Chemistry and Isotope Fractionation of Divalent Mercury during Aqueous Reduction Mediated by Selected Oxygenated Organic Ligands

We have investigated the chemistry and Hg isotope fractionation during the aqueous reduction of Hg-II by oxalic acid, p-quinone, quinol, and anthraquinone-2,6-disulfonate (AQDS), a derivate of anthraquinone (AQ) that is found in secondary organic aerosols (SOA) and building blocks of natural organic matter (NOM). Each reaction was examined for the effects of light, pH, and dissolved O-2. Using an excess of ligand, UVB photolysis of Hg-II was seen to follow pseudo-first-order kinetics, with the highest rate of similar to 10(-3) s(-1) observed for AQDS and oxalic acid. Mass-dependent fractionation (MDF) occurs by the normal kinetic isotope effect (KIE). Only the oxalate ion, rather than oxalic acid, is photoreactive when present in HgC2O4, which decomposes via two separate pathways distinguishable by isotope anomalies. Upon UVB photolysis, only the reduction mediated by AQDS results in a large odd number mass-independent fractionation (odd-MIF) signified by enrichment of odd isotopes in the reactant. Consistent with the rate, MDF, and odd-MIF reported for fulvic acid, our AQDS result confirms previous assumptions that quinones control Hg-II reduction in NOM-rich waters. Given the magnitude of oddMIF triggered via a radical pair mechanism and the significant rate in the presence of air, reduction of Hg-II by photoproducts of AQDS may help explain the positive odd-MIF observed in ambient aerosols depleted of Hg-II.

Automated summary

The study investigated the reduction of Hg-II by oxalic acid, p-quinone, quinol, and anthraquinone-2,6-disulfonate (AQDS), with AQDS and oxalic acid showing the highest rate of reaction under UVB photolysis. Only the oxalate ion in oxalic acid was found to be photoactive, leading to distinguishable isotope anomalies. The reduction mediated by AQDS resulted in a large odd-MIF, indicating an enrichment of odd isotopes in the reactant.