The uptake of selenite in calcite revealed by X-ray absorption spectroscopy and quantum chemical calculations.

Selenium (Se) is an important trace element in the environment, but the interaction of Se with calcite that may control the fate and geochemical behavior of Se is not fully understood. In this study, the molecular-scale mechanism for the uptake of selenite in calcite was investigated by a combination of laboratory experiments, extended X-ray absorption fine structure (EXAFS) spectroscopy, and quantum chemical calculations. Results showed that selenite can be largely distributed to calcite at circumneutral pH. The local structure of Se in calcite obtained from EXAFS analyses, in combination with quantum chemical calculations, demonstrated that selenite can be incorporated into calcite by substituting for the carbonate, and that the geometric incompatibility of selenite could be accommodated by a slight expansion of crystal volume. The findings from this study suggest that calcite could be a potential Se sink, providing an important insight into the understanding of the mobility and geochemical behavior of Se in the subsurface environments particularly in the groundwater system.

Microscale Investigation into Selenium Distribution and Speciation in Se-Rich Soils from Enshi, China.

In this study, we investigated the distribution and chemical speciation of Se in Se-rich soil by using micro-focused X-ray absorption near-edge structure (µ-XANES) spectroscopy coupling with X-ray fluorescence (µ-XRF) mapping. The microscale distribution showed that Se is heterogeneously distributed in the soil from seleniferous areas in Enshi, China. Se K-edge µ-XANES analysis suggested that Se is mainly present as Se(IV), organic Se(-II) or Se(0) species in Se-rich agricultural soil. The findings from this study would help improve the understanding of the fate, mobility, bioavailability, and biogeochemical cycling of Se in the seleniferous soil environment.

Tellurium Distribution and Speciation in Contaminated Soils from Abandoned Mine Tailings: Comparison with Selenium.

The distribution and chemical species of tellurium (Te) in contaminated soil were determined by a combination of microfocused X-ray fluorescence (µ-XRF), X-ray diffraction (µ-XRD), and X-ray absorption fine structure (µ-XAFS) techniques. Results showed that Te was present as a mixture of Te(VI) and Te(IV) species, while selenium (Se) was predominantly present in the form of Se(IV) in the soil contaminated by abandoned mine tailings. In the contaminated soil, Fe(III) hydroxides were the host phases for Se(IV), Te(IV), and Te(VI), but Te(IV) could be also retained by illite. The difference in speciation and solubility of Se and Te in soil can result from different structures of surface complexes for Se and Te onto Fe(III) hydroxides. Furthermore, our results suggest that the retention of Te(IV) in soil could be relatively weaker than that of Te(VI) due to structural incorporation of Te(VI) into Fe(III) hydroxides. These findings are of geochemical and environmental significance for better understanding the solubility, mobility, and bioavailability of Te in the surface environment. To the best of our knowledge, this is the first study reporting the speciation and host phases of Te in field soil by the µ-XRF-XRD-XAFS techniques.

Selenium speciation in seleniferous agricultural soils under different cropping systems using sequential extraction and X-ray absorption spectroscopy.

Selenium (Se) speciation in soil is critically important for understanding the solubility, mobility, bioavailability, and toxicity of Se in the environment. In this study, Se fractionation and chemical speciation in agricultural soils from seleniferous areas were investigated using the elaborate sequential extraction and X-ray absorption near-edge structure (XANES) spectroscopy. The speciation results quantified by XANES technique generally agreed with those obtained by sequential extraction, and the combination of both approaches can reliably characterize Se speciation in soils. Results showed that dominant organic Se (56-81% of the total Se) and lesser Se(IV) (19-44%) were observed in seleniferous agricultural soils. A significant decrease in the proportion of organic Se to the total Se was found in different types of soil, i.e., paddy soil (81%) > uncultivated soil (69-73%) > upland soil (56-63%), while that of Se(IV) presented an inverse tendency. This suggests that Se speciation in agricultural soils can be significantly influenced by different cropping systems. Organic Se in seleniferous agricultural soils was probably derived from plant litter, which provides a significant insight for phytoremediation in Se-laden ecosystems and biofortification in Se-deficient areas. Furthermore, elevated organic Se in soils could result in higher Se accumulation in crops and further potential chronic Se toxicity to local residents in seleniferous areas.

The bioavailability of selenium and risk assessment for human selenium poisoning in high-Se areas, China.

Enshi prefecture of Hubei Province is well known for human selenium (Se) poisoning in the early 1960s in China. Sporadic cases of Se poisoning in livestocks are still being found. In this study, Se levels in water, cropland soils and various crops from high-Se areas of Enshi were measured to investigate the distribution and bioavailability of Se in the environments, as well as probable daily intake (PDI) of Se for local residents. The total Se in surface water ranged from 2.0 to 519.3µg/L with a geometric mean of 46.0±127.8 µg/L (n=48), 70.5-99.5% of which was present in the form of Se(VI). The soil Se concentration varied from 2.89 to 87.3 µg/g with a geometric mean of 9.36±18.6 µg/g (n=45), and most of Se was associated with organic matter (OM-Se). The total Se in rice, corn, and vegetable samples were 2.11±2.87 µg/g (n=21), 3.76±11.6 µg/g (n=16), and 2.09±3.38 µg/g (n=25), respectively. Stream water Se is likely leached from carbonaceous shale and mine wastes, leading to Se accumulation in paddy soils. OM-Se may play an important role in Se uptake by rice plant in high-Se area of Enshi. The PDI of Se is approximately 2144 µg/day, and Se concentration in blood is estimated at about 3248 µg/L, posing a potential chronic Se poisoning risk to local residents. Cereal consumption (48.5%) makes a great contribution to human daily Se intake, followed by vegetables (36.6%), meats (8.5%), and drinking water (6.4%). However, when assessing health risk on human in high-Se areas, the contribution of drinking water to daily Se intake cannot be ignored due to high Se content and dominant Se(VI) species. Local inhabitants should be advised not to grow crops in high-Se lands or irrigate using high-Se water. If possible, they should drink pipe water and consume foods mixed with those from outside the high-Se areas.

Selenium fractions in organic matter from Se-rich soils and weathered stone coal in selenosis areas of China.

A high degree of association between Selenium (Se) and organic matter has been demonstrated in natural environments, but Se fractions and speciation in organic matter is unclear. In this study, a method for quantifying organic matter associated with Se (OM-Se) was developed to investigate Se fractions in organic matter in Se-rich soils and weathered stone coal from Enshi, China, where Se poisoning of humans and livestock has been documented. Initially, Se was extracted using water and a phosphate buffer. Subsequently, OM-Se was extracted using NaOH, and then speciated into Se associated with fulvic acids (FA-Se) and humic acids (HA-Se). Both FA-Se and HA-Se were further speciated into the weakly bound and strongly bound fractions using a customized hydride generation reactor. The results show that FA-Se (1.91-479 mg kg(-1)) is the predominant form of Se in all Se-rich soils and the weathered stone coal samples, accounting for more than 62% of OM-Se (3.07-484 mg kg(-1)). Weakly bound FA-Se (1.33-450 mg kg(-1)) was prevalent in the total FA-Se, while weakly bound HA-Se (0.62-26.2 mg kg(-1)) was variable in the total HA-Se (1.15-32.5 mg kg(-1)). These data indicate that OM-Se could play a significant source and sink role in the biogeochemical cycling of Se in the supergene environment. Weakly bound FA-Se seems to act as a potential source for bioavailable Se, whereas strongly bound HA-Se is a possible OM-Se sink which is not readily transformed into bioavailable Se.