Mercury isotopic evidence for the importance of particles as a source of mercury to marine organisms

The origin of methylmercury in pelagic fish remains unclear, with many unanswered questions regarding the production and degradation of this neurotoxin in the water column. We used mercury (Hg) stable isotope ratios of marine particles and biota to elucidate the cycling of methylmercury prior to incorporation into the marine food web. The Hg isotopic composition of particles, zooplankton, and fish reveals preferential methylation of Hg within small (< 53 mu m) marine particles in the upper 400 m of the North Pacific Ocean. Mass-dependent Hg isotope ratios (delta Hg-202) recorded in small particles overlap with previously estimated delta Hg-202 values for methylmercury sources to Pacific and Atlantic Ocean food webs. Particulate compound specific isotope analysis of amino acids (CSIA-AA) yield delta N-15 values that indicate more-significant microbial decomposition in small particles compared to larger particles. CSIA-AA and Hg isotope data also suggest that large particles (> 53 mu m) collected in the equatorial ocean are distinct from small particles and resemble fecal pellets. Additional evidence for Hg methylation within small particles is provided by a statistical mixing model of even mass-independent (Delta Hg-200 and Delta Hg-204) isotope values, which demonstrates that Hg within near-surface marine organisms (0-150 m) originates from a combination of rainfall and marine particles. In contrast, in meso- and upper bathypelagic organisms (200-1,400 m), the majority of Hg originates from marine particles with little input from wet deposition. The occurrence of methylation within marine particles is supported further by a correlation between Delta Hg-200 and Delta Hg-204 values, demonstrating greater overlap in the Hg isotopic composition of marine organisms with marine particles than with total gaseous Hg or wet deposition.