For divalent metals, the Biotic Ligand Model (BLM) has been proven to be an effective tool to predict biological effects by taking into account speciation calculations and competitive interactions. Nonetheless, the BLM has only rarely been validated for trivalent metals (e.g. rare earth elements), and the potential competitive effects of protons has been understudied. In this paper, the short-term biouptake of indium (In), a trivalent metal that is a byproduct of zinc extraction and used in numerous applications including the semiconductor industry, was evaluated under controlled conditions. Short-term (i.e. 60 min) indium biouptake by Chlamydomonas reinhardtii was measured as a function of pH in order to verify the validity of the BLM. At a given pH, In biouptake could be well described by the Michaelis-Menten equation with conditional stability constants of KIn,pH=4.0 = 106.7 M-1, KIn,pH=5.0 = 108.6 M-1, KIn,pH=6.0 = 109.3 M-1 and maximum internalization fluxes of Jmax, pH=4.0 = 0.74 × 10−14 mol cm−2 s−1, Jmax, pH=5.0 = 1.60 × 10−14 mol cm−2 s−1, Jmax, pH=6.0 = 2.22 × 10−14 mol cm−2 s−1. Although several potential mechanisms for the role of pH were examined, the results were best explained by a competitive interaction of H+ with the In uptake sites using overall stability constants of logKIn = 9.76 M-1 and logKH = 15.66 M-1. Based on these results, pH will play a critical role in bioavailability measurements of the trivalent cations in natural waters.

The main objectives of this study were to evaluate global uncertainty in the prediction of Distribution coefficients (Kds) for several Trace Metals (TM) (Cd, Cu, Pb, Zn) through the probabilistic use of a geochemical speciation model, and to conduct sensitivity analysis in speciation modeling in order to identify the main sources of uncertainty in Kd prediction. As a case study, data from the Loire river (France) were considered. The geochemical speciation model takes into account complexation of TM with inorganic ligands, sorption of TM with hydrous ferric oxides, complexation of TM with dissolved and particulate organic matter (i.e. dissolved and particulate humic acids and fulvic acids) and sorption and/or co-precipitation of TM to carbonates. Probability Density Functions (PDFs) were derived for physico-chemical conditions of the Loire river from a comprehensive collection of monitoring data. PDFs for model parameters were derived from literature review. Once all the parameters were assigned PDFs that describe natural variability and/or knowledge uncertainty, a stepwise structured sensitivity analysis (SA) was performed, by starting from computationally ‘inexpensive’ Morris method to most costly variance-based EFAST method. The most sensitive parameters on Kd predictions were thus ranked and their contribution to Kd variance was quantified. Uncertainty analysis was finally performed, allowing quantifying Kd ranges that can be expected when considering all the sensitive parameters together.

We conducted an exposure experiment with Diffusive Gradients in Thin- Films (DGT), fathead minnow (Pimephales promelas), and yellow lampmussel (Lampsilis cariosa) to estimate bioavailability and bioaccumulation of Cu. We hypothesized that Cu concentrations measured by DGT can be used to predict Cu accumulation in aquatic animals and alterations of water chemistry can affect DGT's predict ability. Three water chemistries (control soft water, hard water, and addition of natural organic matter (NOM)) and three Cu concentrations (0, 30, and 60 μg/L) were selected, so nine Cu-water chemistry combinations were used. NOM addition treatments resulted in decreased concentrations of DGT-measured Cu and free Cu ion predicted by Biotic Ligand Model (BLM). Both hard water and NOM addition treatments had reduced concentrations of Cu ion and Cu-dissolved organic matter complexes compared to other treatments. DGT-measured Cu concentrations were linearly correlated to fish accumulated Cu, but not to mussel accumulated Cu. Concentrations of bioavailable Cu predicted by BLM, the species complexed with biotic ligands of aquatic organisms and, was highly correlated to DGT-measured Cu. In general, DGT-measured Cu fit Cu accumulations in fish, and this passive sampling technique is acceptable at predicting Cu concentrations in fish in waters with low NOM concentrations.

