November 2019 in Brussels, Belgium. The central aim of the SESSS14 was to provide information on how to include soil biodiversity and soil functions as protection goal options in the risk assessment and quantification of the effects of chemicals and other stressors (including their respective regulations). This paper is based on the presentations and discussions at the SESSS14 and will give a brief update on the scientific state-of-the art on soil biodiversity, novel scientific developments, experimental and modeling approaches, as well as case studies. It will also discuss how these approaches could inform future risk assessment of chemicals and other stressors in the regulatory context of protecting soil ecosystems. Integr Environ Assess Manag 2021;17:541-551. © 2020 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC)., (© 2020 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).)

Earthworms are important ecosystem engineers, and assessment of the risk of plant protection products toward them is part of the European environmental risk assessment (ERA). In the current ERA scheme, exposure and effects are represented simplistically and are not well integrated, resulting in uncertainty when the results are applied to ecosystems. Modeling offers a powerful tool to integrate the effects observed in lower tier laboratory studies with the environmental conditions under which exposure is expected in the field. This paper provides a summary of the (In)Field Organism Risk modEling by coupling Soil Exposure and Effect (FORESEE) Workshop held 28-30 January 2020 in Düsseldorf, Germany. This workshop focused on toxicokinetic-toxicodynamic (TKTD) and population modeling of earthworms in the context of ERA. The goal was to bring together scientists from different stakeholder groups to discuss the current state of soil invertebrate modeling and to explore how earthworm modeling could be applied to risk assessments, in particular how the different model outputs can be used in the tiered ERA approach. In support of these goals, the workshop aimed at addressing the requirements and concerns of the different stakeholder groups to support further model development. The modeling approach included 4 submodules to cover the most relevant processes for earthworm risk assessment: environment, behavior (feeding, vertical movement), TKTD, and population. Four workgroups examined different aspects of the model with relevance for risk assessment, earthworm ecology, uptake routes, and cross-species extrapolation and model testing. Here, we present the perspectives of each workgroup and highlight how the collaborative effort of participants from multidisciplinary backgrounds helped to establish common ground. In addition, we provide a list of recommendations for how earthworm TKTD modeling could address some of the uncertainties in current risk assessments for plant protection products. Integr Environ Assess Manag 2021;17:352-363. © 2020 SETAC., (© 2020 SETAC.)

The soil-living mite Oppia nitens Koch has recently been proposed as a promising test species for the ecotoxicological risk assessment of contaminated boreal soils. Adding oribatid mites to the assemblage of test species for soil is highly desirable given the enormous diversity and ecological significance of these microarthropods. The authors aimed at revealing how toxicity, lethal body concentration, and bioaccumulation of cadmium (Cd) changed over a period of 7 wk when mites were exposed to Cd-spiked natural soils. The estimated median lethal concentration (LC50) values showed a gradual decrease with time, but a steady state was not reached within 7 wk. Estimates for lethal body concentration varied from 44 μg Cd/g to 91 μg Cd/g dry body weight, with a tendency to increase with time. The estimated 50% effective concentration (EC50) for effects on reproduction after 7-wk exposure was 345 μg Cd/g dry soil. Accumulation of Cd in mites was extremely variable but overall showed a nonsaturating increase. A simple 1-compartment toxicokinetic model did not describe the data well. The analysis suggests that O. nitens has a storage-detoxification strategy that is not at equilibrium under chronic exposure. Considering the tiny body size of the animal, it is remarkable that long exposure times are necessary to reveal chronic toxicity. The use of oribatids provides a clear added value to soil risk assessment but trades off with exposure length. Environ Toxicol Chem 2017;36:408-413. © 2016 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC., (© 2016 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC.)

To assess the influence of soil properties and aging on the availability and toxicity of zinc (Zn) applied as nanoparticles (Zn oxide [ZnO]-NPs) or as Zn 2+ ions (Zn chloride [ZnCl 2 ]), 3 natural soils were individually spiked with either ZnO-NPs or ZnCl 2 and incubated for up to 6 mo. Available Zn concentrations in soil were measured by porewater extraction (ZnPW), whereas earthworms (Eisenia andrei) were exposed to study Zn bioavailability. Porewater extraction concentrations were lower when Zn was applied as NPs compared to the ionic form and decreased with increasing soil pH. For both Zn forms and Zn-PW values were affected by aging, but they varied among the tested soils, highlighting the influence of soil properties. Internal Zn concentration in the earthworms (ZnE) was highest for the soil with high organic carbon content (5.4%) and basic pH (7.6) spiked with Zn-NPs, but the same soil spiked with ZnCl 2 showed the lowest increase in ZnE compared to the control. Survival, weight change, and reproduction of the earthworms were affected by both Zn forms; but differences in toxicity could not be explained by soil properties or aging. This shows that ZnO-NPs and ZnCl 2 behave differently in soils depending on soil properties and aging processes, but differences in earthworm toxicity remain unexplained. Environ Toxicol Chem 2017;36:137-146. © 2016 SETAC., (© 2016 SETAC.)

Polycyclic aromatic hydrocarbons (PAHs) continue to cause environmental challenges as a result of their release into the environment by a great variety of anthropogenic activities and their accumulation in soils. Studies were conducted on the toxicological effect of the model PAH phenanthrene using the soil invertebrate model Enchytraeus crypticus at the individual, tissue, and molecular levels. Animals were exposed for 2 d and 21 d to phenanthrene concentrations corresponding to the (previously estimated) 3-wk effective concentration, 10% (EC10) and EC50 for effects on reproduction. Gene expression profiling did not reveal a typical phenanthrene-induced biotransformation signature, as it usually does in arthropods and vertebrates. Instead, after 2 d of exposure, only general metabolic processes were affected, such as translation and adenosine triphosphate synthesis-coupled electron transport. Histological sections of tissues of 2-d exposed animals showed no deviations from control. In contrast, after prolonged exposure of up to 21 d, histopathological effects were found: chloragogenous cells were highly vacuolated and hypertrophic. This was corroborated by differential expression of genes related to immune response and oxidative stress at the transcriptomic level. The data exemplify the complexity and species-specific features of PAH toxicity among soil invertebrate communities, which restricts read-across and extrapolation in the context of soil ecological risk assessment. Environ Toxicol Chem 2016;35:2713-2720. © 2016 SETAC., (© 2016 SETAC.)

The bioavailability of metals in soil is a dynamic process. For a proper extrapolation to the field of laboratory studies on fate and effects, it is important to understand the dynamics of metal bioavailability and the way it is influenced by soil properties. The aim of this study was to assess the parallel (concurrent) effect of pH and aging time on the partitioning of cadmium in natural LUFA 2.2 soil. Cadmium nitrate-spiked pH-amended LUFA 2.2 soils were incubated under laboratory conditions for up to 30 weeks. Measured pHpw was lower after 3 weeks and decreased only slightly toward the end of the test. Cadmium concentrations in the pore water increased with time for all soil pH levels, while they decreased with increasing pH. Freundlich kf values ranged between 4.26 and 934 L kg(-1) (n = 0.79 to 1.36) and were highest at the highest pH tested (pH = 6.5). Multiple linear regression analysis, based on a soil ligand modeling approach, resulted in affinity constants of 2.61 for Ca(2+) (log KCa-SL) and 5.05 for H(+) (log KH-SL) for their binding to the active sites on the soil surface. The results showed that pH and aging time are two important factors which together affect cadmium partitioning and mobility in spiked natural soils.

