Rate of formation and dissolution of mercury sulfide nanoparticles: The dual role of natural organic matter

Geochimica et Cosmochimica Acta
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Abstract

Mercury is a global contaminant of concern due to its transformation by microorganisms to form methylmercury, a toxic species that accumulates in biological tissues. The effect of dissolved organic matter (DOM) isolated from natural waters on reactions between mercury(II) (Hg) and sulfide (S(-II)) to form HgS(s) nanoparticles across a range of Hg and S(-II) concentrations was investigated. Hg was equilibrated with DOM, after which S(-II) was added. Dissolved Hg (Hgaq) was periodically quantified using ultracentrifugation and chemical analysis following the addition of S(-II). Particle size and identity were determined using dynamic light scattering and X-ray absorption spectroscopy. S(-II) reacts with Hg to form 20 to 200nm aggregates consisting of 1-2 nm HgS(s) subunits that are more structurally disordered than metacinnabar in the presence of 2 x 10-9 to 8 x 10-6M Hg and 10 (mg C)L-1 DOM. Some of the HgS(s) nanoparticle aggregates are subsequently dissolved by DOM and (re)precipitated by S(-II) over periods of hours to days. At least three fractions of Hg-DOM species were observed with respect to reactivity toward S(-II): 0.3 μmol reactive Hg per mmol C (60 percent), 0.1 μmol per mmol C (20 percent) that are kinetically hindered, and another 0.1 μmol Hg per mmol C (20 percent) that are inert to reaction with S(-II). Following an initial S(-II)-driven precipitation of HgS(s), HgS(s) was dissolved by DOM or organic sulfur compounds. HgS(s) formation during this second phase was counterintuitively favored by lower S(-II) concentrations, suggesting surface association of DOM moieties that are less capable of dissolving HgS(s). DOM partially inhibits HgS(s) formation and mediates reactions between Hg and S(-II) such that HgS(s) is susceptible to dissolution. These findings indicate that Hg accessibility to microorganisms could be controlled by kinetic (intermediate) species in the presence of S(-II) and DOM, undermining the premise that equilibrium Hg species distributions should correlate to the extent or rate of Hg methylation in soils and sediments.

Additional publication details

Publication type Article
Publication Subtype Journal Article
Title Rate of formation and dissolution of mercury sulfide nanoparticles: The dual role of natural organic matter
Series title Geochimica et Cosmochimica Acta
DOI 10.1016/j.gca.2010.05.012
Volume 74
Issue 16
Year Published 2010
Language English
Publisher Elsevier
Publisher location Amsterdam, Netherlands
Contributing office(s) Branch of Regional Research-Western Region
Larger Work Type Article
Larger Work Subtype Journal Article
Larger Work Title Geochimica et Cosmochimica Acta
First page 4693
Last page 4708
Additional Online Files (Y/N) N