Factors controlling the photochemical degradation of methylmercury in coastal and oceanic waters.

Many studies have recognized abiotic photochemical degradation as an important sink of methylmercury (CH3 Hg) 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 CH3 Hg 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 CH3 Hg 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 CH3 Hg 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 CH3 Hg 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 CH3 Hg. Overall, this study provides additional insights and information to better constrain the importance of photochemical degradation in the cycling of CH3 Hg in marine surface waters and its transport from coastal waters to the open ocean.