International audience | Although high PAH content and detection of PAH-degraders, the PAH biodegradation is limited in aged-contaminated soils due to low PAR availability (i.e., 1%). Here, we tried to experimentally increase the soil PAH availability by keeping both soil properties and contamination composition. Organic extract was first removed and then re-incorporated in the raw soil as fresh contaminants. Though drastic, this procedure only allowed a 6-time increase in the PAH availability suggesting that the organic constituents more than ageing were responsible for low availability. In the re-contaminated soil, the mineralization rate was twice more important, the proportion of 5-6 cycles PAH was higher indicating a preferential degradation of lower molecular weight PAH. The extraction treatment induced bacterial and fungal community structures modifications, Pseudomonas and Fusarium solani species were favoured, and the relative quantity of fungi increased. In re-contaminated soil the percentage of PAH-dioxygenase gene increased, with 10 times more Gram negative representatives.

Stable isotope 111Cd was spiked into sediments of different organic content levels for 3 days to 2 months. Bioavailability of spiked Cd to deposit-feeders, assessed by in vitro Cd solubilization, generally decreased with contact time but became comparable with that of background Cd after 2 months. This could be explained by the gradual transfer of Cd from the more mobile geochemical phase (carbonate associated phase) to more refractory phases (Fe–Mn oxide associated phase, and organic associated phase) within 2 months. The sedimentary organic content had a weak effect on Cd solubilization, while the distribution of Cd in carbonate or Fe–Mn oxide associated phase could have a larger influence on the solubilization of sedimentary Cd and its change with contact time. The observations in this study emphasize the need to consider Cd sequestration over time in sediments of various compositions, which would be useful in risk assessment of contaminated sediments.

To assess the effect of long-term dissolution on bioavailability and toxicity, triethoxyoctylsilane coated and uncoated zinc oxide nanoparticles (ZnO-NP), non-nano ZnO and ZnCl2 were equilibrated in natural soil for up to twelve months. Zn concentrations in pore water increased with time for all ZnO forms but peaked at intermediate concentrations of ZnO-NP and non-nano ZnO, while for coated ZnO-NP such a clear peak only was seen after 12 months. Dose-related increases in soil pH may explain decreased soluble Zn levels due to fixation of Zn released from ZnO at higher soil concentrations. At T = 0 uncoated ZnO-NP and non-nano ZnO were equally toxic to the springtail Folsomia candida, but not as toxic as coated ZnO-NP, and ZnCl2 being most toxic. After three months equilibration toxicity to F. candida was already reduced for all Zn forms, except for coated ZnO-NP which showed reduced toxicity only after 12 months equilibration.

The use of accumulation bioindicator to assess metal bioavailability has mainly concerned individual species. This work addresses this issue at the plant community level. Metal content within different species from plant communities found at three contaminated and one uncontaminated site was compared. Results showed that for two contaminated sites, leaf metals concentrations were comparable to those in plants from control site, i.e. approx (mg/kg) 0.1 Cd, 0.2 Cr, 9.2 Cu, 1.8 Ni, 0.5 Pb and 42 Zn. Only plants from the third site showed higher metal contents, ranging from 1.5- to 8-fold those of the control community. This contrasted with ammonium acetate–EDTA extractions, which indicated a very high “availability” of metals at the three sites, as compared to the control site. Thus, metal content in plant communities provided accurate information on actual transfer toward the ensemble of vegetation, which could be used to establish site-specific “fingerprints” of metal bioavailability.

We evaluated the correlation between soil organic carbon (OC) content and metabolic responses of Eisenia fetida earthworms after exposure to phenanthrene (58 ± 3 mg/kg) spiked into seven artificial soils with OC contents ranging from 1 to 27% OC. Principal component analysis of 1H nuclear magnetic resonance (NMR) spectra of aqueous extracts identified statistically significant differences in the metabolic profiles of control and phenanthrene-exposed E. fetida in the 1% OC soil only. Partial least squares analysis identified a metabolic response in the four soils with OC values ≤11% which was well correlated to estimated phenanthrene porewater concentrations. The results suggest that the higher sorption capability of high OC soils decreased the bioavailability of phenanthrene and the subsequent metabolic response of E. fetida.

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.

A number of studies have shown the potential of in vitro assays to predict contaminant in vivo relative bioavailability in order to refine human health exposure assessment. Although the term ‘validated’ has been used to describe the goodness of fit between in vivo and in vitro observations, its misuse has arisen from semantic considerations in addition to the lack of defined criteria for establishing performance validation. While several internal validation methods may be utilised, performance validation should preferably focus on assessing the agreement of model predictions with a set of data which are independent of those used to construct the model. In order to achieve robust validated predictive models, a number of parameters (e.g. size of data set, source of independent soils, contaminant concentration range, animal model, relative bioavailability endpoint) need to be considered in addition to defined criteria for establishing performance validation which are currently lacking.

Selective supercritical fluid extraction (SSFE) was used as a measurement of compound chemical accessibility and as a predictor of compound bioavailability from three natural soils and artificial analogues prepared to have comparable total organic carbon content. Soils spiked with phenanthrene, pyrene, PCB 153, lindane, and p,p′-DDT were aged for 0, 14, 28, or 56 days and then selectively extracted by supercritical fluid extraction. Compounds exhibited decreasing extractability with increasing pollutant–soil contact time and increasing total organic carbon content in tested soils. However, the different extractability of compounds from artificial and natural pairs having comparable TOC indicates the limitations of using TOC as an extrapolation basis between various soils. The comparison of extractability with bioaccumulation by earthworms (Eisenia fetida) previously published by Vlčková and Hofman (2012) showed that only for PAHs it was possible to predict their bioaccumulation by means of selective SFE.

Many important environmental contaminants are hydrophobic organic contaminants (HOCs), which include PCBs, PAHs, PBDEs, DDT and other chlorinated insecticides, among others. Owing to their strong hydrophobicity, HOCs have their final destination in soil or sediment, where their ecotoxicological effects are closely regulated by sorption and thus bioavailability. The last two decades have seen a dramatic increase in research efforts in developing and applying partitioning based methods and biomimetic extractions for measuring HOC bioavailability. However, the many variations of both analytical methods and associated measurement endpoints are often a source of confusion for users. In this review, we distinguish the most commonly used analytical approaches based on their measurement objectives, and illustrate their practical operational steps, strengths and limitations using simple flowcharts. This review may serve as guidance for new users on the selection and use of established methods, and a reference for experienced investigators to identify potential topics for further research.

The distribution and chemical speciation of typical metals (Cu, Zn, Cd and Pb) in agricultural and non-agricultural soils were investigated in the area of Nanpan River, upstream of the Pearl River. The investigated four metals showed higher concentrations in agricultural soils than in non-agricultural soils, and the site located in factory district contained metals much higher than the other sampling sites. These observations suggested that human activities, such as water irrigation, fertilizer and pesticide applications might have a major impact on the distribution of metals. Metal speciation analysis presented that Cu, Zn and Cd were dominated by the residual fraction, while Pb was dominated by the reducible fraction. Because of the low mobility of the metals in the investigated area, no remarkable difference could be observed between upstream and downstream separated by the factory site.