Dimethyl Hg Research Articles

Environmental inventory of mercury (Hg) for the marine shallow water hydrothermal system at Panarea, Italy

Hydrothermal fluids, hydrothermal gases, porewater and seawater were collected from the La Calcara (LC) hydrothermal area (n = 34). Additional samples were taken at Bottaro North (n = 2), Black Point (n = 3) and Panarea Harbor (n = 3). Total Hg (THg) porewater concentrations ranged from 300 to 6200 pM, while dissolved Hgdiss concentrations were generally lower by two to three orders of magnitude. Hydrothermal fluids had concentrations up to 26,000 pM. Mono- and dimethyl Hg (MeHg) were below detection. Total Hg in the gases (Hggas) ranged from 0.9 to 1899 nmol/m3.The THg concentration correlated positively with temperature (r = 0.86), while Hgdiss did not show any correlation (r = −0.02). The origin of Hg in the study area was interpreted to be hydrothermal. However, a clear trend was absent since ambient temperature porewaters had Hg concentrations as high as those porewaters with elevated temperatures. This was considered to be due to a combination of chemical reactions and complex flow patterns beneath the hydrothermal system. The concentration of Hg in the hydrothermal gases ranged from 0.9 to 1899 nmol/m3. This large range was ascribed to subsurface reactions with H2S and CH4 combined with the presence or absence of a sediment cover.Above the LC area, Hg concentrations were higher than those in Mediterranean seawater, indicating that the hydrothermal discharge adds Hg to the Panarea coastal ocean and its ecosystem. This effect is local regarding seawater chemistry and global Hg budgets since with distance Hg concentrations returned to values as expected for Mediterranean seawater. However, since most, if not all, marine food chains originate in coastal water, hydrothermal Hg may bioaccumulate in a given food chain. With >70 known marine shallow-water hydrothermal systems, this may be a worldwide phenomenon that warrants further study.

Aircraft Measurements of Total Mercury and Monomethyl Mercury in Summertime Marine Stratus Cloudwater from Coastal California, USA.

Water samples from marine stratus clouds were collected during 16 aircraft flights above the Pacific Ocean near the Central California coast during the summer of 2016. These samples were analyzed for total mercury (THg), monomethyl mercury (MMHg), and 32 other chemical species in addition to aerosol physical parameters. The mean concentrations of THg and MMHg in the cloudwater samples were 9.2 ± 6.0 ng L-1 (2.3-33.8 ng L-1) ( N = 97) and 0.87 ± 0.66 ng L-1 (0.17-2.9 ng L-1) ( N = 22), respectively. This corresponds to 9.5% (3-21%) MMHg as a fraction of THg. Low and high nonsea salt calcium ion (nss-Ca2+) concentrations in cloudwater were used to classify flights as "marine" and "continental", respectively. Mean [MMHg]marine was significantly higher ( p < 0.05) than [MMHg]continental consistent with an ocean source of dimethyl Hg (DMHg) to the atmosphere. Mean THg in cloudwater was not significantly different between the two categories, indicating multiple emissions sources. Mean [THg]continental was correlated with pH, CO, NO3-, NH4+, and other trace metals, whereas [THg]marine was correlated with MMHg and Na+. THg concentrations were negatively correlated with altitude, consistent with ocean and land emissions, coupled with removal at the cloud-top due to drizzle formation.

Distribution of mercury species across a zonal section of the eastern tropical South Pacific Ocean (U.S. GEOTRACES GP16)

Monomethylmercury is a neurotoxin formed in the ocean that accumulates in fish. To better understand the chemical cycling of mercury (Hg) in the ocean, multiple Hg species were measured during the 2013 U.S. GEOTRACES section in the eastern tropical South Pacific Ocean (GP16) from Peru to Tahiti. Total Hg (HgT), elemental Hg (Hg0), monomethyl-Hg (MMHg), and dimethyl-Hg (DMHg) were measured in high resolution across the section, which included productive surface waters in the Peru upwelling region, a suboxic oxygen minimum zone (OMZ), and an expansive hydrothermal vent plume from the East Pacific Rise (EPR). Filtered HgT accumulated in upwelled waters near the coast of Peru where oxygen concentrations were the lowest, and MMHg represented 10–20% of the total Hg upwelling flux. The buoyant hydrothermal plume was not enriched with Hg; however, water below 2500m had anomalously high concentrations of filtered HgT beneath the plume and in warmer bottom waters in the eastern part of the section. Elemental Hg averaged <10% of HgT in the water column and concentrations were greatest near the Peru margin. Concentrations of MMHg and DMHg were greatest in low-oxygen thermocline waters, and in the upwelling region, vertical maxima of MMHg were found at the top, core, and bottom of the suboxic OMZ. The MMHg:DMHg molar ratio was variable throughout the upper water column, however, DMHg was the dominant form of methylated Hg in deep water masses. This section is the first examination of Hg speciation and distributions near the Peru coast, a region that supports a highly productive fishery and a potential source of MMHg to consumers of seafood.

