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Marine mammals detoxify organic methylmercury (MeHg) as inorganic mercury selenide (HgSe), yet the nature of the reaction intermediate species and the tissue-specific redistribution of Hg species in the body are unknown. We report that the identity and proportion of the dominant Hg species in long-finned pilot whale (Globicephala melas) tissues can be obtained from the bulk variation of isotopic values of δ202Hg against the extent of demethylation (percentage of total Hg as MeHg, %MeHg) using an alternating regularized inversion method. Our analysis of isotope data from two previous studies supports that MeHg is demethylated as a tetraselenolate species (Hg(Sec)4), which further transforms into HgSe. Hg(Sec)4 occurs in the liver, kidneys, muscle, heart, and brain, whereas HgSe biomineralization occurs only in the liver and kidneys. This study provides a mathematical approach that facilitates probing the molecular-level chemistry of mercury in biological tissues using bulk isotopic data.

The robust application of stable mercury (Hg) isotopes for mercury source apportionment and risk assessment necessitates the understanding of mass-dependent fractionation (MDF) as a result of internal transformations within organisms. Here, we used high energy-resolution X-ray absorption near edge structure spectroscopy and isotope ratios of total mercury (δ202THg) and methylmercury (δ202MeHg) to elucidate the chemical speciation of Hg and the resultant MDF as a result of internal MeHg demethylation in waterbirds. In three waterbirds (Clark's grebe, Forster's tern, and south polar skua), between 17 and 86% of MeHg was demethylated to inorganic mercury (iHg) species primarily in the liver and kidneys as Hg-tetraselenolate [Hg(Sec)4] and minor Hg-dithiolate [Hg(SR)2] complexes. Tissular differences between δ202THg and δ202MeHg correlated linearly with %iHg [Hg(Sec)4 + Hg(SR)2] and were interpreted to reflect a kinetic isotope effect during in vivo MeHg demethylation. The product-reactant isotopic enrichment factor (ϵp/r) for the demethylation of MeHg → Hg(Sec)4 was -2.2 ± 0.1‰. δ202MeHg values were unvarying within each bird, regardless of Hg(Sec)4 abundance, indicating fast internal cycling or replenishment of MeHg relative to demethylation. Our findings document a universal selenium-dependent demethylation reaction in birds, provide new insights on the internal transformations and cycling of MeHg and Hg(Sec)4, and allow for mathematical correction of δ202THg values as a result of the MeHg → Hg(Sec)4 reaction.

This article presents a Python‐based program, DFT2FEFFIT, to regress theoretical extended X‐ray absorption fine structure (EXAFS) spectra calculated from density functional theory structure models against experimental EXAFS spectra. To showcase its application, Ce‐doped fluorapatite [Ca10(PO4)6F2] is revisited as a representative of a material difficult to analyze by conventional multi‐shell least‐squares fitting of EXAFS spectra. The software is open source and publicly available. [ABSTRACT FROM AUTHOR]

The speciation of Mn, Fe, As and Zn in a fast-growing (0.02mm/yr), shallow-marine ferromanganese nodule has been examined by micro X-ray fluorescence, micro X-ray diffraction, and micro X-ray absorption spectroscopy. This nodule exhibits alternating Fe-rich and Mn-rich layers reflecting redox variations in water chemistry. Fe occurs as two-line ferrihydrite. The As is strictly associated with Fe and is mostly pentavalent, with an environment similar to that of As sorbed on or coprecipitated with synthetic ferrihydrite. The Mn is in the form of turbostratic birnessite with ~;10 percent trivalent manganese in the layers and probably ~;8 percent corner-sharing metal octahedra in the interlayers. The Zn is enriched on the rim of the nodule, associated with Mn. The Zn is completely (>90 percent) tetrahedrally coordinated and sorbed in the interlayers of birnessite on vacant layer Mn sites. The Zn and Mn species are similar to ones found in soils, suggesting common structural principles, despite the differing formation conditions in these systems.

