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Dimethyl mercury (DMHg) is commonly detected in the world's oceans, but little is known about the mechanisms responsible for DMHg degradation in natural waters or the products of this degradation. Similarly, the potential for the conversion of DMHg to monomethyl mercury (MMHg) under the acidic conditions commonly used to preserve samples for MMHg analysis has not been fully addressed. We provide evidence suggesting that DMHg in natural seawater is not readily photodegraded by sunlight as previously thought. Other experiments demonstrated that DMHg in seawater is, however, readily decomposed under acidic conditions, with MMHg as the predominant product. This facile conversion of DMHg to MMHg at low pH both necessitates an alternative preservation method to acidification for samples to be analyzed for MMHg when DMHg is present, and requires that data from previous studies of MMHg in seawater employing sample acidification be revisited in instances where appreciable DMHg concentrations were possible.

Fluxes of total mercury (Hg(T)) and monomethylmercury (MMHg) associated with submarine groundwater discharge (SGD) at two sites onthe central California coast were estimated by combining measurements of Hg(T) and MMHg in groundwater with the use of short-lived, naturally occurring radium isotopes as tracers of groundwater inputs. Concentrations of Hg(T) were relatively low, ranging from 1.2 to 28.3 pM in filtered groundwater, 0.8 to 11.6 pM in filtered surface waters, and 2.5 to 12.9 pM in unfiltered surface waters. Concentrations of MMHg ranged from < 0.04 to 3.1 pM in filtered groundwater, < 0.04 to 0.53 pM in filtered surface waters, and 0.07 to 1.2 pM in unfiltered surface waters. Multiple linear regression analysis identified significant (p < 0.05) positive correlations between dissolved groundwater concentrations of Hg(T) and those of NH4+ and SiO2, and between dissolved groundwater concentrations of MMHg and those of Hg(T) and NH4+. However, such relationships did not account for the majority of the variability in concentration data for either mercury species in groundwater. Fluxes of Hg(T) via SGD were estimated to be 250 +/- 160 nmol day m(-1) of shoreline at Stinson Beach and 3.0 +/- 2.0 nmol m(-2) day(-1) at Elkhorn Slough. These Hg(T) fluxes are substantially greater than net atmospheric inputs of Hg(T) reported for waters in nearby San Francisco Bay. Calculated fluxes of MMHg to coastal waters via SGD were 10 +/- 12 nmol day(-1) m(-1) of shoreline at Stinson Beach and 0.24 +/- 0.21 nmol m(-2) day at Elkhorn Slough. These MMHg fluxes are similar to benthic fluxes of MMHg out of surface sediments commonly reported for estuarine and coastal environments. Consequently, this work demonstrates that SGD is an important source of both Hg(T) and MMHg to coastal waters along the central California coast.

Depth profiles of dimethylmercury (DMHg) concentration were determined at nearshore to offshore sites in Monterey Bay, California. The onset of spring upwelling in the bay was accompanied by increases in DMHg concentrations. Profiles show DMHg increasing gradually with depth in fall and winter from <0.03 pM at the surface to 0.5 pM at 200 m. During the spring, DMHg concentrations increased between 30 and 100 m, first within Monterey Bay, then offshore. This change was accompanied by an increase in DMHg concentrations in the surface water DMHg between fall/winter (<0.03 pM) and spring (0.06-0.29 pM). Microbial activity associated with the remineralization of sinking organic matter produced by the high primary production in the bay may result in the relatively high DMHg in subsurface water in the bay, which when upwelled may facilitate the incorporation of organomercury into biota. As a result, productive coastal upwelling areas may represent an important source of methylated mercury to surface waters, and thus be an important source of mercury to marine ecosystems.

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