Mercury Cycling in the North Pacific Subtropical Gyre as Revealed by Mercury Stable Isotope Ratios

The oceans are an important global reservoir for mercury (Hg), and marine fish consumption is the dominant human exposure pathway for its toxic methylated form. A more thorough understanding of the global biogeochemical cycle of Hg requires additional information on the mechanisms that control Hg cycling in pelagic marine waters. In this study, Hg isotope ratios and total Hg concentrations are used to explore Hg biogeochemistry in oligotrophic marine environments north of Hawaii. We present the first measurements of the vertical water column distribution of Hg concentrations and the Hg isotopic composition in precipitation, marine particles, and zooplankton near Station ALOHA (22 degrees 45N, 158 degrees W). Our results reveal production and demethylation of methylmercury in both the euphotic (0-175 m) and mesopelagic zones (200-1,000 m). We document a strong relationship between Hg isotopic composition and depth in particles, zooplankton, and fish in the water column and diurnal variations in Delta Hg-199 values in zooplankton sampled near the surface (25 m). Based on these observations and stable Hg isotope relationships in the marine food web, we suggest that the Hg found in large pelagic fish at Station ALOHA was originally deposited largely by precipitation, transformed into methyl-Hg, and bioaccumulated in situ in the water column. Our results highlight how Hg isotopic compositions reflect abiotic and biotic production and degradation of methyl-Hg throughout the water column and the importance of particles and zooplankton in the vertical transport of Hg.