The nature and proportion of Zn species present in an agricultural soil overlaid by a dredged contaminated sediment have been untangled by the novel combination of three non-invasive synchrotron-based x-ray techniques: x-ray microfluorescence ({mu}SXRF), microdiffraction ({mu}XRD), and absorption spectroscopy (EXAFS). One primary (franklinite) and two secondary (phyllomanganate and phyllosilicate) Zn-containing minerals were identified in the initial soil, and another primary (ZnS) and a new secondary (Fe-(oxyhydr)oxide) Zn species in the covered soil. The quantitative analysis of EXAFS spectra recorded on bulk samples indicated that ZnS and Zn-Fe (oxyhydr)oxides amounted to 71+-10% and 27+-10%, respectively, and the other Zn species to less than 10%. The two new Zn species found in the covered soil result from the gravitational migration of ZnS particles initially present in the sediment, and from their further oxidative dissolution and fixation of leached Zn on Fe (oxyhydr) oxides.

The crystal structures of biogenic Mn oxides produced by three fungal strains isolated from stream pebbles were determined using chemical analyses, XANES and EXAFS spectroscopy, and powder X-ray diffraction. The fungi-mediated oxidation of aqueous [Mn.Sup.2+] produces layered Mn oxides analogous to vernadite, a natural nanostructured and turbostratic variety of birnessite. The crystallites have domain dimensions of ~10 nm in the layer plane (equivalent to ~35 Mn[O.sub.6] octahedra), and ~1.5-2.2 nm perpendicularly (equivalent to ~2-3 layers), on average. The layers have hexagonal symmetry and from 22 to 30% vacant octahedral sites. This proportion likely includes edge sites, given the extremely small lateral size of the layers. The layer charge deficit, resulting from the missing layer [Mn.sup.4+] cations, is balanced mainly by interlayer [Mn.sup.3+] cations in triple-corner sharing position above and/or below vacant layer octahedra. The high surface area, defective crystal structure, and mixed Mn valence confer to these bio-minerals an extremely high chemical reactivity. They serve in the environment as sorption substrate for trace elements and possess catalytic redox properties. Keywords: Manganese oxide, birnessite, biominerals, phyllomanganate, crystal structure DOI: 10.2138/am.2010.3516

X-ray diffraction (XRD) and Mn K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy were combined to elaborate a structural model for phyllomanganates (layer-type Mn oxides) lacking 3D ordering (turbostratic stacking). These techniques were applied to a sample produced by a common soil and freshwater bacterium (Pseudomonas putida), and to two synthetic analogs, [delta]-Mn[O.sub.2] and acid birnessite, obtained by the reduction of potassium permanganate with Mn[Cl.sub.2] and HCl, respectively. To interpret the diffraction and spectroscopic data, we applied an XRD simulation technique utilized previously for well-crystallized birnessite varieties, complementing this approach with single-scattering-path simulations of the Mn K-edge EXAFS spectra. Our structural analyses revealed that all three Mn oxides have an hexagonal layer symmetry with layers comprising edge-sharing [Mn.sup.4+][O.sub.6] octahedra and cation vacancies, but no layer [Mn.sup.3+][O.sub.6] octahedra. The proportion of cation vacancies in the layers ranged from 6 to 17%, these vacancies being charge-compensated in the interlayer by protons, alkali metals, and Mn atoms, in amounts that vary with the phyllomanganate species and synthesis medium. Both vacancies and interlayer Mn were most abundant in the biogenic oxide. The diffracting crystallites contained three to six randomly stacked layers and have coherent scattering domains of 19-42 [Angstrom] in the [c.sup.*] direction, and of 60-85 [Angstrom] in the a-b plane. Thus, the Mn oxides investigated here are nanoparticles that bear significant permanent structural charge resulting from cation layer vacancies and variable surface charge from unsaturated O atoms at layer edges. Keywords: Geomicrobiology, Pseudomonas putida, Mn oxide, XAS, biogenic Mn oxide, XRD data, crystal structure, new minerals