Particles-involved photochemical processes: A review for the case of mercury reduction in relation to aquatic mercury cycling.

Mercury (Hg) is one of the toxic metals of global and environmental concern, with aquatic Hg cycling being central in determining the production of highly toxic methylmercury and the air-water Hg exchange influencing the long-range intercontinental atmospheric Hg transport. Both inorganic and organic forms of Hg can be bound by suspended particles, including inorganic minerals (in particular metal oxides/sulfides) and particulate organic matter. Photochemical transformation is a critical process in surface water, and the role of suspended particles in Hg redox photoreactions has increasingly emerged, albeit in limited studies in comparison to extensive studies on aqueous (homogeneous) photoreactions of Hg. The lack of understanding of what roles suspended particles play might result in inaccurate estimation of how Hg species transform and/or cycle in the environment. In view of this gap, this paper critically reviews and synthesizes information on the studies conducted on different natural surface waters with respect to the potential roles of suspended particles on Hg photo-redox reactions. It robustly discusses the various possible pathways and/or mechanisms of particle-mediated Hg (II) reduction, in enhancing or lowering the production of dissolved gaseous mercury. These processes include photo hole-electron pair formation and reactive oxygen species generation from particle excitation and their involvement in Hg photoreduction, in addition to the light attenuation effect of particles. This paper highlights the necessity of future studies exploiting these particles-mediated Hg photoreactions pathways and the implications of including these heterogeneous photoreactions (together with particulate elemental Hg species) on the air-water Hg exchange estimation.
Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
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