The usage of Engineered Nanoparticles (ENPs) in consumer products is relatively new and there is a need to conduct environmental risk assessment (ERA) to evaluate their impacts on the environment. However, alternative approaches are required for ERA of ENPs because of the huge gap in data and knowledge compared to conventional pollutants and their unique properties that make it difficult to apply existing approaches. This study aims to propose an ERA approach for ENPs by integrating Analytical Hierarchy Process (AHP) and fuzzy inference models which provide a systematic evaluation of risk factors and reducing uncertainty about the data and information, respectively. Risk is assumed to be the combination of occurrence likelihood, exposure potential and toxic effects in the environment. A hierarchy was established to evaluate the sub factors of these components. Evaluation was made with fuzzy numbers to reduce uncertainty and incorporate the expert judgements. Overall score of each component was combined with fuzzy inference rules by using expert judgements. Proposed approach reports the risk class and its membership degree such as Minor (0.7). Therefore, results are precise and helpful to determine the risk management strategies. Moreover, priority weights calculated by comparing the risk factors based on their importance for the risk enable users to understand which factor is effective on the risk. Proposed approach was applied for Ag (two nanoparticles with different coating) and TiO2 nanoparticles for different case studies. Results verified the proposed benefits of the approach., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Many microbial ecology studies have demonstrated profound changes in community composition caused by environmental pollution, as well as adaptation processes allowing survival of microbes in polluted ecosystems. Soil microbial communities in polluted areas with a long-term history of contamination have been shown to maintain their function by developing metal-tolerance mechanisms. In the present work, we review recent experiments, with specific emphasis on studies that have been conducted in polluted areas with a long-term history of contamination that also applied DNA-based approaches. We evaluate how the "costs" of adaptation to metals affect the responses of metal-tolerant communities to other stress factors ("stress-on-stress"). We discuss recent studies on the stability of microbial communities, in terms of resistance and resilience to additional stressors, focusing on metal pollution as the initial stress, and discuss possible factors influencing the functional and structural stability of microbial communities towards secondary stressors. There is increasing evidence that the history of environmental conditions and disturbance regimes play central roles in responses of microbial communities towards secondary stressors.

Silver nanoparticles (Ag NPs) have been used in numerous consumer products and may enter the soil through the land application of biosolids. However, little is known about the relationship between Ag NP exposure and their bioavailability for soil organisms. This study aims at comparing the uptake and elimination kinetics of Ag upon exposures to different Ag forms (NPs and ionic Ag (as AgNO3)) in the isopod Porcellionides pruinosus. Isopods were exposed to contaminated Lufa 2.2 soil or alder leaves as food. Uptake and elimination rate constants for soil exposure did not significantly differ between Ag NPs and ionic Ag at 30 and 60 mg Ag/kg. For dietary exposure, the uptake rate constant was up to 5 times higher for Ag NPs than for AgNO3, but this was related to feeding activity and exposure concentrations, while no difference in the elimination rate constants was found. When comparing both routes, dietary exposure resulted in lower Ag uptake rate constants but elimination rate constants did not differ. A fast Ag uptake was observed from both routes and most of the Ag taken up seemed not to be eliminated. Synchrotron X-ray fluorescence showed Ag in the S-cells of the hepatopancreas, thus supporting the observations from the kinetic experiment (i.e. low elimination). In addition, our results show that isopods have an extremely high Ag accumulation capacity, suggesting the presence of an efficient Ag storage compartment.

The aim of the present study was to evaluate the effect of silver nanoparticles (AgNPs) on Enchytraeus crypticus, applying a combined toxicokinetics and toxicodynamics approach to understand the relationship between survival and the development of internal Ag concentrations in the animals over time. Toxicity tests were conducted in medium composed of well-defined aqueous solutions added to inert quartz sand to avoid the complexity of soil conditions. Citrate-coated AgNPs (AgNP-Cit) and polyvinylpyrrolidone-coated AgNPs (AgNP-PVP) were tested and compared with silver nitrate (AgNO3), which was used as a positive control for Ag ion effects. The median lethal concentration (LC50) values based on Ag concentrations in the solution phase of the test medium decreased over time and reached steady state after 7 d, with AgNO3 and AgNP-PVP being more toxic than AgNP-Cit. Slow dissolution may explain the low uptake kinetics and lower toxicity of AgNP-Cit compared with the other 2 Ag forms. The LC50 values based on internal Ag concentrations in the animals were almost stable over time, highlighting the importance of integrating toxicokinetics and toxicodynamics and relating survival with internal Ag concentrations. Neither survival-based elimination rates nor internal LC50s in the organisms showed any significant evidence of nano-specific effects for both AgNPs, although they suggested some uptake of particulate Ag for AgNP-Cit. The authors conclude that the toxicity of both types of AgNP probably is mainly attributable to the release of Ag ions., (© 2015 SETAC.)

Uptake and toxicity of Ni, Co and their mixtures in Enchytraeus crypticus after different exposure times (4, 7, 10 and 14d) were predicted using the WHAM-FTOX model, which incorporates the effects of metal speciation, affinity and competition of metals for binding sites. The combined toxicity of metals was quantified by the toxicity function (FTOX), a linear combination of the amount of metal binding to non-specific ligand sites (vi) and a toxicity coefficient (αi). Observed body concentrations of Ni and Co in the animals correlated well with the WHAM-calculated amounts binding to humic acid, supporting the use of humic acid as a surrogate for metal binding sites of E. crypticus. The toxicity of metals at different exposure times was well predicted by the WHAM-FTOX model. The derived αNi increased with time and reached equilibrium after approximately 14d, while αCo remained almost independent of time. This suggests for Ni more time is needed than for Co to reach equilibrium of body concentrations, so the toxicity of Ni is much more time-dependent. The WHAM-FTOX model provides a new tool for evaluating the potential mixture toxicity of metals to soil organisms in a dynamic environment. However, as αi varied with exposure time, caution is warranted when using the parameters estimated from acute toxicity experiments for predicting the chronic toxicity of metal mixtures., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

This study aimed at assessing the influence of soil properties on the uptake and toxicity effects of arsenic in the earthworm Eisenia andrei exposed for 4 weeks to seven natural soils spiked with different arsenic concentrations. Water-soluble soil concentrations (AsW) and internal As concentrations in the earthworms (AsE) were greatly different between soils. These two variables were highly correlated and were key factors in earthworm toxicity response. AsW was explained by some soil properties, such as the pH, calcium carbonate content, ionic strength, texture or oxide forms. Toxicity showed a clear variation between soils, in some cases without achieving 50 % adverse effect at the highest As concentration added (600 mg kg(-1)). Nevertheless, soil properties did not show, in general, a high relation with studied toxicity endpoints, although the high correlation with AsW could greatly reduce indirectly As bioavailability and toxicity risk for earthworms. Obtained results suggest that soil properties should be part of the criteria to establishing thresholds for contaminated soils because they will be key in controlling As availability and thus result in different degrees of toxicity.

