International audience | The use of the Diffusive Gradient in Thin Film sampler (DGT) as a monitoring tool for regulatory programs is currently evaluated. In this context, the impact of commonly followed procedures on the accuracy of DGT-labile As, Cd, Cu, and Ni quantification was studied. Initial sampler contamination yields to define quantification limits instead of using blank subtraction, thus avoiding artifact concentrations. Not considering the alteration of element diffusion by the filter membrane leads to significant underestimation. However, diffusion coefficients determined on a non-fouled membrane were found to be suitable for the studied site, making it possible to use data from the literature. When diffusive boundary layer formation is neglected, no loss of accuracy is recorded provided the layer is thinner than 0.5 mm. Finally, exploration of potential biases allowed initiating a framework that might help limit inaccuracies in DGT-labile concentration estimation and interpretation, especially in a low contamination context.

Despite the mercury (Hg) control measures adopted by the international community, Hg still poses a significant risk to ecosystem and human health. This is primarily due to the ability of atmospheric Hg to travel intercontinentally and contaminating terrestrial and aquatic environments far from its natural and anthropogenic point sources. The issue of Hg pollution is further complicated by its unique physicochemical characteristics, most noticeably its multiple chemical forms that vary in their toxicity and environmental mobility. This meant that most of the risk evaluation protocols developed for other metal(loid)s are not suitable for Hg. Soil is a major reservoir of Hg and a key player in its global cycle. To fully assess the risks of soil Hg it is essential to estimate its bioavailability and/or availability which are closely linked to its toxicity. However, the accurate determination of the (bio)-available pools of Hg in soils is problematic, because the terms ‘bioavailable’ and ‘available’ are ill-defined. In particular, the term ‘bioavailable pool’, representing the fraction of Hg that is accessible to living organisms, has been consistently misused by interchanging with other intrinsically different terms e.g. mobile, labile, reactive and soluble pools. A wide array of physical, chemical, biological and isotopic exchange methods were developed to estimate the (bio)-available pools of Hg in soil in an attempt to offer a plausible assessment of its risks. Unfortunately, many of these methods do not mirror the (bio)-available pools of soil Hg and suffer from technical drawbacks. In this review, we discuss advantages and disadvantages of methods that are currently applied to quantify the (bio)-availability of Hg in soils. We recommended the most feasible methods and give suggestions how to improve the determination of (bio)-available Hg in soils.

This study assessed the effectiveness of dredging in controlling arsenic (As), selenium (Se), and antimony (Sb) contamination in sediments, by examining contaminant concentrations in sediments six years after dredging was completed. High-resolution diffusive gradients in thin films (DGT) and dialysis (HR-Peeper) techniques were used to monitor the concentrations of DGT-labile metalloids and soluble metalloids in sediments, respectively. Results revealed that dredging effectively remediated metalloid contamination in sediments only in April, July and/or January. Compared to non-dredged sediments, the concentrations of soluble and DGT-labile As, Se, and Sb in dredged sediments decreased on average by 42%, 52%, and 43% (soluble), and 54%, 50%, and 53% (DGT), respectively. The effectiveness of the dredging was primarily due to the transformation of metalloids from labile to inert fractions, which increased the ability of the sediments to retain the metalloids, and the slowed rate of resupplied metalloids from available solid pools. In contrast, negligible/negative effects of dredging were seen in October, and the concentrations of soluble and DGT-labile metalloids even increased in some profiles of dredged sediments. This was mainly caused by a release of the metalloids from algal degradation, which may offset the dredging effectiveness.

