Properties influencing flux and diatom uptake of mercury and methylmercury from estuarine sediments.

Mercury (Hg) is a conspicuous and persistent global pollutant. Ionic Hg can be methylated into noxious methylmercury (CH3Hg), which biomagnifies in marine tropic webs and poses a health risk to humans and organisms. Sediment Hg methylation rates are variable, and the output flux of created CH3Hg are dependent on sediment characteristics and environmental factors. Thus, uncertainties remain about the formation and flux of CH3Hg from sediment, and how this could contribute to the bioaccumulative burden for coastal organisms in shallow ecosystems. Cores were collected from 3 estuarine locations along the Eastern USA to examine how sediments characteristics influence the introduction of Hg and CH3Hg into the base of the food chain. Stable isotopes of inorganic 200Hg and CH3199Hg were injected into sediments of individual cores, with cultured diatoms constrained to overlying waters. Five different treatments were done on duplicate cores, spiked with: (1) no Hg isotopes (control); (2) inorganic 200Hg; (3) CH3199Hg; (4) both 200Hg and CH3199Hg isotopes, (5) both 200Hg and CH3199Hg into overlying waters (not sediment). Experimental cores were incubated for 3 days under temperature and light controlled conditions. These results demonstrate that upper sediments characteristics lead to high variability in Hg cycling. Notably, sediments which contained abundant and peaty organic material (∼28 %LOI), had the highest pore water DOC (3206 µM) and displayed bands of sulfur reducing bacteria yielded the greatest methylation rate (1.97 % day-1) and subsequent diatom uptake of CH3200Hg (cell quota 0.18 amol/cell) in the overlying water.

The interaction of mercury and methylmercury with chalcogenide nanoparticles.

Mercury (Hg) and methylmercury (CH3Hg) bind strongly to micro and nano (NP) particles and this partitioning impacts their fate and bioaccumulation into food webs, and, as a result, potential human exposure. This partitioning has been shown to influence the bioavailability of inorganic Hg to methylating bacteria, with NP-bound Hg being more bioavailable than particulate HgS, or organic particulate-bound Hg. In this study we set out to investigate whether the potential interactions between dissolved ionic Hg (HgII) and CH3Hg and NPs was due to incorporation of Hg into the core of the cadmium selenide and sulfide (CdSe; CdS) nanoparticles (metal exchange or surface precipitation), or due purely to surface interactions. The interaction was assessed based on the quenching of the fluorescence intensity and lifetime observed during HgII or CH3Hg titration experiments of these NP solutions. Additional analysis using inductively coupled plasma mass spectrometry of CdSe NPs and the separated solution, obtained after HgII additions, showed that there was no metal exchange, and X-ray photoelectron spectroscopy confirmed this and further indicated that the Hg was bound to cysteine, the NP capping agent. Our study suggests that Hg and CH3Hg adsorbed to the surfaces of NPs would have different bioavailability for release into water or to (de)methylating organisms or for bioaccumulation, and provides insights into the behavior of Hg in the environment in the presence of natural or manufactured NPs.

The precipitation, growth and stability of mercury sulfide nanoparticles formed in the presence of marine dissolved organic matter.

The methylation of mercury is known to depend on the chemical forms of mercury (Hg) present in the environment and the methylating bacterial activity. In sulfidic sediments, under conditions of supersaturation with respect to metacinnabar, recent research has shown that mercury precipitates as ß-HgS(s) nanoparticles (ß-HgS(s)nano). Few studies have examined the precipitation of ß-HgS(s)nano in the presence of marine dissolved organic matter (DOM). In this work, we used dynamic light scattering (DLS) coupled with UV-Vis spectroscopy and transmission electron microscopy (TEM) to investigate the formation and fate of ß-HgS(s)nano formed in association with marine DOM extracted from the east and west of Long Island Sound, and at the shelf break of the North Atlantic Ocean, as well as with low molecular weight thiols. We found that while the ß-HgS(s)nano formed in the presence of oceanic DOM doubled in size after 5 weeks, those forming in solutions with coastal DOM did not grow over time. In addition, when the HgII : DOM ratio was varied, ß-HgS(s)nano only rapidly aggregated at high ratios (>41 µmol HgII per mg C) where the concentration of thiol groups was determined to be substantially low relative to HgII. This suggests that functional groups other than thiols could be involved in the stabilization of ß-HgS(s)nano. Furthermore, we showed that ß-HgS(s)nano forming under anoxic conditions remained stable and could therefore persist in the environment sufficiently to impact the methylation potential. Exposure of ß-HgS(s)nano to sunlit and oxic environments, however, caused rapid aggregation and sedimentation of the nanoparticles, suggesting that photo-induced changes or oxidation of organic matter adsorbed on the surface of ß-HgS(s)nano affected their stability in surface waters.