The effects of Ag-NPs and AgNO3 on the isopod Porcellionides pruinosus were determined upon soil and dietary exposures. Isopods avoided Ag in soil, with EC50 values of ∼16.0 and 14.0 mg Ag/kg for Ag-NPs and AgNO3, respectively. Feeding inhibition tests in soil showed EC50s for effects on consumption ratio of 127 and 56.7 mg Ag/kg, respectively. Although similar EC50s for effects on biomass were observed for nanoparticulate and ionic Ag (114 and 120 mg Ag/kg dry soil, respectively), at higher concentrations greater biomass loss was found for AgNO3. Upon dietary exposure, AgNO3 was more toxic, with EC50 for effects on biomass change being >1500 and 233 mg Ag/kg for Ag-NPs and AgNO3, respectively. The difference in toxicity between Ag-NPs and AgNO3 could not be explained from Ag body concentrations. This suggests that the relation between toxicity and bioavailability of Ag-NPs differs from that of ionic Ag in soils., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The biotic ligand model (BLM) approach is used to assess metal toxicity, taking into account the competition of other cations with the free metal ions for binding to the biotic ligand sites of aquatic and soil organisms. The bioavailable fraction of metals, represented by the free metal ion, is a better measure than the total concentration for assessing their potential risk to the environment. Because BLMs are relating toxicity to the fraction of biotic ligands occupied by the metal, they can be useful for investigating factors affecting metal bioaccumulation and toxicity. In the present review, the effects of major cations on the toxicity of metals to soil and aquatic organisms were comprehensively studied by performing a meta-analysis of BLM literature data. Interactions at the binding sites were shown to be species- and metal-specific. The main factors affecting the relationships between toxicity and conditional binding constants for metal binding at the biotic ligand appeared to be Ca(2+) , Mg(2+) , and protons. Other important characteristics of the exposure medium, such as levels of dissolved organic carbon and concentrations of other cations, should also be considered to obtain a proper assessment of metal toxicity to soil and aquatic organisms., (© 2015 SETAC.)

Climate change may alter physical, chemical and biological properties of ecosystems, affecting organisms but also the fate of chemical pollutants. This study aimed to find out how changes in climate conditions (air temperature, soil moisture content) affect the toxicity of metal-polluted soils to the soft-bodied soil organism Enchytraeus crypticus, linking enchytraeid performance with changes in soil available and body metal concentrations. Bioassays with E. crypticus were performed under different combinations of air temperature (20 and 25 °C) and soil moisture content (50% and 30% of the soil water holding capacity, WHC) in dilution series of three metal-polluted soils (mine tailing, forest and watercourse). After 21 d exposure, enchytraeid reproduction was determined, and soil available (extracted with 0.01 M CaCl2) and body Cd, Cu, Pb and Zn concentrations in surviving adults were determined. In general, Cd, Pb and Zn availability decreased upon incubation under the different climate scenarios. In the watercourse soil, with initially higher available metal concentrations (678 µg Cd kg(-1), 807 µg Pb kg(-1) and 31,020 µg Zn kg(-1)), decreases were greatest at 50% WHC probably due to metal immobilization as carbonates. Enchytraeid reproduction was negatively affected by higher available metal concentrations, with reductions up to 98% in the watercourse soil compared to the control soil at 30% WHC. Bioaccumulation of Cd, Pb and Zn was higher when drier conditions were combined with the higher temperature of 25 °C. Changes in metal bioavailability and bioaccumulation explained the toxicity of soil polluted by metal mine wastes to enchytraeids under changing environmental conditions., (Copyright © 2015 Elsevier Inc. All rights reserved.)

Current bioavailability models, such as the free ion activity model and biotic ligand model, explicitly consider that metal exposure will be mainly to the dissolved metal in ionic form. With the rise of nanotechnology products and the increasing release of metal-based nanoparticles (NPs) to the environment, such models may increasingly be applied to support risk assessment. It is not immediately clear, however, whether the assumption of metal ion exposure will be relevant for NPs. Using an established approach of oral gluing, a toxicokinetics study was conducted to investigate the routes of silver nanoparticles (AgNPs) and Ag(+) ion uptake in the soil-dwelling earthworm Lumbricus rubellus. The results indicated that a significant part of the Ag uptake in the earthworms is through oral/gut uptake for both Ag(+) ions and NPs. Thus, sealing the mouth reduced Ag uptake by between 40% and 75%. An X-ray analysis of the internal distribution of Ag in transverse sections confirmed the presence of increased Ag concentrations in exposed earthworm tissues. For the AgNPs but not the Ag(+) ions, high concentrations were associated with the gut wall, liver-like chloragogenous tissue, and nephridia, which suggest a pathway for AgNP uptake, detoxification, and excretion via these organs. Overall, the results indicate that Ag in the ionic and NP forms is assimilated and internally distributed in earthworms and that this uptake occurs predominantly via the gut epithelium and less so via the body wall. The importance of oral exposure questions the application of current metal bioavailability models, which implicitly consider that the dominant route of exposure is via the soil solution, for bioavailability assessment and modeling of metal-based NPs., (© 2015 SETAC.)

We examined the short-term toxicity of AgNPs and AgNO3 to Daphnia magna at sublethal levels using (1)H NMR-based metabolomics. Two sizes of polyvinylpyrrolidone-coated AgNPs (10 and 40nm) were synthesized and characterized and their Ag(+) release was studied using centrifugal ultrafiltration and inductively coupled plasma mass spectrometry. Multivariate statistical analysis of the (1)H NMR spectra showed significant changes in the D. magna metabolic profiles following 48h exposure to both AgNP particle sizes and Ag(+) exposure. Most of the metabolic biomarkers for AgNP exposure, including 3-hydroxybutyrate, arginine, lysine and phosphocholine, were identical to those of the Ag(+)-exposed groups, suggesting that the dominant effects of both AgNPs were due to released Ag(+). The observed metabolic changes implied that the released Ag(+) induced disturbance in energy metabolism and oxidative stress, a proposed mechanism of AgNP toxicity. Elevated levels of lactate in all AgNP-treated but not in Ag(+)-treated groups provided evidence for Ag-NP enhanced anaerobic metabolism. These findings show that (1)H NMR-based metabolomics provides a sensitive measure of D. magna response to AgNPs and that further targeted assays are needed to elucidate mechanisms of action of nanoparticle-induced toxicity., (Copyright © 2015 Elsevier Inc. All rights reserved.)

To what extent chemical contamination affects genetic diversity of wild populations remains an open question in ecotoxicology. Here we used a genome-wide approach (615 nuclear RADseq loci containing 3017 SNPs) and a mtDNA fragment (ATP6) to analyze the effect of long-term exposure to elevated concentrations of metals (Cd, Pb, Zn) on genetic diversity in rove beetle (Staphylinus erythropterus) populations living along a pollution gradient in Poland. In total, 96 individuals collected from six sites at increasing distance from the source of pollution were analyzed. We found weak differentiation between populations suggesting extensive gene flow. The highest genetic diversity was observed in a population inhabiting the polluted site with the highest metal availability. This may suggest increased mutation rates, possibly in relation to elevated oxidative stress levels. The polluted site could also act as an ecological sink receiving numerous migrants from neighboring populations. Despite higher genetic diversity at the most polluted site, there was no correlation between the genetic diversity and metal pollution or other soil properties. We did not find a clear genomic signature of local adaptation to metal pollution. Like in some other cases of metal tolerance in soil invertebrates, high mobility may counteract possible effects of local selective forces associated with soil pollution., (Copyright © 2015 Elsevier Inc. All rights reserved.)