An experimental approach to investigate mercury species transformations under redox oscillations in coastal sediments

This work describes a laboratory experiment designed to unravel mercury species reactivity in superficial coastal sediments oscillating between oxic and anoxic conditions. The experimental set-up has been applied to a sediment slurry from the Arcachon Bay (France) to follow the evolution of both naturally occurring (i.e. endogenous) and isotopically enriched added mercury species (i.e. exogenous, 199IHg and 201MMHg) at environmental levels. The transformation and partition between the different phases (aqueous, solid and gaseous) of the endogenous and exogenous mercury species (inorganic Hg (IHg), monomethyl Hg (MMHg), elemental Hg (Hg°) and dimethyl Hg (DMHg)) have been investigated by isotopic speciation methods throughout the experiment. The results demonstrate that the experimental approach is able to promote sediment redox oscillations and to simultaneously follow the biogeochemical fate of naturally occurring or added mercury species. Experimentally driven redox transition events were found to significantly enhance the aqueous Hg species concentrations, while the MMHg burden is not greatly affected. Indeed, during the anoxic-oxic transition, while aqueous endogenous IHg and MMHg exhibited a two-fold increase, aqueous exogenous IHg and MMHg increased 7 and 4 times, respectively. Transient increases of the net IHg methylation were recorded during the redox transitions with the largest increase of the MMHg contents (factor 1.8) observed during the oxic-anoxic transition. High resolution in situ redox experiments have not been performed up to now, therefore the developed experimental set-up provides novel insights in both the influence of redox conditions on Hg methylation/demethylation and adsorption/desorption processes and kinetics in superficial sediments.

Methylated Mercury Species in Marine Waters of the Canadian High and Sub Arctic

Distribution of total mercury (THg), gaseous elemental Hg(0) (GEM), monomethyl Hg (MMHg), and dimethyl Hg (DMHg) was examined in marine waters of the Canadian Arctic Archipelago (CAA), Hudson Strait, and Hudson Bay. Concentrations of THg were low throughout the water column in all regions sampled (mean +/- standard deviation; 0.40 +/- 0.47 ng L(-1)). Concentrations of MMHg were also generally low atthe surface (23.8 +/- 9.9 pg L(-1)); however at mid- and bottom depths, MMHg was present at concentrations sufficient to initiate bioaccumulation of MMHg through Arctic marine foodwebs (maximum 178 pg L(-1); 70.3 +/- 37.3 pg L(-1)). In addition, at mid- and bottom depths, the % of THg that was MMHg was high (maximum 66%; 28 +/- 16%), suggesting that active methylation of inorganic Hg(II) occurs in deep Arctic marine waters. Interestingly, there was a constant, near 1:1, ratio between concentrations of MMHg and DMHg at all sites and depths, suggesting that methylated Hg species are in equilibrium with each other and/or are produced by similar processes throughout the water column. Our results also demonstrate that oceanographic processes, such as water regeneration and vertical mixing, affect Hg distribution in marine waters. Vertical mixing, for example, likely transported MMHg and DMHg upward from production zones at some sites, resulting in elevated concentrations of these species in surface waters (up to 68.0 pg L(-1)) where primary production and thus uptake of MMHg by biota is potentially highest. Finally, calculated instantaneous ocean-atmosphere fluxes of gaseous Hg species demonstrated that Arctic marine waters are a substantial source of DMHg and GEM to the atmosphere (27.3 +/- 47.8 and 130 +/- 138 ng m(-2) day(-1), respectively) during the ice-free season.

Methylated Mercury Species in Canadian High Arctic Marine Surface Waters and Snowpacks