Selenium (Se) is an essential trace element for humans and animals, although controversial for different plant species. There exists a narrow line between essential, beneficial and toxic levels of Se to living organisms which greatly varies with Se speciation, as well as the type of living organisms. Therefore, it is crucial to monitor its solid- and solution-phase speciation, exposure levels and pathways to living organisms. Consumption of Se-laced food (cereals, vegetables, legumes and pulses) is the prime source of Se exposure to humans. Thus, it is imperative to assess the biogeochemical behavior of Se in soil-plant system with respect to applied levels and speciation, which ultimately affect Se status in humans. Based on available relevant literature, this review traces a plausible link among (i) Se levels, sources, speciation, bioavailability, and effect of soil chemical properties on selenium bioavailability/speciation in soil; (ii) role of different protein transporters in soil-root-shoot transfer of Se; and (iii) speciation, metabolism, phytotoxicity and detoxification of Se inside plants. The toxic and beneficial effects of Se to plants have been discussed with respect to speciation and toxic/deficient concentration of Se. We highlight the significance of various enzymatic (catalase, peroxidase, superoxide dismutase, ascorbate peroxidase, glutathione peroxidase) and non-enzymatic (phytochelatins and glutathione) antioxidants which help combat Se-induced overproduction of reactive oxygen species (ROS). The review also delineates Se accumulation in edible plant parts from soils containing low or high Se levels; elucidates associated health disorders or risks due to the consumption of Se-deficient or Se-rich foods; discusses the potential role of Se in different human disorders/diseases.

Correct characterization of metal speciation and reactivity is a prerequisite for the risk assessment and remedial activity management of contaminated soil. To better understand the intrinsic reactivity of Pb and Zn, nine heavily and poorly contaminated soils were investigated using the combined approaches of chemical extractions, multi-element stable isotopic dilution (ID) method, and multi-surface modelling. The ID results show that 0.1–38% of total Pb and 3–45% of total Zn in the studied soils are isotopically exchangeable after a 3-day equilibration. The intercomparison between experimental and modelling results evidences that single extraction with 0.43 M HNO3 solubilizes part of non-isotopically exchangeable fraction of Pb and Zn in the studied soils, and cannot be used as a surrogate for ID to assess labile Pb and Zn pools in soil. Both selective sequential extraction (SSE) and modelling reveal that Mn oxides are the predominant sorption surface for Pb in the studied soils; while Zn is predicted to be mainly associated with soil organic matter in the soil with low pH and Fe/Mn oxides in the soils with high pH. Multi-surface modelling can provide a reasonable prediction of Pb and Zn adsorption onto different soil constituents for the most of the studied soils. The modelling could be a promising tool to decipher the underlying mechanism that controls metal reactivity in soil, but the submodel for Mn oxides should be incorporated and the model parameters, especially for the 2-pK diffuse layer model for Mn oxides, should be updated in the further studies.

Calcination of Hg ores has resulted in serious contamination of mercury (Hg) in the environment. To understand the mobilization of Hg in the calcine pile, the speciation of Hg in a profile of a large calcine pile in the Wanshan Mercury Mine, SW China was investigated using the X-ray absorption spectroscopy (XANES), to understand the mobilization of Hg in the calcine pile. Higher concentrations of Hg were observed at the 30–50 cm depth of the profile, corresponding to a cemented layer. This layer is observed in the entire pile, and was formed due to cementation of calcines. Hg species in calcines include cinnabar (α-HgS), metacinnabar (β-HgS), elemental Hg(0), and minor mercuric chloride (HgCl2), but these Hg species show dramatic changes in the profile. Variations in Hg speciation suggest that extensive mobilization of Hg can occur during weathering processes. We show that the cemented layer can prevent the leaching of Hg and the emission of Hg(0) from the pile. High MeHg concentrations were found near the cemented layer, indicating Hg methylation occurs. This study provides important insights into the environmental risk of Hg in mining areas.