To understand the toxicity of Pb-polluted shooting fields, oribatid mites Platynothrus peltifer were exposed to shooting field soils containing 47-2398 mg Pb/kg dry weight (DW) and having pH(CaCl2) 3.2-6.8 and 3.8-13% organic matter (OM). Exposures also included artificial soils with different pH and OM contents as well as two natural soils used as controls. Exposures lasted for 2 (acute) and 12 weeks (chronic). Survival, reproduction and uptake of Pb in the mites were related to total, water-extractable and 0.01 M CaCl2-extractable and porewater Pb concentrations as well as soil characteristics. After both the acute and chronic exposures, adult survival was not significantly affected, while upon chronic exposure reproduction was remarkably reduced in the acidic forest soils with Pb concentrations ≥2153 mg/kg DW and pH(CaCl2) ≤ 3.5. P. peltifer juvenile numbers were significantly negatively and internal Pb concentrations in the mites were significantly positively related with total, extractable and porewater Pb concentrations. This study shows that P. peltifer is not very sensitive to Pb and therefore may not be a suitable indicator of Pb-polluted soils.

Diclofenac is widely used as nonsteroidal anti-inflammatory drug leaving residues in the environment. To investigate effects on terrestrial ecosystems, we measured dissipation rate in soil and investigated ecotoxicological and transcriptome-wide responses in Folsomia candida. Exposure for 4 weeks to diclofenac reduced both survival and reproduction of F. candida in a dose-dependent manner. At concentrations ≥ 200 mg/kg soil diclofenac remained stable in the soil during a 21-day incubation period. Microarrays examined transcriptional changes at low and high diclofenac exposure concentrations. The results indicated that development and growth were severely hampered and immunity-related genes, mainly directed against bacteria and fungi, were significantly up-regulated. Furthermore, neural metabolic processes were significantly affected only at the high concentration. We conclude that diclofenac is toxic to non-target soil invertebrates, although its mode of action is different from the mammalian toxicity. The genetic markers proposed in this study may be promising early markers for diclofenac ecotoxicity., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Biotic ligand models (BLMs) predicting metal toxicity for a fixed exposure time are available, but it is uncertain how to extrapolate predictions to a dynamic environment with time-variable exposure. Three BLM-based models were developed to describe change of Ni toxicity to Enchytraeus crypticus in time. These models assumed that: (a) biotic ligand binding constants of Ni and competing cations (K(NiBL) and K(CBL)) and the fraction of biotic ligands occupied by Ni to produce 50% mortality (f50) are fixed with time, (b) K(NiBL) and K(CBL) remain constant while f50 varies with time, and (c) K(NiBL), K(CBL), and f50 are all time-dependent. Model (a) successfully described the 7-d toxicity of Ni but failed in explaining Ni toxicity at longer exposure times. Both models (b) and (c) well described Ni toxicity, within a factor of 2, at varying solution chemistries and different exposure times. This shows that the acute BLM cannot directly be applied for predicting chronic metal toxicity and that some BLM parameters may vary with time. Our findings provide plausible explanations for differences in mechanisms of acute and chronic toxicity, offering a framework for incorporating toxicokinetic and toxicodynamic processes in describing Ni toxicity in time., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Chlorantraniliprole (CAP) is a newly developed, widely applied insecticide. In the aquatic environment, several transformation products are formed under natural conditions, one by dehydration and others by photoinduced degradation. Data on aquatic ecotoxicity of CAP can mainly be found in registration and regulatory evaluation reports. Moreover, the toxicity of its transformation products and especially effects upon chronic exposure remain completely unknown. Hence, our aim was to investigate the acute and chronic toxicity of CAP and its transformation products to the daphnid Daphnia magna. The results showed that CAP is extremely toxic to D. magna, with an acute and chronic LC50 of 9.4 and 3.7 μg/L, respectively. No effects on daphnid reproduction were observed, but the impact on daphnid survival also affected population growth rate, with an EC50 of 3.5 μg/L. In contrast, no negative effects of the two main degradation products were observed. The present study demonstrated a high sensitivity of nontarget microcrustaceans to CAP. However, the actual risk of CAP in water diminishes with its spontaneous or light-induced degradation into two transformation products, showing no toxicity to the daphnids in the present study.

Cerium oxide nanoparticles (CeO2 NPs) are used as diesel fuel additives to catalyze oxidation. Phenanthrene is a major component of diesel exhaust particles and one of the most common pollutants in the environment. This study aimed at determining the effect of CeO2 NPs on the toxicity of phenanthrene in Lufa 2.2 standard soil for the isopod Porcellionides pruinosus and the springtail Folsomia candida. Toxicity tests were performed in the presence of CeO2 concentrations of 10, 100 or 1000mg Ce/kg dry soil and compared with results in the absence of CeO2 NPs. CeO2 NPs had no adverse effects on isopod survival and growth or springtail survival and reproduction. For the isopods, LC50s for the effect of phenanthrene ranged from 110 to 143mg/kg dry soil, and EC50s from 17.6 to 31.6mg/kg dry soil. For the springtails, LC50s ranged between 61.5 and 88.3mg/kg dry soil and EC50s from 52.2 to 76.7mg/kg dry soil. From this study it may be concluded that CeO2 NPs have a low toxicity and do not affect toxicity of phenanthrene to isopods and springtails., (Copyright © 2014 Elsevier Inc. All rights reserved.)

The use of synthetic pesticides in tropical countries has increased over the years, following the intensification of agriculture. However, awareness among farmers of the importance of protecting themselves from hazards associated with pesticide application is still lacking, especially in Indonesia. This paper reports results of an inventory on knowledge and attitudes regarding pesticide use by melon farmers of a village in Central Java, Indonesia. The importance of using personal protective equipment such as hats, masks, goggles, boots, and gloves on agricultural land is known and well understood by the farmers. However, in practice, only 3.8 % were wearing glasses and 1.9 % were using boots. In fact, the masks used only consisted of a part of their shirt tied around the mouth. The farmers were not wearing long pants and shirts with long sleeves and used the same clothes for more than 1 day without washing. Almost no farmers used personal protective equipment that was standard, in good condition, and complete. Based on the results of statistical analysis, no significant relationship was found between knowledge and attitude on the required practices on the one hand and the use of personal protective equipment in practice on the other hand. This shows that improved knowledge and attitudes are not enough to change the behavior of farmers to work in a healthy and safe way. The gap between knowledge and practice needs to be bridged by a more interactive and participatory training model. It is therefore of paramount importance to develop a special toolkit for pesticide risk reduction which is developed in a participatory manner involving the farmers as the main actors through a series of focus group discussions and field simulations.

Uptake and toxicity of Ni-Co mixtures in Enchytraeus crypticus were determined after 4 d, 7 d, 10 d, and 14 d exposure. Generally, body concentrations of Ni and Co increased with increasing exposure concentrations. Ni body concentration was significantly reduced in the presence of Co, whereas Ni only marginally affected Co uptake. When expressed as free ion activities, individual toxicity of Ni and Co increased with time, with median lethal concentrations (LC50) decreasing from 78.3 μM and 511 μM at 4 d to 40.4 μM and 393 μM at 14 d, respectively. When expressed as body concentrations, LC50BodyNi remained constant with time whereas LC50BodyCo increased during the first 7 d but remained stable afterwards. As identified by the MIXTOX model, interactions between Ni and Co were mainly antagonistic when based on free ion activities, however, no interaction was observed when based on body concentrations. A process-based model, incorporating exposure time to analyze the mechanisms underlying the dynamic mixture toxicity confirmed the differences in toxicokinetics of the 2 metals. The author's findings suggest that body concentrations, which incorporate bioaccumulation processes, are time-independent and can act as a more constant indicator of metal toxicity. The observed antagonism was mainly caused by competition between Co and Ni for binding sites and subsequent inhibition of Ni uptake. This competitive interaction occurred at the uptake level (toxicokinetics), but not at the target level (toxicodynamics)., (© 2014 SETAC.)