We sampled seawater and snowpacks in the Canadian high Arctic for methylated species of mercury (Hg). We discovered that, although seawater sampled under the sea ice had very low concentrations of total Hg (THg, all forms of Hg in a sample; on average 0.14-0.24 ng L(-1)), 30-45% of the THg was in the monomethyl Hg (MMHg) form (on average 0.057-0.095 ng L(-1)), making seawater itself a direct source of MMHg for biomagnification through marine food webs. Seawater under the ice also contained high concentrations of gaseous elemental Hg (GEM; 129 +/- 36 pg L(-1)), suggesting that open water regions such as polynyas and ice leads were a net source of approximately 130 +/- 30 ng Hg m(-2) day(-1) to the atmosphere. We also found 11.1 +/- 4.1 pg L(-1) of dimethyl Hg (DMHg) in seawater and calculated that there could be a significant flux of DMHg to the atmosphere from open water regions. This flux could then resultin MMHg deposition into nearby snowpacks via oxidation of DMHg to MMHg in the atmosphere. In fact, we found high concentrations of MMHg in a few snowpacks near regions of open water. Interestingly, we discovered a significant log-log relationship between Cl- concentrations in snowpacks and concentrations of THg. We hypothesize that as Cl- concentrations in snowpacks increase, inorganic Hg(II) occurs principally as less reducible chloro complexes and, hence, remains in an oxidized state. As a result, snowpacks that receive both marine aerosol deposition of Cl- and deposition of Hg(II) via springtime atmospheric Hg depletion events, for example, may contain significant loads of Hg(II). Overall, though, the median wet/dry loads of Hg in the snowpacks we sampled in the high Arctic (5.2 mg THg ha(-1) and 0.03 mg MMHg ha(-1)) were far below wet-only annual THg loadings throughout southern Canada and most of the U.S. (22-200 mg ha(-1)). Therefore, most Arctic snowpacks contribute

Time Course Transformations and Fate of Mercury in Aquatic Model Ecosystems

Model aquatic ecosystems have been used to study the natural mechanisms involved in the distribution and transformation of inorganic mercury (IHg) in the different compartments and its interactions with the biota. Laboratory incubations in indoor freshwater microcosms, presenting a simple biological organization, were carried out at various spiked concentrations (3, 25 and 257 nmol l−1 of IHg, as mercuric chloride) and from a single initial contamination of the water column. The different compartments of the model ecosystems (water, sediment, macrophytes Elodea canadensis and snails Lymnaea stagnalis) were investigated for mercury distribution and speciation during a 2-month experimental period. The principal results obtained have evidenced different Hg biogeochemical pathways including biotic IHg methylation and reduction and transfer to the biota. A fast transfer of IHg from the water to the aquatic organisms and to the sediment was first observed with IHg half-lives of 24 h and 8 days, respectively. IHg methylation, clearly related to biogenic processes, was also demonstrated in all contaminated microcosms after 1 week of exposure. Finally, gaseous mercury species were determined in the different microcosms and significant biological induced production of elemental Hg (Hg°) and dimethyl Hg (DMHg) was observed. This overall investigation, based on the time courses evolution of IHg and in situ produced monomethylmercury (MMHg) concentrations allows to determine uptake and elimination rate constants for IHg as well as the bioaccumulation kinetics of MMHg in macrophytes and snails. The applicability of these aquatic model ecosystems to provide real insights for pollution impact and ecotoxicological risk assessments has been demonstrated.

Mercury speciation in surface and deep waters of the Mediterranean Sea

Mercury speciation and its distribution in surface and deep waters of the Mediterranean Sea were studied during two oceanographic cruises on board the Italian research vessel URANIA in summer 2003 and spring 2004 as part of the Med Oceaneor and MERCYMS projects. The study included deep water profiles of dissolved gaseous Hg (DGM), reactive Hg (RHg), total Hg (THg), monomethyl Hg (MeHg) and dimethyl Hg (DMeHg) in open ocean waters. Average concentrations of measured Hg species were characterized by seasonal and spatial variations. Overall average THg concentrations ranged between 0.41 and 2.65 pM (1.32 ± 0.48 pM) and were comparable to those obtained in previous studies of the Mediterranean Sea. A significant fraction of Hg was present as “reactive” Hg (average 0.33 ± 0.32 pM). Dissolved gaseous Hg (DGM), which consists mainly of Hg 0, represents a considerable proportion of THg (average 20%, 0.23 ± 0.11 pM). The portion of DGM typically increased towards the bottom, especially in areas with strong tectonic activity (Alboran Sea, Strait of Sicily, Tyrrhenian Sea), indicating its geotectonic origin. No dimethyl Hg was found in surface waters down to the depth of 40 m. Below this depth, its average concentration was 2.67 ± 2.9 fM. Dissolved fractions of total Hg and MeHg were measured in filtered water samples and were 0.68 ± 0.43 pM and 0.29 ± 0.17 pM for THg and MeHg respectively. The fraction of Hg as MeHg was in average 43%, which is relatively high compared to other ocean environments. The concentrations reported in this study are among the lowest found in marine environments and the quality of analytical methods are of key importance. Speciation of Hg in sea water is of crucial importance as THg concentrations alone do not give adequate data for understanding Hg sources and cycling in marine environments. For example, photoinduced transformations are important for the presence of reactive and elemental mercury in the surface layers, biologically mediated reactions are important for the production/degradation of MeHg and DGM in the photic zones of the water column, and the data for DGM in deep sea indicate the natural sources of Hg in geotectonicaly active areas of the Mediterranean Sea.