The Athabasca's oil sands exploitation is controversial due to its potential risks to water quality but little is known about the temporal changes in the most bioavailable fraction of metal, the free/labile species. In this study, diffusive gradient in thin films (DGT) and the Windermere Humic Aqueous Model (WHAM VII) equilibrium model were used to examine the temporal changes in free/labile metal (Cu, Ni, Zn, Pb) species in three tributaries of the north-flowing Athabasca River in the Athabasca oil sands region (AOSR). The influence of dissolved organic matter (DOM) composition (i.e. fulvic: humic ratio) on modeled Cu and Ni speciation showed a negligible effect on the labile concentration. The best agreements (92 ± 8%) between DGT-labile and WHAM calculated labile concentrations were found assuming the formation of iron oxyhydroxides (FeO(OH)). The agreement was only 70 ± 7% in the presence of inorganic colloidal aluminum oxyhydroxides (AlO(OH)) and in the absence of any inorganic colloids. Together these results suggest that a change in DOM composition had limited impacts on modeled free metal ion concentrations. Although the concentration of the main metal ligand (i.e. DOM), varied from 9 to 40 ppm, no significant temporal differences in the abundance of WHAM-modeled labile species were found, suggesting mobility and bioavailability of Cu, Ni, Pb and Zn were comparable over the 2003–2012 period.

Patterns of arsenic excretion were followed in a cohort (n = 6) eating a defined rice diet, 300 g per day d.wt. where arsenic speciation was characterized in cooked rice, following a period of abstinence from rice, and other high arsenic containing foods. A control group who did not consume rice were also monitored. The rice consumed in the study contained inorganic arsenic and dimethylarsinic acid (DMA) at a ratio of 1:1, yet the urine speciation was dominated by DMA (90%). At steady state (rice consumption/urinary excretion) ∼40% of rice derived arsenic was excreted via urine. By monitoring of each urine pass throughout the day it was observed that there was considerable variation (up to 13-fold) for an individual's total arsenic urine content, and that there was a time dependent variation in urinary total arsenic content. This calls into question the robustness of routinely used first pass/spot check urine sampling for arsenic analysis.

Even though antimony (Sb) and arsenic (As) are chemical analogs, differences exist on how they are taken up and translocated in plants. We investigated 1) Sb uptake, efflux and speciation in arsenic hyperaccumulator Pteris vittata after 1 d exposure to 1.6 or 8 mg/L antimonite (SbIII) or antimonate (SbV), 2) Sb uptake by PV accessions from Florida, China, and Brazil after 7 d exposure to 8 mg/L SbIII, and 3) Sb uptake and oxidation by excised PV fronds after 1 d exposure to 8 mg/L SbIII or SbV. After 1 d exposure, P. vittata took 23–32 times more SbIII than SbV, with all Sb being accumulated in the roots with the highest at 4,192 mg/kg. When exposed to 8 mg/L SbV, 98% of Sb existed as SbV in the roots. In comparison, when exposed to 8 mg/L SbIII, 81% of the total Sb remained as SbIII and 26% of the total Sb was effluxed out into the media. The three PV accessions had a similar ability to accumulate Sb at 12,000 mg/kg in the roots, with >99% of total Sb in the roots. Excised PV fronds translocated SbV more efficiently from the petioles to pinnae than SbIII and were unable to oxidize SbIII. Overall, P. vittata displayed efficient root uptake and efflux of SbIII with limited ability to translocate and transform in the roots.

International audience | Siderophores are chelators with a high selectivity for Fe(III) and a good affinity for divalent metals, including Cd(II) and Ni(II). Inoculation with siderophore-producing bacteria (SPB) has thus been proposed as an alternative to chelator supply in phytoremediation. Accurate assessments of the potential of this association require a dissection of the interaction of siderophores with metals at the soil–root interface. This study focuses on pyoverdine (Pvd), the main siderophore produced by Pseudomonas aeruginosa. We first assessed the ability of Pvd to coordinate Ni(II). The stability constant of Pvd–Ni(II) (log K L′Ni = 10.9) was found to be higher than that of Pvd–Cd(II) (log K L′Cd = 8.2). We then investigated the effect of a direct supply of Pvd on the mobilization, speciation, and phytoavailability of Cd and Ni in hydroponics. When supplied at a concentration of 50 μM, Pvd selectively promoted Ni mobilization from smectite. It decreased plant Ni and Cd contents and the free ionic fractions of these two metals, consistent with the free ion activity model. Pvd had a more pronounced effect for Ni than for Cd, as predicted from its coordination properties. Inoculation with P. aeruginosa had a similar effect on Ni phytoavailability to the direct supply of Pvd.