The present study aimed to assess the effects of climate change on the toxicity of metal-polluted soils. Bioassays with Enchytraeus crypticus were performed in soils polluted by mine wastes (mine tailing, forest, and watercourse) and under different combinations of temperature (20 °C and 25 °C) and soil moisture content (50% and 30% of the soil water-holding capacity). Survival and reproduction were set as endpoints. No effect was observed on survival (average survival ≥ 80%). Reproduction was the most sensitive endpoint, and it was reduced between 65% and 98% compared with control after exposure to watercourse soil (lower pH, higher salinity, and higher available metal(loid) concentrations). In this soil, effective concentrations at 50% and 10% (EC50 and EC10) significantly decreased with decreasing soil moisture content. In general, the worst-case scenario was found in the driest soil, but the toxicity under a climate change scenario differed among soil types in relation to soil properties (e.g., pH, salinity) and available metal(loid) concentrations., (© 2014 SETAC.)

To disentangle the contribution of ionic and nanoparticulate Ag to the overall toxicity to the earthworm Eisenia fetida, a semi-permeable membrane strategy was used to separate Ag(+) released from silver nanoparticles (AgNPs) in an aqueous exposure. Internal Ag fractionation, activities of antioxidant enzymes and metabolites in E. fetida were determined after 96 h of exposure to two sizes of polyvinylpyrrolidone-coated AgNPs. The response of the antioxidant system combined with the content of malondialdehyde indicated that the Ag(+) released from AgNPs induced significant oxidative stress to the earthworms. Ag accumulated from AgNPs was predominantly associated with the granules and cell membrane compartments, whereas dissolved Ag was localized in the cytosol-containing fraction. In both Ag(+) exposures, two intermediates in the Krebs cycle, succinate and fumarate, were significantly elevated and depleted, respectively. A similar alteration pattern was seen in groups exposed to both smaller AgNPs (S AgNP, 10 nm) and larger AgNP (L AgNP, 40 nm), indicating that these effects in E. fetida were induced by exposure to released Ag(+). In addition, unique metabolic responses including decreased malate and glucose levels in S AgNP-exposed earthworms could be associated with exposure to nanoparticulate silver. Increased leucine and arginine and decreased ATP and inosine levels were observed in L AgNP exposures only, which clearly demonstrated a size-specific effect of AgNPs. Collectively, this study provided strong evidence that nanosilver acts by a different mechanism than ionic silver to cause acute toxicity to E. fetida, but further verification under different environmental conditions is needed.

Despite the global importance of forests, it is virtually unknown how their soil microbial communities adapt at the phylogenetic and functional level to long-term metal pollution. Studying 12 sites located along two distinct gradients of metal pollution in Southern Poland revealed that functional potential and diversity (assessed using GeoChip 4.2) were highly similar across the gradients despite drastically diverging metal contamination levels. Metal pollution level did, however, significantly impact bacterial community structure (as shown by MiSeq Illumina sequencing of 16S rRNA genes), but not bacterial taxon richness and community composition. Metal pollution caused changes in the relative abundance of specific bacterial taxa, including Acidobacteria, Actinobacteria, Bacteroidetes, Chloroflexi, Firmicutes, Planctomycetes and Proteobacteria. Also, a group of metal-resistance genes showed significant correlations with metal concentrations in soil. Our study showed that microbial communities are resilient to metal pollution; despite differences in community structure, no clear impact of metal pollution levels on overall functional diversity was observed. While screens of phylogenetic marker genes, such as 16S rRNA genes, provide only limited insight into resilience mechanisms, analysis of specific functional genes, e.g. involved in metal resistance, appears to be a more promising strategy., (© FEMS 2014. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.)

Raphidocelis subcapitata is a freshwater algae species that constitutes the basis of many aquatic trophic chains. In this study, R. subcapitata was used as a model species to investigate the kinetics of uptake and elimination of silver nanoparticles (AgNP) in comparison to silver nitrate (AgNO3) with particular focus on the Ag sized-fractions in solution. AgNP used in this study were provided in a suspension of 1 mg Ag/l, with an initial size of 3-8 nm and coated with an alkane material. Algae was exposed for 48 h to both AgNP and AgNO3 and sampled at different time points to determine their internal Ag concentration over time. Samples were collected and separated into different sized fractions: total (Agtot), water column Ag (Agwater), small particulate Ag (Agsmall.part.) and dissolved Ag (Agdis). At AgNO3 exposures algae reached higher bioconcentration factor (BCF) and lower elimination rate constants than at AgNP exposures, meaning that Ag is more readily taken up by algae in its dissolved form than in its small particulate form, however slowly eliminated. When modelling the kinetics based on the Agdis fraction, a higher BCF was found. This supports our hypothesis that Ag would be internalised by algae only in its dissolved form. In addition, algae images obtained by Coherent Anti-stokes Raman Scattering (CARS) microscopy demonstrated large aggregates of nanoparticles external to the algae cells with no evidence of its internalisation, thus providing a strong suggestion that these AgNP were not able to penetrate the cells and Ag accumulation happens through the uptake of Ag ions.

The biotic ligand model (BLM) is a theoretical, potentially mechanistic approach to assess metal bioavailability in soil and aquatic systems. In a BLM, toxicity is linked to the fraction of biotic ligand occupied, which in turn, depends on the various components of the solution, including activity of the metal. Bioavailability is a key factor in determining toxicity and uptake of metals in organisms. In this study, the present status of BLM development for soil and aquatic organisms is summarized. For all species and all metals, toxicity was correlated with the conditional biotic ligand binding constants. For almost all organisms, values for Ag, Cu, and Cd were higher than those for Zn and Ni. The constants derived for aquatic systems seem to be equally valid for soil organisms, but in the case of soils, bioavailability from the soil solution is greatly influenced by the presence of the soil solid phase., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The growing use of silver nanoparticles (Ag-NP) triggered an increasing interest in their environmental fate and possible ecotoxicological impacts. To investigate the potential risk of Ag-NP to soil organisms, the springtail Folsomia candida was exposed to Ag-NP (reported diameter size 3-8 nm) and AgNO3 in Lufa 2.2 natural soil for 28 days to determine effects on survival and reproduction. Also, the kinetics of uptake and elimination of Ag were studied for F. candida exposed in Lufa 2.2 soil to Ag-NP (at 168 mg Ag/kg dry soil) and AgNO3 (at 30 and 60 mg Ag/kg dry soil). AgNO3 was toxic with an LC50 was 284 mg Ag/kg dry soil for effects on survival and EC10 and EC50 values of 47.6 and 99.5 mg Ag/kg dry soil, respectively for the effect on reproduction. These values did correspond with porewater concentrations of 0.801, 0.042 and 0.082 mg Ag/l, respectively. No effects on survival and reproduction of Ag-NP were observed up to 673 mg Ag/kg dry soil, although porewater concentration was similar to the EC50 for AgNO3. Exposure to both Ag forms caused a fast uptake of Ag, but the Ag elimination rate was significantly higher for Ag-NP than for AgNO3. Bioaccumulation factor was higher for AgNO3 (on average 5.64) than for Ag-NP (1.12). These findings indicate that silver ions are more toxic than Ag-NP and have a higher potential to accumulate in F. candida.