Some Sources and Sinks of Monomethyl and Inorganic Mercury on Ellesmere Island in the Canadian High Arctic

We identified some of the sources and sinks of monomethyl mercury (MMHg) and inorganic mercury (HgII) on Ellesmere Island in the Canadian High Arctic. Atmospheric Hg depletion events resulted in the deposition of Hg(II) into the upper layers of snowpacks, where concentrations of total Hg (all forms of Hg) reached over 20 ng/L. However, our data suggest that much of this deposited Hg(II) was rapidly photoreduced to Hg(0) which then evaded back to the atmosphere. As a result, we estimate that net wet and dry deposition of Hg(II) during winter was lower at our sites (0.4-5.9 mg/ha) than wet deposition in more southerly locations in Canada and the United States. We also found quite high concentrations of monomethyl Hg (MMHg) in snowpacks (up to 0.28 ng/L), and at times, most of the Hg in snowpacks was present as MMHg. On the Prince of Wales Icefield nearthe North Water Polynya, we observed a significant correlation between concentrations of Cl and MMHg in snow deposited in the spring, suggesting a marine source of MMHg. We hypothesize that dimethyl Hg fluxes from the ocean to the atmosphere through polynyas and open leads in ice, and is rapidly photolyzed to MMHgCl. We also found that concentrations of MMHg in initial snowmelt on John Evans Glacier (up to 0.24 ng/L) were higher than concentrations of MMHg in the snowpack (up to 0.11 ng/L), likely due to either sublimation of snow or preferential leaching of MMHg from snow during the initial melt phase. This springtime pulse of MMHg to the High Arctic, in conjunction with climate warming and the thinning and melting of sea ice, may be partially responsible for the increase in concentrations of Hg observed in certain Arctic marine mammals in recent decades. Concentrations of MMHg in warm and shallow freshwater ponds on Ellesmere Island were also quite high (up to 3.0 ng/L), leading us to conclude that there are very active regions of microbial Hg(II) methylation in freshwater systems during the short summer season in the High Arctic.

Determination of total urinary mercury by on-line sample microwave digestion followed by flow injection cold vapour inductively coupled plasma mass spectrometry or atomic absorption spectrometry.

The total mercury content in urine was determined by inductively coupled plasma mass spectrometry with the so-called cold vapour method after on-line oxidative treatment of the sample in a microwave oven (FI-MW-CV-ICPMS). Use of a KBr/KBrO(3) mixture, microwave digestion, and the final oxidation with KMnO(4), assure the complete recovery of the organic forms of Hg which would be difficult to determine otherwise if using only the CV-ICPMS apparatus. Quantitative recoveries were obtained for phenyl Hg chloride (PMC), dimethyl Hg (DMM), Hg acetate (MA) and methyl Hg chloride (MMC). Use of automatic flow injection microwave systems (FI-MW) for sample treatment reduces environmental contamination and allows detection limits suitable for the determination of reference values. Since no certified reference materials were commercially available in the concentration ranges of interest, the accuracy of the proposed procedure has been assessed by analysing a series of urine samples with two independent techniques, ICP-MS and AAS. When using the FI-MW-CV-ICP-MS technique, the detection limit was assessed at 0.03microg/L Hg, while with FI-MW-CV-AAS it was 0.2microg/L Hg. The precision of the method was less than 2-3% for FI-MW-CV-ICP-MS and about 3-5% for FI-MV-CV-AAS at concentrations below 1microg/L Hg. These results show that ICP-MS can be considered as a "reference technique" for the determination of total urinary Hg at very low concentrations, such as are present in non-exposed subjects.

Gaseous mercury profiles in the tropical Pacific Ocean

The distribution of dissolved gaseous mercury (DGM) was determined at four hydrographic stations in the tropical Pacific Ocean. These vertical profiles of DGM, to a depth of 400 meters, are the first obtained for the open ocean. Dissolved gaseous Hg concentrations generally increased with depth. The major portion of DGM in surface sea water was of an inorganic gaseous form, probably elemental Hg (Hgo). In two instances, organic gaseous Hg, presumably dimethyl Hg [(CH3)2Hg], was observed in the deeper waters. These results suggest that bacteria may be responsible for producing Hgo and (CH3)2Hg at depth in this ocean region.