Even though the Amazon region is widely studied, there is still a gap regarding Cr exposure and its risk to human health. The objectives of this study were to 1) determine Cr concentrations in seven chemical fractions and 6 particle sizes in Amazon soils, 2) quantify hexavalent Cr (CrVI) concentrations using an alkaline extraction, 3) determine the oral and lung bioaccessible Cr, and 4) assess Cr exposure risks based on total and bioaccessible Cr in soils. The total Cr in both A (0–20 cm) and B (80–100 cm) horizons was high at 2346 and 1864 mg kg⁻¹. However, sequential extraction indicated that available Cr fraction was low compared to total Cr, with Cr in the residual fraction being the highest (74–76%). There was little difference in total Cr concentrations among particle sizes. Hexavalent Cr concentration was also low, averaging 0.72 and 2.05 mg kg⁻¹ in A and B horizon. In addition, both gastrointestinal (21–22 mg kg⁻¹) and lung (0.95–1.25 mg kg⁻¹) bioaccessible Cr were low (<1.2%). The low bioavailability of soil Cr and its uniform distribution in different particle sizes indicated that Cr was probably of geogenic origin. Exposure based on total Cr resulted in daily intake > the oral reference dose for children, but not when using CrVI or bioaccessible Cr. The data indicated that it is important to consider both Cr speciation and bioaccessibility when evaluating risk from Cr in Amazon soils.

Simulating the storage of aerobic soils under water, the chemical speciation of heavy metals and arsenic was studied over a long-term reduction period. Time-dynamic and redox-discrete measurements in reactors were used to study geochemical changes. Large kinetic differences in the net-complexation quantities of heavy metals with sulfides was observed, and elevated pore water concentrations remained for a prolonged period (>1 year) specifically for As, B, Ba, Co, Mo, and Ni. Arsenic is associated to the iron phases as a co-precipitate or sorbed fraction to Fe-(hydr)oxides, and it is being released into solution as a consequence of the reduction of iron. The composition of dissolved organic matter (DOM) in reducing pore water was monitored, and relative contributions of fulvic, humic and hydrophylic compounds were measured via analytical batch procedures. Quantitative and qualitative shifts in organic compounds occur during reduction; DOM increased up to a factor 10, while fulvic acids become dominant over humic acids which disappear altogether as reduction progresses. Both the hydrophobic and hydrophilic fractions increase and may even become the dominant fraction.Reactive amorphous and crystalline iron phases, as well as dissolved FeII/FeIII speciation, were measured and used as input for the geochemical model to improve predictions for risk assessment to suboxic and anaerobic environments. The release of arsenic is related to readily reducible iron fractions that may be identified by 1 mM CaCl2 extraction procedure. Including DOM concentration shifts and compositional changes during reduction significantly improved model simulations, enabling the prediction of peak concentrations and identification of soils with increased emission risk. Practical methods are suggested to facilitate the practice of environmentally acceptable soil storage under water.

Uranium (U) can enter aquatic environments from natural and anthropogenic processes, accumulating in sediments to concentrations that could, if bioavailable, adversely affect benthic organisms. To better predict the sorption and mobility of U in aquatic ecosystems, we investigated the sediment-solution partition coefficients (Kd) of U for nine uncontaminated freshwater sediments with a wide range of physicochemical characteristics over an environmentally relevant pH range. Test solutions were reconstituted to mimic water quality conditions and U(VI) concentrations (0.023–2.3 mg U/L) found downstream of Canadian U mines. Adsorption of U(VI) to each sediment was greatest at pH 6 and 7, and significantly reduced at pH 8. There were significant differences in pH-dependent sorption among sediments with different physicochemical properties, with sorption increasing up until thresholds of 12% total organic carbon, 37% fine fraction (≤50 μm), and 29 g/kg of iron content. The Kd values for U(VI) were predicted using the Windermere Humic Aqueous Model (WHAM) using total U(VI) concentrations, and water and sediment physicochemical parameters. Predicted Kd-U values were generally within a factor of three of the observed values. These results improve the understanding and assessment of U sorption to field sediment, and quantify the relationship with sediment properties that may influence the bioavailability and ecological risk of U-contaminated sediments.