Selenium (Se) is a metalloid of potential interest from both a toxicological and nutritional perspective, having a range of safe intake. The adverse neuro-behavioural effects of Se have been investigated in both humans and fishes, but little is known about its effects on social behaviours or the serotonergic signaling pathway in the brain. In the present study, we investigated the effects of chorionic dietary exposure to Se (as selenomethionine) at different concentrations (control, 2.1, 11.6 or 31.5 μg/g dry wt.) on antipredator avoidance, shoaling behaviour, and social group preferences in adult zebrafish (Danio rerio). In addition, we also measured the expression of important genes in the serotonergic pathway that influence social behaviours. After 60 days of exposure, the highest dose (31.5 μg/g dry wt.) caused the highest level of baseline fear behaviour, with fish swimming lower in the water column and in tighter shoals compared to fish in the other treatments. With high levels of baseline fear, these fish did not significantly intensify fear behaviours in response to predation risk in the form of exposure to chemical alarm cues. When individual fish were given an opportunity to shoal with groups of differing sizes (3 vs. 4 individuals), fish exposed to the high dose spent less time with groups in general, and only control fish showed a significant preference for the larger group. In the zebrafish brain, we found significant upregulation in the mRNA expression of serotonin receptors (htr1aa and htr1b), a transporter (slc6a4a), and tryptophan hydroxylase-2 (tph2), whereas there was a downregulation of the monoamine oxidase (mao) gene. The results of this study suggest that disruption of serotonergic neurotransmission might have been responsible for Se-induced impairment of antipredator and social behaviour in zebrafish.

The increased bioeconomy targets for the biomass share of renewable energy production across Europe should be met using land unsuitable for food production. Miscanthus breeding programs targeted the production of plants with a diverse range of traits allowing a wider utilization of land resources for biofuel production without competing with arable crops. These traits include increasing tolerances to drought, chilling, and to metal(loid)s excess. Two novel Miscanthus hybrids, GNT41 and GNT34, were compared against Miscanthus x giganteus (Mxg) on metal-contaminated arable land in Poland. This study aimed at evaluating their yield, biomass quality and quantifying seasonal differences in photosynthetic and transpiration parameters. A secondary objective was to identify key physiological mechanisms underlying differences in metal accumulation between the investigated plants. The new hybrids produced a similar yield to Mxg (13–15 t ha−1 yr−1), had shorter shoots, higher Leaf Area Index and stem number. Based on gas exchange measurements, GNT34 exhibited isohydric (water-conserving) behavior. The stomatal response to light of the new hybrids was at least twice as fast as that of Mxg, a trait that is often associated with increased seasonal water use efficiency. This contributed to the almost 40% reduction in shoot Pb and Cd concentrations for the new hybrids as compared to Mxg. This suggested that promoting stomatal regulation in conjunction with improved water conservation may be a target for improving plants for wider use on metals contaminated land.

Contamination of soils by metals and metalloids is an important environmental problem in many residential and industrial sites around the world. Lead is a common contaminant, which enters the soil through mining, industrial activities and waste disposal. A range of technologies can be used to remediate soil lead, however most remediation technologies adversely affect the environment and particularly soil biota. We have assessed the efficacy of vermiremediation (the use of earthworms for remediation) to reduce water extractable lead concentrations in soil. Earthworms were introduced to a sandy soil spiked with the common lead minerals cotunnite (PbCl2), cerussite (PbCO3), massicot (PbO) or galena (PbS) at 1000 mg (Pb) kg−1. Lead concentrations in pore water extracted during the experiment were not significantly different in contaminated soil with and without worms. However, concentrations of lead in water from a deionised water extraction (washing) of contaminated soil were significantly lower in soil with earthworms than in soil without. Earthworms accumulated on average (±1 standard deviation) 276 ± 118, 235 ± 66, 241 ± 58 and 40 ± 30 mg kg−1 (dry weight of earthworms) of lead in their bodies, in PbCl2, PbCO3, PbO and PbS-dosed soils, respectively. During the experiment, earthworms lost weight in all contaminated soils, except those containing PbS.

