Photoreactions of mercury in surface ocean water: gross reaction kinetics and possible pathways

We present pseudofirst order rate constants for gross photoreduction and gross photooxidation of mercury in surface water from the open Atlantic Ocean, determined under controlled laboratory conditions. Experiments using both unfiltered and filtered ocean water were carried out to characterize the importance of microbes and colloids on reaction kinetics. Results indicate that reduction and oxidation of mercury in ocean water does not follow a simple two-species reversible reaction pathway. We suggest two possible redox pathways that reproduce the pattern of dissolved gaseous mercury (DGM) concentrations observed in our laboratory experiments, and evaluate them using a controlled outdoor experiment. In both proposed pathways Hg(0), the major constituent of DGM, is converted to an unidentified oxidized species that is different from the reducible form present initially. This reaction step plays a major role in the net formation of DGM in our experiments. Our results represent new quantitative information about the gross reaction kinetics for both reduction and oxidation of mercury in open ocean surface water. Pseudofirst order rate constants for reduction reactions that form DGM were determined to be in the range of 0.15-0.93 h(-1) and pseudofirst order rate constants for oxidation of Hg(0) to be in the range of 0.4-1.9 h(-1). Microbes and colloids did not appreciably influence the reduction and oxidation kinetics.