TY  - JOUR
AU  - Alain Manceau, Romain Brossier
PY  - 2021//
TI  - Mercury Isotope Fractionation by Internal Demethylation and Biomineralization Reactions in Seabirds: Implications for Environmental Mercury Science
N2  - 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 → 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 → 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.
SN  - 0013-936X
UR  - http://dx.doi.org/10.1021/acs.est.1c04388
N1  - exported from refbase (http://publi.ipev.fr/polar_references/show.php?record=8427), last updated on Sat, 18 May 2024 23:58:02 +0200
ID  - AlainManceau2021
ER  -