Precipitation of Mercuric Sulfide Nanoparticles in NOM-Containing Water: Implications for the Natural Environment

Speciation of mercury(II) in the aquatic environment and coordination to natural organic matter (NOM) and sulfides governs the bioavailability and mobility of mercury in water and sediment. While previous studies on aqueous Hg(II) speciation have focused on competitive binding of dissolved species, the purpose of this study was to explore the potential for HgS nanoparticles that coprecipitate with NOM in solution. Dynamic light scattering was used to monitor the size of HgS colloids growing over time. The results indicated that humic substances decreased observed growth rates of particles and stabilized aggregates smaller than 0.2 μm for at least 8 h. Thiol-containing organic acids such as cysteine and thioglycolate also decreased growth of HgS particles. Growth rates were also monitored as a function of monovalent electrolyte concentration, humic type, and humic concentration. HgS particles that formed in the presence of humics and thiolates were able to pass through conventional filters (<0.2 μm) and appeared to consist of aggregates of nanocrystals in TEM images. Furthermore, 96% of HgS aggregates were removed from aqueous suspension when exposed to octanol, indicating that the particles could be incorrectly identified as dissolved complexes (e.g., HgS0(aq)) in bioavailability models. Hg speciation calculations were conducted to consider lower Hg concentrations observed in sediment porewater. While the calculations depended on Hg binding constants that can vary by orders of magnitude, the results indicated that HgS(s) could be oversaturated in filtered porewater, particularly at low dissolved sulfide levels (micromolar or lower). These insights suggest that nanoparticulate HgS can exist in surface waters and porewater of contaminated sediments as a result of kinetically hindered aggregation/precipitation reactions. Further studies are needed to address the importance of nanoscale HgS particles for governing the reactivity and bioavailability of mercury in the environment.