Behavior of antimony(V) during the transformation of ferrihydrite and its environmental implications.

In this study, we investigated the behavior of Sb(V) during the transformation of poorly crystalline Fe(III) oxyhydroxides (two-line ferrihydrite) with various Sb/Fe molar ratios at pH 6.0. Both XRD and Fe EXAFS analyses confirmed that goethite and hematite are the primary transformation products of the ferrihydrite in the presence of Sb(V). The crystallization kinetics showed that the transformation rate with Sb(V) was approximately the same as that of the control (without Sb(V)), which indicates that the presence of Sb(V) does not influence the transformation rate to a noticeable extent. Throughout the transformation, Sb(V) dominantly partitioned in the solid phase and no desorption of Sb(V) was observed. Furthermore, Sb EXAFS analyses suggested that Sb(V) in the solid phase is structurally incorporated into crystalline goethite and/or hematite generated by the ferrihydrite transformation. Hence, Sb(V) transfers into the thermodynamically stable solids from the metastable ferrihydrite with aging, indicating a rigid immobilization of Sb(V). These findings are valuable for making predictions on the long-term fate of Sb associated with ferrihydrite in natural environments.

Microcalorimeter-type energy dispersive X-ray spectrometer for a transmission electron microscope.

A new energy dispersive X-ray spectrometer (EDS) with a microcalorimeter detector equipped with a transmission electron microscope (TEM) has been developed for high- accuracy compositional analysis in the nanoscale. A superconducting transition-edge-sensor-type microcalorimeter is applied as the detector. A cryogen-free cooling system, which consists of a mechanical and a dilution refrigerator, is selected to achieve long-term temperature stability. In order to mount these detector and refrigerators on a TEM, the cooling system is specially designed such that these two refrigerators are separated. Also, the detector position and arrangement are carefully designed to avoid adverse affects between the superconductor detector and the TEM lens system. Using the developed EDS system, at present, an energy resolution of 21.92 eV full-width-at-half maximum has been achieved at the Cr K alpha line. This value is about seven times better than that of the current typical commercial Si(Li) detector, which is usually around 140 eV. The developed microcalorimeter EDS system can measure a wide energy range, 1-20 keV, at one time with this high energy resolution that can resolve peaks from most of the elements. Although several further developments will be needed to enable practical use, highly accurate compositional analysis with high energy resolution will be realized by this microcalorimeter EDS system.

Biogeochemical signals from deep microbial life in terrestrial crust.

In contrast to the deep subseafloor biosphere, a volumetrically vast and stable habitat for microbial life in the terrestrial crust remains poorly explored. For the long-term sustainability of a crustal biome, high-energy fluxes derived from hydrothermal circulation and water radiolysis in uranium-enriched rocks are seemingly essential. However, the crustal habitability depending on a low supply of energy is unknown. We present multi-isotopic evidence of microbially mediated sulfate reduction in a granitic aquifer, a representative of the terrestrial crust habitat. Deep meteoric groundwater was collected from underground boreholes drilled into Cretaceous Toki granite (central Japan). A large sulfur isotopic fractionation of 20-60‰ diagnostic to microbial sulfate reduction is associated with the investigated groundwater containing sulfate below 0.2 mM. In contrast, a small carbon isotopic fractionation (<30‰) is not indicative of methanogenesis. Except for 2011, the concentrations of H2 ranged mostly from 1 to 5 nM, which is also consistent with an aquifer where a terminal electron accepting process is dominantly controlled by ongoing sulfate reduction. High isotopic ratios of mantle-derived 3He relative to radiogenic 4He in groundwater and the flux of H2 along adjacent faults suggest that, in addition to low concentrations of organic matter (<70 µM), H2 from deeper sources might partly fuel metabolic activities. Our results demonstrate that the deep biosphere in the terrestrial crust is metabolically active and playing a crucial role in the formation of reducing groundwater even under low-energy fluxes.