Organic matter (OM) and pH may influence nanoparticle fate and effects in soil. This study investigated the influence of soil organic matter content and pH on the toxicity of ZnO-NP and ZnCl2 to Folsomia candida in four natural soils, having between 2.37% and 14.7% OM and [Formula: see text] levels between 5.0 and 6.8. Porewater Zn concentrations were much lower in ZnO-NP than in ZnCl2 spiked soils, resulting in higher Freundlich sorption constants for ZnO-NP. For ZnCl2 the porewater Zn concentrations were significantly higher in less organic soils, while for ZnO-NP the highest soluble Zn level (23mgZn/l) was measured in the most organic soil, which had the lowest pH. Free Zn(2+) ion concentrations were higher for ZnCl2 than for ZnO-NP and were greatly dependent on pH (pHpw) and dissolved organic carbon content of the pore water. The 28-d EC50 values for the effect of ZnCl2 on the reproduction of F. candida increased with increasing OM content from 356 to 1592mgZn/kg d.w. For ZnO-NP no correlation between EC50 values and OM content was found and EC50 values ranged from 1695 in the most organic soil to 4446mgZn/kg d.w. in the higher pH soil. When based on porewater and free Zn(2+) concentrations, EC50 values were higher for ZnCl2 than for ZnO-NP, and consistently decreased with increasing pHpw. This study shows that ZnO-NP toxicity is dependent on soil properties, but is mainly driven by soil pH., (Copyright © 2014 Elsevier Inc. All rights reserved.)

Understanding bioavailability and toxicity is essential for effective ecological assessment of contaminated soils. Total, water and 0.01 M CaCl2 extractable and porewater Pb concentrations and soil properties in different shooting field soils were investigated. Three artificial soils containing different pH and organic matter contents and two natural soils were included as controls. Survival, reproduction and avoidance responses of Folsomia candida exposed to these soils as well as internal Pb concentrations were measured. In the shooting range soils, total Pb concentrations were 47-2,398 mg/kg dw, [Formula: see text] 3.2-6.8 and organic matter content 3.8-7.0%. Pb concentrations in F. candida linearly increased with increasing Pb concentrations in the soils. Acid forest soils caused significantly higher collembolan mortality and avoidance responses and significantly lower reproduction than the neutral grassland soils, which could be attributed to differences in pH and especially CaCl2 extractable Pb concentrations. Soil properties significantly affected bioavailability and toxicity of Pb, but overall the collembolans seemed more sensitive to pH than to Pb in soils. This study shows the importance of selecting proper reference soils for assessing the effects of field soils., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Background: Pollution in aquaculture areas may negatively impact edible species and threaten seafood quality and safety. The aim of this study was to determine the interaction between copper and bacteria in the aquatic habitat and their impact upon crustaceans. Marbled crayfish was chosen as a model of aquatic crustaceans and the influence of metal contamination on bacterial community structure in water used to culture crayfish and in crayfish themselves was investigated. Histamine, an allergen commonly formed by certain groups of bacteria in crustacean edible tissue during storage, was also determined., Results: Copper exposure increased its concentration in crayfish meat by 17.4%, but the copper concentration remained within acceptable food safety limits. Elevated copper levels affected the bacterial community both in the water used to cultivate crayfish and in the marbled crayfish themselves. Cluster analysis of 16S rRNA-gene based microbial community fingerprints revealed that copper impacted the bacterial community in the water and in the crayfish meat. However, copper exposure reduced the formation of histamine in crayfish meat during storage by 66.3%., Conclusion: Copper from the habitat appears to reduce histamine accumulation in crayfish meat during storage by affecting the bacterial community structure of the cultivation water and most likely also in the intestine of the crayfish. From a food safety point of view, copper treatment during the aqua culturing of crustaceans has a positive impact on the postharvest stage., (© 2013 Society of Chemical Industry.)

The aim of this study was to estimate the bioavailability of essential (Zn, Cu) and non-essential metals (Cd, Pb) to the earthworm Lumbricus rubellus exposed to soils originating from a gradient of metal pollution in Southern Poland. Metal uptake and elimination kinetics were determined and related to soils properties. Experimental results were compared with tissue metal concentrations observed in earthworms from the studied transect. Cd and Pb were intensively accumulated by the earthworms, with very slow or no elimination. Their uptake rate constants, based on 0.01 M CaCl2-extractable concentrations in the soils, increased with soil pH. Internal concentrations of Cu and Zn were maintained by the earthworms at a stable level, suggesting efficient regulation of these metals by the animals. The estimated uptake and elimination kinetics parameters enabled fairly accurate prediction of metal concentrations reached within a life span of L. rubellus in nature., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The aim of the present study was to improve our understanding of cadmium bioavailability by linking toxicokinetics and toxicodynamics. The springtail Folsomia candida was exposed to different cadmium concentrations in solutions embedded in inert quartz sand. Survival and cadmium uptake in the animals were followed for 21 d. After 10 d, some animals were transferred to clean medium to assess cadmium elimination. Using a first-order one-compartment model, an overall uptake rate constant (k1) of 0.18 L kg(animal)(-1) d(-1) and an elimination rate constant (k(2-TK)) of 0.02 d(-1) were calculated. Survival decreased with time, resulting in an estimated final median lethal concentration (LC50) of 0.51 mM. A lethal body concentration (LBC) of 4.6 µmol Cd g(-1) dry body weight was estimated by multiplying the final LC50 by the bioconcentration factor (k1/k(2-TK)). The LC50(animal) values based on internal cadmium concentrations were between 3.56 µmol Cd g(-1) and 9.91 µmol Cd g(-1) dry body weight, with an overall value of 7.9 µmol Cd g(-1) dry body weight (95% confidence interval [CI]: 3.8-12.0 µmol Cd g(-1) dry body wt). Because the 95% CI of the LC50(animal) included the LBC, there was good agreement of cadmium toxicokinetics and toxicodynamics., (© 2014 SETAC.)

The use of plant protection products (PPPs) in agro-environments can lead to undesired exposure of non-target organisms in non-target compartments. A year-round field survey was conducted in a vineyard in Northern Italy, for monitoring the changes in the structure of soil microarthropod communities under the application of PPPs, focusing on springtails and mites, both inside and 4 and 10 m outside the vineyard. Exposure to PPPs was estimated as time-weighted average soil concentrations. The fluctuations in the abundances of the different organisms after the application of PPPs, especially insecticides, were recorded. A recovery in abundances was observed at the end of the productive season outside the field and at the beginning of the next spring within the vineyard. Using multivariate statistical tools, the behaviour of each taxon in relation to the stressors was assessed. Some organisms were affected by the stressors, while others were favoured because of low vulnerability to PPPs and the indirect effect of the absence of other taxa. The principal response curves (PRC) method was the most sensitive tool for assessing PPP effects on soil arthropod communities. Strong differences were evident in the structure of the communities inside and outside the vineyard, with the communities sampled 4 and 10 m outside the vineyard being fairly similar, the latter considered as control. The role of physical stressors on community composition is recognised. However, chemical stressors, and in particular PPP exposure seemed to have larger effects on structural and functional characteristics of soil arthropod communities than physical stressors.

