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Many studies have recognized abiotic photochemical degradation as an important sink of methylmercury (CH3Hg) in sunlit surface waters, but the rate-controlling factors remain poorly understood. The overall objective of this study was to improve our understanding of the relative importance of photochemical reactions in the degradation of CH3Hg in surface waters across a variety of marine ecosystems by extending the range of water types studied. Experiments were conducted using surface water collected from coastal sites in Delaware, New Jersey, Connecticut, and Maine, as well as offshore sites on the New England continental shelf break, the equatorial Pacific, and the Arctic Ocean. Filtered water amended with additional CH3Hg at environmentally relevant concentrations was allowed to equilibrate with natural ligands before being exposed to natural sunlight. Water quality parameters – salinity, dissolved organic carbon, and nitrate – were measured, and specific UV absorbance was calculated as a proxy for dissolved aromatic carbon content. Degradation rate constants (0.87–1.67 day−1) varied by a factor of two across all water types tested despite varying characteristics, and did not correlate with initial CH3Hg concentrations or other environmental parameters. The rate constants in terms of cumulative photon flux values were comparable to, but at the high end of, the range of values reported in other studies. Further experiments investigating the controlling parameters of the reaction observed little effect of nitrate and chloride, and potential for bromide involvement. The HydroLight radiative transfer model was used to compute solar irradiance with depth in three representative water bodies – coastal wetland, estuary, and open ocean – allowing for the determination of water column integrated rates. Methylmercury loss per year due to photodegradation was also modeled across a range of latitudes from the Arctic to the Equator in the three model water types, resulting in an estimated global demethylation rate of 25.3 Mmol yr−1. The loss of CH3Hg was greatest in the open ocean due to increased penetration of all wavelengths, especially the UV portion of the spectrum which has a greater ability to degrade CH3Hg. Overall, this study provides additional insights and information to better constrain the importance of photochemical degradation in the cycling of CH3Hg in marine surface waters and its transport from coastal waters to the open ocean.

Anthropogenic activities have increased the selenium (Se) concentration in the biosphere, but the overall impact on the ocean has not been examined. While Se is an essential nutrient for microorganisms, there is little information on the impact of biological processes on the concentration and speciation of Se in the ocean. Additionally, other factors controlling the distribution and concentration of Se species are poorly understood. Here we present data gathered in the subtropical Pacific Ocean during a cruise in 2011, and we used these field data and the literature, as well as laboratory photochemical experiments examining the stability and degradation of inorganic Se (both Se (IV) and Se (VI)) and dimethyl selenide, to further constrain the cycling of Se in the upper ocean. We also developed a multibox model for the biosphere to examine the impact of anthropogenic emissions on the concentration and distribution of Se in the ocean. The model concurs with the field data indicating that the Se concentration has increased in the upper ocean waters over the past 30 years. Our observational studies and model results suggest that Se (VI) is taken up by phytoplankton in the surface ocean, in contrast to the results of laboratory culture experiments. In conclusion, while anthropogenic inputs have markedly increased Se in the atmosphere (42%) and net deposition to the ocean (38%) and terrestrial landscape (41%), the impact on Se in the ocean is small (3% increase in the upper ocean). This minimal response reflects its long marine residence time.