Mercury flux from salt marsh sediments: Insights from a comparison between 224Ra/228Th disequilibrium and core incubation methods.

In aquatic environments, sediments are the main location of mercury methylation. Thus, accurate quantification of methylmercury (MeHg) fluxes at the sediment-water interface is vital to understanding the biogeochemical cycling of mercury, especially the toxic MeHg species, and their bioaccumulation. Traditional approaches, such as core incubations, are difficult to maintain at in-situ conditions during assays, leading to over/underestimation of benthic fluxes. Alternatively, the 224Ra/228Th disequilibrium method for tracing the transfer of dissolved substances across the sediment-water interface, has proven to be a reliable approach for quantifying benthic fluxes. In this study, the 224Ra/228Th disequilibrium and core incubation methods were compared to examine the benthic fluxes of both 224Ra and MeHg in salt marsh sediments of Barn Island, Connecticut, USA from May to August, 2016. The two methods were comparable for 224Ra but contradictory for MeHg. The radiotracer approach indicated that sediments were always the dominant source of both total mercury (THg) and MeHg. The core incubation method for MeHg produced similar results in May and August, but an opposite pattern in June and July, which suggested sediments were a sink of MeHg, contrary to the evidence of significant MeHg gradients between overlying water and porewater at the sediment-water interface. The potential reasons for such differences are discussed. Overall, we conclude that the 224Ra/228Th disequilibrium approach is preferred for estimating the benthic flux of MeHg and that sediment is indeed an important MeHg source in this marshland, and likely in other shallow coastal waters.

Dimethylmercury Formation Mediated by Inorganic and Organic Reduced Sulfur Surfaces.

Underlying formation pathways of dimethylmercury ((CH3)2Hg) in the ocean are unknown. Early work proposed reactions of inorganic Hg (Hg(II)) with methyl cobalamin or of dissolved monomethylmercury (CH3Hg) with hydrogen sulfide as possible bacterial mediated or abiotic pathways. A significant fraction (up to 90%) of CH3Hg in natural waters is however adsorbed to reduced sulfur groups on mineral or organic surfaces. We show that binding of CH3Hg to such reactive sites facilitates the formation of (CH3)2Hg by degradation of the adsorbed CH3Hg. We demonstrate that the reaction can be mediated by different sulfide minerals, as well as by dithiols suggesting that e.g. reduced sulfur groups on mineral particles or on protein surfaces could mediate the reaction. The observed fraction of CH3Hg methylated on sulfide mineral surfaces exceeded previously observed methylation rates of CH3Hg to (CH3)2Hg in seawaters and we suggest the pathway demonstrated here could account for much of the (CH3)2Hg found in the ocean.

Enhanced availability of mercury bound to dissolved organic matter for methylation in marine sediments.

The forms of inorganic mercury (HgII) taken up and methylated by bacteria in sediments still remain largely unknown. From pure cultures studies, it has been suggested that dissolved organic matter (DOM) may facilitate the uptake either by acting as a shuttle molecule, transporting the HgII atom to divalent metal transporters, or by binding HgII and then being transported into the cell as a carbon source. Enhanced availability of Hg complexed to DOM has however not yet been demonstrated in natural systems. Here, we show that HgII complexed with DOM of marine origin was up to 2.7 times more available for methylation in sediments than HgII added as a dissolved inorganic complex (HgII(aq)). We argue that the DOM used to complex HgII directly facilitated the bacterial uptake of HgII whereas the inorganic dissolved HgII-complex adsorbed to the sediment matrix before forming bioavailable dissolved HgII complexes. We further demonstrate that differences in net methylation in sediments with high and low organic carbon content may be explained by differences in the availability of carbon to stimulate the activity of Hg methylating bacteria rather than, as previously proposed, be due to differences in HgII binding capacities between sediments.