Dissociation of Mercuric Oxides Drives Anomalous Isotope Fractionation during Net Photo-oxidation of Mercury Vapor in Air

The atmosphere is the primary medium for longdistance transport and transformation of elemental mercury (Hg), a potent neurotoxin. The recent discovery of mass-independent fractionation (MIF) of even-mass Hg isotopes (even-MIF, measured as delta Hg-200 and delta Hg-204) in the atmosphere is surprising and can potentially serve as a powerful tracer in understanding Hg biogeochemistry. Far-ultraviolet (UVC) light-induced gas-phase reactions have been suspected as a likely cause for even-MIF, yet the mechanism remains unknown. Here, we present the first experimental evidence of large-scale even-MIF caused by UVC-induced (wavelength: 254 nm) Hg oxidation in synthetic air at the pressure (46-88 kPa) and temperature (233-298 K) resembling those of the lower atmosphere. We observe negatively correlated delta Hg-200 and delta Hg-204 signatures with values as low as -50 parts per thousand and as high as 550 parts per thousand, respectively, in the remaining atomic Hg pool. The magnitude of even-MIF signatures decreases with decreasing pressure with the delta Hg-200/delta Hg-204 ratio being similar to that observed in global precipitation. This even-MIF can be explained by photodissociation of mercuric oxides that are photochemically formed in the UVC-irradiated Hg-O-2 system. We propose that similar processes occurring in the atmosphere, where mercuric oxide species serve as intermediates, are responsible for the observed even-MIF in the environment.

Automated summary

The recent discovery of mass-independent fractionation of even-mass mercury isotopes in the atmosphere suggests that UVC-induced photodissociation of mercuric oxides may be responsible for this phenomenon. This finding has significant implications for understanding mercury biogeochemistry.