The bioavailability of Cu, Zn, Pb and Cd from field-aged orchard soils in a certified fruit plantation area of the Northeast Jiaodong Peninsula in China was assessed using bioassays with earthworms (Eisenia fetida) and chemical assays. Soil acidity increased with increasing fruit cultivation periods with a lowest pH of 4.34. Metals were enriched in topsoils after decades of horticultural cultivation, with highest concentrations of Cu (132 kg(-1)) and Zn (168 mg kg(-1)) in old apple orchards and Pb (73 mg kg(-1)) and Cd (0.57 mg kg(-1)) in vineyard soil. Earthworm tissue concentrations of Cu and Pb significantly correlated with 0.01 M CaCl2-extractable soil concentrations (R(2) = 0.70, p < 0.001 for Cu; R(2) = 0.58, p < 0.01 for Pb). Because of the increased bioavailability, regular monitoring of soil conditions in old orchards and vineyards is recommended, and soil metal guidelines need reevaluation to afford appropriate environmental protection under acidifying conditions., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

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. Ca(2+), Mg(2+) 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{Ni(2+)} 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 Ni(2+), Mg(2+) and Na(+) on the uptake and toxic action sites were similar, but for Ca(2+) they differed. This indicates that the effect of Ca(2+) on Ni(2+) toxicity cannot simply be explained by the competition for entry into organism., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Background: The soil worm Enchytraeus crypticus (Oligochaeta) is an ecotoxicology model species that, until now, was without genome or transcriptome sequence information. The present research aims at studying the transcriptome of Enchytraeus crypticus, sampled from multiple test conditions, and the construction of a high-density microarray for functional genomic studies., Results: Over 1.5 million cDNA sequence reads were obtained representing 645 million nucleotides. After assembly, 27,296 contigs and 87,686 singletons were obtained, from which 44% and 25% are annotated as protein-coding genes, respectively, sharing homology with other animal proteomes. Concerning assembly quality, 84% of the contig sequences contain an open reading frame with a start codon while E. crypticus homologs were identified for 92% of the core eukaryotic genes. Moreover, 65% and 77% of the singletons and contigs without known homologs, respectively, were shown to be transcribed in an independent microarray experiment. An Agilent 180 K microarray platform was designed and validated by hybridizing cDNA from 4 day zinc- exposed E. crypticus to the concentration corresponding to 50% reduction in reproduction after three weeks (EC50). Overall, 70% of all probes signaled expression above background levels (mean signal + 1x standard deviation). More specifically, the probes derived from contigs showed a wider range of average intensities when compared to probes derived from singletons. In total, 522 significantly differentially regulated transcripts were identified upon zinc exposure. Several significantly regulated genes exerted predicted functions (e.g. zinc efflux, zinc transport) associated with zinc stress. Unexpectedly, the microarray data suggest that zinc exposure alters retro transposon activity in the E. crypticus genome., Conclusion: An initial investigation of the E. crypticus transcriptome including an associated microarray platform for future studies proves to be a valuable resource to investigate functional genomics mechanisms of toxicity in soil environments and to annotate a potentially large number of lineage specific genes that are responsive to environmental stress conditions.

The present study examined how transcriptomics tools can be included in a triad-based soil-quality assessment to assess the toxicity of soils from riverbanks polluted by metals. To that end, the authors measured chemical soil properties and used the International Organization for Standardization guideline for ecotoxicological tests and a newly developed microarray for gene expression in the indicator soil arthropod Folsomia candida. Microarray analysis revealed that the oxidative stress response pathway was significantly affected in all soils except one. The data indicate that changes in cell redox homeostasis are a significant signature of metal stress. Finally, 32 genes showed significant dose-dependent expression with metal concentrations. They are promising genetic markers providing an early indication of the need for higher-tier testing of soil quality. During the bioassay, the toxicity of the least polluted soils could be removed by sterilization. The gene expression profile for this soil did not show a metal-related signature, confirming that a factor other than metals (most likely of biological origin) caused the toxicity. The present study demonstrates the feasibility and advantages of integrating transcriptomics into triad-based soil-quality assessment. Combining molecular and organismal life-history trait stress responses helps to identify causes of adverse effects in bioassays. Further validation is needed for verifying the set of genes with dose-dependent expression patterns linked with toxic stress., (© 2013 SETAC.)

This study aimed at assessing the bioavailability and toxicity of lead to Eisenia andrei in shooting range soils representing different land uses (forest, grassland, bullet plot). Soils contained 47-2398 mg Pb/kg dry weight (dw), but also had different pH-CaCl2 (3.2-6.8) and organic matter contents (3.8-13%). Therefore artificial soils with different pH and organic matter contents and two natural soils were included as control soils. Earthworms were exposed for 28 days and toxicity and uptake of Pb were related to total, water and 0.01 M CaCl2 extractable and porewater Pb concentrations as well as to soil characteristics. Pb uptake in the earthworms linearly increased with increasing soil concentrations. At >2000 mg Pb/kg dw and pH 3.3-3.5, high earthworm mortality with significant weight loss and complete inhibition of reproduction were recorded. At <1000 mg/kg dw, earthworm reproduction was more related to differences in pH and other soil characteristics than to Pb., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

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(+), Ca(2+), Mg(2+), K(+), and Na(+)) on Cd(2+) toxicity was observed, while Mg(2+) was found to significantly alleviate Ni(2+) 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 Cd(2+) toxicity across soils but failed in predicting Ni(2+) toxicity. The free ion approach, in which the protective effects of Mg(2+) were included, explained 89% and 84% of the variations in LC50{Ni(2+)} (expressed as free ion activity) for L. rubellus (log LC50{Ni(2+)} = 1.18log{Mg(2+)}-0.52) and A. longa (log LC50{Ni(2+)} = 0.51log{Mg(2+)}-2.16), respectively. Prediction error was within a factor of 2 for both Cd(2+) and Ni(2+) 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., (© 2013 SETAC.)

This study aimed at assessing the photodegradation of the insecticide chlorantraniliprole (CAP) in deionized water and in tap water amended with humic acids and nitrate. Photolysis was carried out under simulated solar or UV-A light. CAP (39 μM) photodegradation was slightly faster in tap water than in deionized water with half lives of 4.1 and 5.1 days, respectively. Photodegradation rate of CAP was hardly affected by humic acids (up to 100 mg L(-1)) and nitrate. Photodegradation pattern was different in slightly acidic (pH=6.1) deionized water compared to basic (pH=8.0) tap water. Four main degradation products have been isolated and characterized spectroscopically, and crystal structure was recorded for the first two photodegradation products. CAP also degraded in the dark controls, but only at basic pH (23% loss at pH 8.0 in tap water after 6 days), resulting in the formation of one single degradation product. Our study shows that the degradation of chlorantraniliprole in water is a combination of chemical and photochemical reactions, which are highly dependent on the pH of the solution., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

There is no clear consensus in the literature on the metal accumulation pattern and sensitivity of different earthworm species. In the present study, accumulation and toxicity of Cu, Cd, Ni, and Zn in the earthworms Lumbricus rubellus (epigeic), Aporrectodea longa (anecic), and Eisenia fetida (ultra-epigeic) were determined after 28 days exposure in two soils. Metal accumulation and sensitivity were interpreted using the specific traits of different earthworm species. Results showed that for all four metals tested L. rubellus was the most sensitive species, followed by A. longa and E. fetida. At the same exposure concentration, internal concentrations followed the order: L. rubellus > E. fetida > A. longa for Cu and Ni, L. rubellus ≈ E. fetida ≈ A. longa for Cd, and L. rubellus > A. longa > E. fetida for Zn. Langmuir isotherms were used to model metal accumulation at both nontoxic and toxic exposure concentrations. The Cu, Cd, and Zn concentrations in E. fetida generally leveled off at high exposure concentrations but not for the other two species. A. longa showed a high capability of regulating internal Ni concentrations. The traits-based approaches suggested that most likely a group of earthworm traits together determined (differences in) metal accumulation and sensitivity. More research is needed in this respect to build up solid relationships between species-specific responses and traits, enabling cross-species extrapolation of accumulation and toxicity data.

