Unusual Hg isotope compositions in aqueous environments

Preliminary studies have demonstrated both mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) of Hg isotopes in natural samples. Laboratory experiments showed that photochemical reduction of inorganic mercury (iHg) and methylmercury (MMHg) and liquid-vapour evaporation could produce mass-independent fractionation of odd Hg isotopes. This was thought to cause the MIF actually observed in aquatic organisms. Though isotopic measurements of Hg in aqueous environment would give direct evidence, little data was reported for surface water samples. Recent work reported, unexpectedly, positive MIF of odd Hg isotopes in both precipitation and ambient air, in contrast with the prediction of laboratory experiments and measurements of Hg accumulated in lichens. Intriguingly, MIF of even-mass Hg isotope (200Hg) was also recently determined in the atmosphere. In contrast with the now mainstream observation of odd Hg isotope anomaly that has several theoretical explanations, the hitherto mysterious even Hg isotope anomalies were neither reported in laboratory experiments, nor predicted by isotope fractionation mechanisms, highlighting the importance of further study on Hg isotopes in variable systems. Our measurements of lake water samples show for the first time significant ?200Hg in surface terrestrial reservoirs, realizing a direct connection of even Hg isotope anomaly in the terrestrial reservoirs to the atmospheric deposition, and fulfilling the gap of ?200Hg between the atmosphere and the terrestrial receptors. The specific odd Hg isotope compositions determined in lake waters also support the atmosphere contribution, and may be directly linked to the high ?199Hg values largely determined and manifested on the top of aqueous food web. Our data show that the watershed Hg input is another contributing source, rather than the in-lake processes, to explain the lacustrine Hg isotope anomalies. Interestingly, lake sediments are isotopically decoupled from the atmosphere and even the water column. This probably results from the direct solid input from the watershed.