-Selenium deficiency (Keshan Disease) and toxicity diseases in humans occur within 20 km of each other in Enshi District in China and have been linked to environmental levels of Se. Low concentrations of Se are associated with Jurassic siltstones and sandstones, whereas high concentrations occur in areas underlain by Permian carbonaceous strata. Although these broad relationships between Se in the environment and the human population have been established previously, not all villages underlain by the carbonaceous strata suffer Se toxicity problems and the precise controls on Se distribution and availability have not been quantified. In the present study soil, grain, drinking water and human hair samples are examined to determine the controls on Se availability in three Se environments in Enshi District. Five low-Se and Keshan Disease villages, five high-Se and no toxicity villages and five high-Se and toxicity villages were selected for the study. Results show that the majority of samples in the low-Se villages are deficient or marginal in Se and that Se availability to plants is inhibited by adsorption onto organic matter and Fe oxyhydroxides in soil. Therefore, remediation strategies involving the application of Se fertiliser direct to the soil may not increase plant Se levels as expected. In the highSe villages, localised lithological variations result in considerable ranges in Se concentrations in all sample types. Deficient and excessive levels of Se are recorded samples from the same village. Selenium bioavailability in the high-Se toxicity villages is controlled by the total soil Se concentration and pH. A greater proportion of the Se is plant available in villages where the carbonaceous strata are interbedded with limestone. Villagers should be advised to avoid planting crops in these areas if possible.
Black shales of the basal Lower Cambrian Niutitang Formation, southeast China, host a regionally distributed concordant, several centimeter-thick, sulfide layer which displays extreme metal enrichment, i.e., Mo-Ni-Se-Re-Os-As-Hg-Sb >1,000 times enriched and Ag-Au-Pt-Pd >100 times enriched over bulk continental crust. Mineable portions have about 5.5 wt percent Mo, 3.5 wt percent Ni, and 1 g/t PGE + Au. A six-point 187 Os/ 188 Os versus 187 Re/ 188 Os isochron on molybdenum-nickel ore samples defines an age of 541 ± 16 Ma (2σ) with an initial 187 Os/ 188 Os ratio of 0.78 ± 0.19. This age is in agreement with the depositional age of the black shale host; the initial ratio is close to present-day seawater. The sulfide layer/average seawater metal ratio is on the order of 10 6 to 10 8 , about 10 to 100 times higher than that for the black shale host and for average metalliferous black shale. Synsedimentary metal enrichment from seawater under anoxic (sulfate-reducing) conditions appears likely but requires an unusually low sedimentation rate and/or high replenishment rate of fresh seawater to the marine basin. The paleogeographic setting of the Lower Cambrian continental margin of the Yangtze craton indicates local basins controlled by synsedimentary rifting. Stagnant water episodically replenished by upwelling oxidized seawater is thought to be responsible for the formation of the polymetallic sulfide layer and of phosphorite, barite, and sapropelic "stone coal" (combustible black shale) beds.
In the realm of extreme nanophotonics, nanogap plasmons support reliable field enhancements up to 1000, which provide unique opportunities to access a single molecule for strong coupling and a single atom for quantum catalysis. The quantum plasmonics are intriguing but difficult to modulate largely because of the lack of proper spacers that can reversibly actuate the sub–1-nm gaps. Here, we demonstrate that supramolecular systems made of oligoamide sequences can reversibly switch the gap plasmons of Au nanoparticles on mirror between classical and quantum tunneling regimes via supramolecular interactions. The results reveal detailed plasmon shift near the quantum tunneling limit, which fits well with both classical- and quantum-corrected models. In the quantum tunneling regime, we demonstrate that plasmonic hot electron tunneling can further blue shift the quantum plasmons because of the increased conductance in the nanogaps, making it a promising prototype of optical tunable quantum plasmonic devices.
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