Lake Nokoué and Cotonou Lagoon are the most important and most productive continental freshwaters in Bénin, with an estimated fish production of over 2 tonnes per hectare in Lake Nokoué. Organochlorine pesticides are used in agriculture and to repel tsetse flies, malaria mosquitoes and other diseases raised. Sediment, fish, shrimp and oyster species were collected in Lake Nokoué and Cotonou Lagoon for pesticide residues analysis. The main pesticides identified in sediment were pp'-DDT and its metabolites pp-DDE and pp'-DDD, with residue levels between the detection limit and 24.4 μg/kg dry weight. Fish species commonly consumed such as Elops lacerta, Podamasys jubelini, Gobbienellus occidentalis, Ethmalosa fimbriata, Mugil cephalus and Hemichromis fasciatus were contaminated with residues of seven to nine pesticides, including pp-DDE, op'-DDD, pp'-DDD, op'-DDT, pp'-DDT, α-endosulfan, aldrin, dieldrin and γ-hexachlorocyclohexane. The levels ranged from detection limit to 289 ng/g lipid. The same pesticides were also detected in other aquatic species, such as shrimp and oysters. A summed risk assessment, comparing pesticide intake levels through fish consumption with tolerable daily intake levels proposed by the World Health Organization, showed in all cases a low risk for human health.

The effects of soil pH on the toxicity of ZnO nanoparticles (NPs) to the terrestrial isopod Porcellionides pruinosus were evaluated. Isopods were exposed to a natural soil amended with CaCO3 to reach 3 different pH(CaCl2) levels (4.5, 6.2, and 7.3) and to standard LUFA 2.2 soil (pH 5.5) spiked with ZnO NPs (30 nm), non-nano ZnO (200 nm), and ionic Zn as ZnCl₂. Toxicity was expressed based on total Zn concentration in soil, as well as total Zn and free Zn²⁺ ion concentrations in porewater. Compared with ZnO-spiked soils, the ZnCl₂-spiked soils had lower pH and higher porewater Ca²⁺ and Zn levels. Isopod survival did not differ between Zn forms and soils, but survival was higher for isopods exposed to ZnO NPs at pH 4.5. Median effect concentrations (EC50s) for biomass change showed similar trends for all Zn forms in all soils, with higher values at intermediate pH. Median lethal concentration (LC50) and EC50 values based on porewater Zn or free Zn ion concentrations were much lower for ZnO than for ionic zinc. Zn body concentrations increased in a dose-related manner, but no effect of soil pH was found. It is suggested not only that dissolved or free Zn in porewater contributed to uptake and toxicity, but also that oral uptake (i.e., ingestion of soil particles) could be an important additional route of exposure., (© 2013 SETAC.)

To improve our understanding of metal bioavailability to soil-living invertebrates, the effect of porewater composition on the toxicodynamics of copper and cadmium in Folsomia candida (Collembola) was investigated. Assuming that porewater is the main exposure route, F. candida was exposed to simulated soil solutions of different composition. Toxicity of copper was slightly lower in a calcium-only solution than in a multication solution. With increasing copper concentrations from 0.005 mM to 1.37 mM, internal copper concentrations similarly increased in both exposure solutions, suggesting that a single cation nutrient solution is suitable for testing F. candida. In the second experiment, animals were exposed for 7 d to copper and cadmium in simplified soil solutions with different calcium (0.2 mM, 0.8 mM, 3.2 mM, 12.8 mM) and pH (5.0, 6.0, 7.0) levels. The median lethal concentration (LC50) values decreased with time in both the calcium and pH series. A hormetic-type effect was observed for copper in the second test, as well as in the calcium-only solution in the first experiment. Because of stronger hormesis, LC50s for copper were higher at lower calcium concentrations. For cadmium, LC50 values were higher at higher calcium concentrations, suggesting competition of calcium with the free cadmium ion. Toxicity of cadmium increased with decreasing pH, while copper was more toxic at intermediate pH. The results show that a toxicodynamics approach can help to improve the interpretation of metal toxicity to soil invertebrates, taking into account soil solution properties., (© 2013 SETAC.)

Metal-contaminated soil, from the El Arteal mining district (SE Spain), was remediated with organic (6% compost) and inorganic amendments (8% marble sludge) to reduce the mobility of metals and to modify its potential environmental impact. Different measures of metal bioavailability (chemical analysis; survival, growth, reproduction and bioaccumulation in the earthworm Eisenia andrei), were tested in order to evaluate the efficacy of organic and inorganic amendments as immobilizing agents in reducing metal (bio)availability in the contaminated soil. The inorganic amendment reduced water and CaCl2-extractable concentrations of Cd, Pb, and Zn, while the organic amendment increased these concentrations compared to the untreated soil. The inorganic treatment did not significantly reduce toxicity for the earthworm E. andrei after 28 days exposure. The organic amendment however, made the metal-contaminated soil more toxic to the earthworms, with all earthworms dying in undiluted soil and completely inhibiting reproduction at concentrations higher than 25%. This may be due to increased available metal concentrations and higher electrical conductivity in the compost-amended soil. No effects of organic and inorganic treatments on metal bioaccumulation in the earthworms were found and metal concentrations in the earthworms increased with increasing total soil concentrations.

The aim of the present study was to investigate the influence of Ca and pH on the uptake and effects of Cu in Folsomia candida (Collembola). Assuming that soil pore water is the main route of exposure, F. candida were exposed for seven days to Cu in simplified soil solutions at different Ca concentrations and different pH levels. A hormetic-type effect was seen for the effect of Cu on F. candida survival. Toxicity of Cu was slightly decreased and Cu uptake increased at the highest Ca concentrations. Cu toxicity and uptake were not significantly affected by pH. Conditional binding constants for Cu(2+), Ca(2+) and H(+), calculated with a Langmuir isotherm, were used to relate Cu toxicity to the fraction of occupied binding sites (BL). The estimated 50% effect level (fCu-BL50) was 0.14 when all data were combined. To verify the Langmuir parameters, binding constants calculated based on internal Cu concentrations were used to estimate predicted effects and compared with the measured values. A good correlation between predicted and measured survival indicated that the principles of a biotic ligand model may be applicable to explain Cu toxicity to F. candida in simplified soil solutions., (Copyright © 2013 Elsevier B.V. All rights reserved.)