Due to diffuse atmospheric fallouts of process particles enriched by metals and metalloids, polluted soils concern large areas at the global scale. Useful tools to assess ecotoxicity induced by these polluted soils are therefore needed. Earthworms are currently used as biotest, however the influence of specie and earthworm behaviour, soil characteristics are poorly highlighted. Our aim was therefore to assess the toxicity of various polluted soils with process particles enriches by metals and metalloids (Pb, Cd, Cu, Zn, As and Sb) collected from a lead recycling facility on two earthworm species belonging to different ecological types and thus likely to have contrasted behavioural responses (Eiseina hortensis and Lumbricus terrestris).The combination of behavioural factors measurements (cast production and biomass) and physico-chemical parameters such as metal absorption, bioaccumulation by earthworms and their localization in invertebrate tissues provided a valuable indication of pollutant bioavailability and ecotoxicity. Soil characteristics influenced ecotoxicity and metal uptake by earthworms, as well as their soil bioturbation.

The mobilization behaviour of metalloids and metals when leached by water from highly polluted soil/sediment samples was studied using static and dynamic approaches employing batch methodology and rotating coiled columns (RCC), respectively. Increasing the solution-to-solid ratios during batch leaching resulted in different enhanced mobilization rates, which are element-specific and matrix-specific. When dynamic leaching is employed with continuous replacement of the eluent, a higher portion is mobilized than when using batch elution with an identical solid-to-water ratio. Using RCC the time-resolved leaching of the elements was monitored to demonstrate the leaching patterns. For the majority of elements a significant decrease could be shown in the mobilized portion of the elements with ongoing leaching process. The data were discussed targeted at solid liquid partitioning coefficients of the metal(loid)s. The capabilities in application of Kd values was demonstrated for dynamic leaching which is relevant for environmental processes.

In this work, possible relationships between global DNA methylation and metal/metalloid concentrations in earthworms have been explored. Direct correlation was observed between soil and tissue As, Se, Sb, Zn, Cu, Mn, Ag, Co, Hg, Pb (p<0.05). Speciation results obtained for As and Hg hint at the capability of earthworms for conversion of inorganic element forms present in soil to methylated species. Inverse correlation was observed between the percentage of methylated DNA cytosines and total tissue As, As+Hg, As+Hg+Se+Sb (β=−0.8456, p=0.071; β=−0.9406, p=0.017; β=−0.9526, p=0.012 respectively), as well as inorganic As+Hg (β=−0.8807, p=0.049). It was concluded that earthworms would be particularly helpful as bioindicators of elements undergoing in vivo methylation and might also be used to assess the related risk of epigenetic changes in DNA methylation.

Assessments of antimony (Sb) and arsenic (As) contamination in sediments are reported on a wide range of different particle size fractions, including <63 μm, < 180 μm and <2 mm. Guidelines vary between jurisdictions which limits comparative assessment between contamination events and complicates ecotoxicity assessment, and almost no information exists on Sb size distribution in contaminated sediments. This study quantified and compared the size distribution of Sb and As in 11 sediments (and 2 floodplain soils) collected along 320 km of waterway contaminated by historic mining activity. Sediment particle size distribution was the primary determinant of total metalloid load in size fractions across the varying substrates of the waterway. Minerals and sorption complexes influenced metalloid particle distribution but relative importance depended on location. Arsenic concentrations were greatest in the fine <63 μm fraction across all the different river environments (7.3–189 mg kg⁻¹, or 1–26% of total sample As), attributed to fine-grained primary arsenopyrite and/or sorption of As(V) to fine solid-phases. The Sb particle size concentrations were greatest in mid-size fractions (205–903 mg kg⁻¹) in the upper catchment and up to 100 km downstream to the mid-catchment as a result of remnant Sb minerals. Antimony concentrations in the lower catchment were greatest in the <63 μm fraction (8.8–12.1 mg kg⁻¹), reflecting the increasing importance of sorption for Sb particle associations. This work demonstrates the importance of particle size analysed for assessment of sediment quality, and provides support for analysis of at least the <250 μm fraction for Sb and As when comparing pollutant distribution in events impacted by primary contamination. Analysis of the <63 μm fraction, however, provides good representation in well-dispersed contaminated sediments.