The main objective of this study was to unravel the chemical reactions and processes dictating the potential bioavailability of vanadium (V). In environmental solutions V exists in two stable oxidation states, +IV and +V, of which + V is considered to be more toxic. In this study, the effect of speciation and soil pH on the chemical accessibility of V was investigated with two soils: 1) field soil rather rich in soil organic matter (SOM) and 2) coarse mineral soil low in SOM. Fresh soil samples treated with V(+V) (added as NaVO3) or V(+IV) (added as VOSO4) (pH adjusted to the range 4.0–6.9) were incubated for 3 months at 22 °C. The adsorption tendency of V species was explored by water extraction (Milli-Q water, 1:50 dw/V) and by sequential extraction (0.25 M KCl; 0.1 M KH2/K2HPO4; 0.1 M NaOH; 0.25 M H2SO4, 1:10 dw/V). The potential bioavailability of V was found to be dictated by soil properties. SOM reduced V(+V) to V(+IV) and acted as a sorbent for both species, which lowered the bioaccessibility of V. A high pH, in turn, favored the predominance of the V(+V) species and thus increased the chemical accessibility of V.

Increasing commercial use of nanosilver has focussed attention on the fate of silver (Ag) in the wastewater release pathway. This paper reports the speciation and lability of Ag in archived, stockpiled, and contemporary biosolids from the UK, USA and Australia, and indicates that biosolids Ag concentrations have decreased significantly over recent decades. XANES revealed the importance of reduced-sulfur binding environments for Ag speciation in materials ranging from freshly produced sludge to biosolids weathered under ambient environmental conditions for more than 50 years. Isotopic dilution with 110mAg showed that Ag was predominantly non-labile in both fresh and aged biosolids (13.7% mean lability), with E-values ranging from 0.3 to 60 mg/kg and 5 mM CaNO3 extractable Ag from 1.2 to 609 μg/kg (0.002–3.4% of the total Ag). This study indicates that at the time of soil application, biosolids Ag will be predominantly Ag-sulfides and characterised by low isotopic lability.

We investigated the effects of chromate (CrVI) and phosphate (P) on their uptake and translocation in As-hyperaccumulator Pteris vittata (PV). Plants were exposed to 1) 0.10 mM CrVI and 0, 0.25, 1.25, or 2.50 mM P or 2) 0.25 mM P and 0, 0.50, 2.5 or 5.0 mM CrVI for 24 h in hydroponics. PV accumulated 2919 mg/kg Cr in the roots at CrVI0.10, and 5100 and 3500 mg/kg P in the fronds and roots at P0.25. When co-present, CrVI and P inhibited each other's uptake in PV. Increasing P concentrations reduced Cr root concentrations by 62–82% whereas increasing CrVI concentrations reduced frond P concentrations by 52–59% but increased root P concentrations by 11–15%. Chromate reduced P transport, with more P being accumulated in PV roots. Though CrVI was supplied, 64−78% and 92−93% CrIII were in PV fronds and roots. Based on X-ray diffraction, Cr2O3 was detected in the roots confirming CrVI reduction to CrIII by PV. In short, CrVI and P inhibited each other in uptake and translocation by PV, and CrVI reduction to CrIII in PV roots served as its detoxification mechanism. The finding helps to understand the interactions of P and Cr during their uptake in PV.

Amending contaminated soils with organic wastes can influence trace element mobility and toxicity. Soluble concentrations of metals and arsenic were measured in pore water and aqueous soil extracts following the amendment of a heavily contaminated mine soil with compost and biochar (10% v:v) in a pot experiment. Speciation modelling and toxicity assays (Vibrio fischeri luminescence inhibition and Lolium perenne germination) were performed to discriminate mechanisms controlling metal mobility and assess toxicity risk thereafter. Biochar reduced free metal concentrations furthest but dissolved organic carbon primarily controlled metal mobility after compost amendment. Individually, both amendments induced considerable solubilisation of arsenic to pore water (>2500 μg l−1) related to pH and soluble phosphate but combining amendments most effectively reduced toxicity due to simultaneous reductions in extractable metals and increases in soluble nutrients (P). Thus the measure–monitor-model approach taken determined that combining the amendments was most effective at mitigating attendant toxicity risk.

