RESUMEN
A prerequisite for environmental and toxicological applications of mercury (Hg) stable isotopes in wildlife and humans is quantifying the isotopic fractionation of biological reactions. Here, we measured stable Hg isotope values of relevant tissues of giant petrels (Macronectes spp.). Isotopic data were interpreted with published HR-XANES spectroscopic data that document a stepwise transformation of methylmercury (MeHg) to Hg-tetraselenolate (Hg(Sec)4) and mercury selenide (HgSe) (Sec = selenocysteine). By mathematical inversion of isotopic and spectroscopic data, identical δ202Hg values for MeHg (2.69 ± 0.04), Hg(Sec)4 (-1.37 ± 0.06), and HgSe (0.18 ± 0.02) were determined in 23 tissues of eight birds from the Kerguelen Islands and Adélie Land (Antarctica). Isotopic differences in δ202Hg between MeHg and Hg(Sec)4 (-4.1 ± 0.1) reflect mass-dependent fractionation from a kinetic isotope effect due to the MeHg â Hg(Sec)4 demethylation reaction. Surprisingly, Hg(Sec)4 and HgSe differed isotopically in δ202Hg (+1.6 ± 0.1) and mass-independent anomalies (i.e., changes in Δ199Hg of ≤0.3), consistent with equilibrium isotope effects of mass-dependent and nuclear volume fractionation from Hg(Sec)4 â HgSe biomineralization. The invariance of species-specific δ202Hg values across tissues and individual birds reflects the kinetic lability of Hg-ligand bonds and tissue-specific redistribution of MeHg and inorganic Hg, likely as Hg(Sec)4. These observations provide fundamental information necessary to improve the interpretation of stable Hg isotope data and provoke a revisitation of processes governing isotopic fractionation in biota and toxicological risk assessment in wildlife.
Asunto(s)
Mercurio , Compuestos de Metilmercurio , Contaminantes Químicos del Agua , Animales , Biomineralización , Aves , Fraccionamiento Químico , Desmetilación , Monitoreo del Ambiente , Humanos , Mercurio/análisis , Isótopos de Mercurio/análisis , Contaminantes Químicos del Agua/análisisAsunto(s)
Mercurio , Animales , Biomineralización , Aves , Fraccionamiento Químico , Desmetilación , Isótopos , Isótopos de MercurioRESUMEN
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.
RESUMEN
For shallow-water waveguides and mid-frequency broadband acoustic signals, ocean acoustic tomography (OAT) is based on the multi-path aspect of wave propagation. Using arrays in emission and reception and advanced array processing, every acoustic arrival can be isolated and matched to an eigenray that is defined not only by its travel time but also by its launch and reception angles. Classically, OAT uses travel-time variations to retrieve sound-speed perturbations; this assumes very accurate source-to-receiver clock synchronization. This letter uses numerical simulations to demonstrate that launch-and-reception-angle tomography gives similar results to travel-time tomography without the same requirement for high-precision synchronization.