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.

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.

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.

Globally, millions of people who rely on groundwater for potable purposes and agriculture have been inadvertently exposed to toxic arsenic (As) because of its natural occurrence in groundwater in several countries of Asia, Europe and America. While the presence of As in groundwater and its impacts on human health have been documented in many countries, there is little information on As contamination in Pakistan. This review highlights, for the first time, the extent and severity of As-induced problems in Pakistan based on relevant published papers; discusses possible sources of As contamination of aquifers; and estimates As-induced potential health hazards in the country in relation to global data. Data from 43 studies (>9882 groundwater samples) were used to describe As variability in groundwater of Pakistan and for comparison with global data. The mean groundwater As content reported in these studies was 120 μg/L (range: 0.1–2090 μg/L; SD: ±307). About 73% of the values for mean As contents in the 43 studies were higher than the World Health Organization (WHO) permissible limit (10 μg/L) for drinking water, while 41% were higher than the permissible limit of As in Pakistan (50 μg/L). It was observed that groundwater samples in some areas of Punjab and Sindh provinces contained high As concentrations which were almost equal to concentrations reported in the most contaminated areas of the world. We predicted that the mean values of ADD, HQ and CR were 4.4 μg kg⁻¹day⁻¹ (range: 0–77 μg kg⁻¹day⁻¹), 14.7 (range: 0–256) and 0.0029 (range: 0–0.0512), respectively, based on mean As concentrations reported in Pakistan. In addition, this article proposes some integrated sustainable solutions and future perspectives keeping in view the regional and global context, as well as the on-ground reality of the population drinking As-contaminated water, planning issues, awareness among civil society and role of the government bodies. Based on available data, it is predicted that almost 47 million people in Pakistan are residing in areas where more than 50% of groundwater wells contain As concentrations above the WHO recommended limit of As in drinking water.

Estuarine sediments can be a source of Phosphorus (P) to coastal waters, contributing to nutrient budgets and geochemical cycles. In this work, the concentration and speciation of P in 47 cores were examined from the inter-tidal mud flats of the tidal river Thames (~120km). Results of P concentration and speciation were combined with published data relating to known sediment dynamics and water chemistry (salinity) within the estuary to produce a conceptual model of sediment-P behaviour. Results demonstrated significant P desorption occurring after sediment passed through the Estuarine Turbidity Maximum and when the salinity of the river water exceeded ~6ppt. It was found that organic P was desorbed to a greater extent than inorganic P in the lower estuary. Models were used to identify those geochemical parameters that contributed to the Total P (R²=0.80), oxalate extractable P (R²=0.80) and inorganic P (R²=0.76) concentrations within the Thames estuary.

Carbon-capture and storage is considered to be a potential mitigation option for climate change. However, accidental leaks of CO2 can occur, resulting in changes in ocean chemistry such as acidification and metal mobilization. Laboratory experiments were performed to provide data on the effects of CO2-related acidification on the chemical fractionation of metal(loid)s in marine-contaminated sediments using sequential extraction procedures. The results showed that sediments from Huelva estuary registered concentrations of arsenic, copper, lead, and zinc that surpass the probable biological effect level established by international protocols. Zinc had the greatest proportion in the most mobile fraction of the sediment. Metals in this fraction represent an environmental risk because they are weakly bound to sediment, and therefore more likely to migrate to the water column. Indeed, the concentration of this metal was lower in the most acidified scenarios when compared to control pH, indicating probable zinc mobilization from the sediment to the seawater.