Identifying the bioavailability and release-desorption mechanism of heavy metals (HMs) in soil is critical to understand the release risk of HMs. Simultaneously, the mechanistic investigation of affecting the bioavailability of HMs in soil is necessary, such as the grain-size distribution and soil mineralogy. Herein, the bioavailability of HMs (Cu, Cd, Ni, Pb, and Zn) in different area soils near a typical copper-smelter was evaluated by the sequential extraction technique (BCR), diffusive gradients in thin-films (DGT), and DGT-induced fluxes in sediments (DIFS) model. Results showed that the HMs proportion of the residual fraction in all soils was the highest. The average bioavailability concentration (CDGT) of Cu and Cd in industrial soil was the highest, with 45.12 μg· L⁻¹ and 9.06 μg· L⁻¹. The result of DIFS model revealed that the decreased order of the mean value of desorption rate constant (K₋₁) was Cd > Zn > Ni > Cu > Pb, 5.91 × 10⁻⁵, 4.96 × 10⁻⁵, 2.89 × 10⁻⁵, 9.64 × 10⁻⁶, and 8.69 × 10⁻⁶, respectively. According to the spatial distribution of release potential (R-value), the release potential of labile-Cu in agricultural soil was the highest, which was mainly attributed to fertilizer application in farmland. Simultaneously, the reduced hydroxyl was also related to the agricultural activities, resulting in the weakened adsorption capacity of HMs by soil. Redundancy analysis (RDA) results showed that the bioavailability of Cd, Ni, and Zn was mainly driven by soil pH, while the bioavailability of Cu and Pb was primarily driven by dissolved organic carbon (DOC). Meanwhile, carbonate minerals had a positive correlation with the bioavailability of Cd, Ni, and Zn, which could promote the release of HMs in mining soil as chemical weathering progresses. In conclusion, this study provides a structured method which can be used as a standard approach for similar scenarios to determine the geochemical fractionation, bioavailability, and release kinetics of heavy metals in soils.

Rare earth elements (REE) have become essential in high- and green-technologies. Their increasing use lead to the release of anthropogenic REE into the environment including aquatic systems. The limited data available on the aquatic ecotoxicology of REE indicate their biological effects are highly dependent on their speciation, posing challenges for a reliable environmental risk assessment (ERA). The current study assessed the influence of speciation on the toxicity of neodymium (Nd), gadolinium (Gd) and ytterbium (Yb) in the Daphnia magna mobility inhibition test (ISO 6341:2012). REE toxicity was assessed individually and in ternary mixture, in the absence and presence of dissolved organic matter (DOM). Speciation was predicted by modeling and REE bioaccumulation by D. magna was measured to better understand the relationship between REE speciation and toxicity. DOM decreased significantly the toxicity of Nd, Gd and the mixture towards this freshwater crustacean. This was explained by a lower REE bioaccumulation in the presence of DOM due to REE-DOM complexation, which reduced REE bioavailability. DOM effects on Yb toxicity and bioaccumulation were limited because of Yb precipitation. We show that the way of expressing EC50 values (based on nominal, measured or predicted REE concentrations in solution) drastically changed REE toxicity assessment and that these changes were influenced by REE speciation. This study demonstrates for the first time that REE speciation, and especially REE-DOM complexation, significantly influences REE bioaccumulation and toxicity towards D. magna. Our results have implications for the subsequent ERA of REE.

Arsenic (As) contamination of water poses severe threats to human health and thus requires effective remediation methods. In this study, Synechocystis PCC6803, a model cyanobacterium common in aquatic environments, was used to investigate the role of extracellular polymeric substances (EPS) in As toxicity, accumulation, and transformation processes. We monitored the growth of Synechocystis with As exposure, measured the zeta potential and binding sites on the cell surface, and analysed As accumulation and speciation in Synechocystis cells with and without EPS. After EPS removal, the binding sites and zeta potential of the cell surface decreased by 44.43% and 31.9%, respectively. The growth of Synechocystis decreased 49.4% and 43.7% with As⁽ᴵᴵᴵ⁾ and As⁽ⱽ⁾ exposure, and As accumulation in the cells decreased by 12.8–44.5% and 14–42.7%, respectively. As absorption was enhanced in cells with EPS removed. The oxidation of As⁽ᴵᴵᴵ⁾ and reduction of As⁽ⱽ⁾ were significantly greater in cells with intact EPS compared to those with EPS removed. Fourier transform infrared spectroscopy (FTIR) showed that functional groups of EPS and Synechocystis cells, including –NH, –OH, CO, and CC, interacted with As species. Together the results of this work demonstrate that EPS have significant impacts on cell surface properties, thereby affecting As accumulation and transformation in Synechocystis PCC6803. This work provides a basis for using EPS to remedy As pollution in aquatic environments.