Gretchen J. Swarr

Mercury species concentrations and fluxes in the Central Tropical Pacific Ocean

The formation of the toxic and bioaccumulating monomethylmercury (MMHg) in marine systems is poorly understood, due in part to sparse data from many ocean regions. We present dissolved mercury (Hg) speciation data from 10 stations in the North and South Equatorial Pacific spanning large water mass differences and gradients in oxygen utilization. We also compare the mercury content in suspended particles from six stations and sinking particles from three stations to constrain local Hg sources and sinks. Concentrations of total Hg (THg) and methylated Hg in the surface and intermediate waters of the Equatorial and South Pacific suggest Hg cycling distinct from that of the North Pacific gyre. Maximum concentrations of 180 fM for both MMHg and dimethylmercury (DMHg) are observed in the Equatorial Pacific. South of the equator, concentrations of MMHg and DMHg are less than 100 fM. Sinking fluxes of particulate THg can reasonably explain the shape of dissolved THg profiles, but those of MMHg are too low to account for dissolved MMHg profiles. However, methylated Hg species are lower than predicted from remineralization rates based on North Pacific data, consistent with limitation of methylation in Equatorial and South Pacific waters. Full water column depth profiles were also measured for the first time in these regions. Concentrations of THg are elevated in deep waters of the North Pacific, compared to those in the intermediate and surface waters, and taper off in the South Pacific. Comparisons with previous measurements from nearby regions suggest little enrichment of THg or MMHg over the past 20 years.

Mercury speciation and mobilization in a wastewater-contaminated groundwater plume.

We measured the concentration and speciation of mercury (Hg) in groundwater down-gradient from the site of wastewater infiltration beds operated by the Massachusetts Military Reservation, western Cape Cod, Massachusetts. Total mercury concentrations in oxic, mildly acidic, uncontaminated groundwater are 0.5-1 pM, and aquifer sediments have 0.5-1 ppb mercury. The plume of impacted groundwater created by the wastewater disposal is still evident, although inputs ceased in 1995, as indicated by anoxia extending at least 3 km down-gradient from the disposal site. Solutes indicative of a progression of anaerobic metabolisms are observed vertically and horizontally within the plume, with elevated nitrate concentrations and nitrate reduction surrounding a region with elevated iron concentrations indicating iron reduction. Mercury concentrations up to 800 pM were observed in shallow groundwater directly under the former infiltration beds, but concentrations decreased with depth and with distance down-gradient. Mercury speciation showed significant connections to the redox and metabolic state of the groundwater, with relatively little methylated Hg within the iron reducing sector of the plume, and dominance of this form within the higher nitrate/ammonium zone. Furthermore, substantial reduction of Hg(II) to Hg(0) within the core of the anoxic zone was observed when iron reduction was evident. These trends not only provide insight into the biogeochemical factors controlling the interplay of Hg species in natural waters, but also support hypotheses that anoxia and eutrophication in groundwater facilitate the mobilization of natural and anthropogenic Hg from watersheds/aquifers, which can be transported down-gradient to freshwaters and the coastal zone.

Continuous proxy measurements reveal large mercury fluxes from glacial and forested watersheds in Alaska

In this study, a stream from a glacially dominated watershed and one from a wetland, temperate forest dominated watershed in southeast Alaska were continuously monitored for turbidity and fluorescence from dissolved organic matter (FDOM) while grab samples for unfiltered (UTHg), particulate (PTHg), and filtered mercury (FTHg) where taken over three 4-day periods (May snowmelt, July glacial melt, and September rainy season) during 2010. Strong correlations were found between FDOM and UTHg concentrations in the wetland, temperate forest watershed (r2=0.81), while turbidity and UTHg were highly correlated in the glacially dominated watershed (r2=0.82). Both of these parameters (FDOM and turbidity) showed stronger correlations than concentration-discharge relationships for UTHg (r2=0.55 for glacial stream, r2=0.38 for wetland/forest stream), thus allowing for a more precise determination of temporal variability in UTHg concentrations and fluxes. The association of mercury with particles and dissolved organic matter (DOM) appears to depend on the watershed characteristics, such as physical weathering and biogeochemical processes regulating mercury transport. Thus employing watershed-specific proxies for UTHg (such as FDOM and turbidity) can be effective for quantifying mercury export from watersheds with variable landcover. The UTHg concentration in the forest/wetland stream was consistently higher than in the glacial stream, in which most of the mercury was associated with particles; however, due to the high specific discharge from the glacial stream during the melt season, the watershed area normalized flux of mercury from the glacial stream was 3-6 times greater than the wetland/forest stream for the three sampling campaigns. The annual specific flux for the glacial watershed was 19.9gUTHgkm-2y-1, which is higher than any non-mining impacted stream measured to date. This finding indicates that glacial watersheds of southeast Alaska may be important conduits of total mercury to the Gulf of Alaska.