Photochemical Reduction of Particle Bound Mercury in Atmospheric Aerosol Water

Particle bound mercury (PBM) deposition on the Earth's surface threatens biota and humans. The photoreduction of PBM competes with deposition and thereby modifies global mercury cycling; yet, its pathway and mechanism remain poorly understood. Herein, we reveal the photoreduction process of PBM by comprehensively using field observation, mercury stable isotope analysis, and controlled experiment. We found the Δ199Hg values in wet haze episodes (0.34‰ ± 0.30‰) were significantly higher than those in clean periods (0.14‰ ± 0.19‰), majorly attributed to the elevated aerosol water content (AWC), which shifts the aerosol phase from the solid state to the liquid state, promoting soluble HgCl2 and HgBr2 photoreduction reactions. The carboxyl functional groups of water-soluble organic carbon (WSOC) were further identified as the crucial compounds that induce PBM photoreduction, whose reaction rates were ∼2 times higher than those of phenol and ketone ligands and 3–6 times higher than those observed in other atmospheric aqueous phases. Considering the ubiquitously distributed carboxyl ligands and significant positive Δ199Hg signals in the atmospheric aqueous phases, the PBM photoreduction mediated by carboxyl ligands is highlighted to significantly influence global mercury transformations, regional depositions, and isotopic compositions of atmospheric mercury pools.