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1.
Considerable fractions of the Hg content of lake and river systems in Scandinavia are discharged from the soil of the catchments. An important soil type in Scandinavia is the iron–humus podzol. The sorption characteristics of this soil type for inorganic Hg(II) and monomethyl mercury were investigated by batch experiments. The solubility of Hg2+ and CH3Hg+ in the soil horizons containing organic matter increases with increasing pH of the soil solution by favoring the formation of solute organic matter–mercury complexes. While the solubility of Hg2+ is strongly dependent on complexation to dissolved organic matter, the solubility of CH3Hg+ is more dependent on ion exchange. The concentration of solute inorganic Hg(II) increased with increasing temperature probably because of an increase in the concentration of dissolved organic carbon. There was no effect of temperature on the concentration of solute CH3Hg+. At pH values where inorganic mercury–hydroxo complexes are formed, inorganic Hg(II) is efficiently sorbed to the metal oxides of the mineral soil. The soil–water distributions of inorganic Hg(II) in the different soil horizons were described by Freundlich isotherms or linear isotherms for common and contaminated mercury contents in the soils.  相似文献   

2.
In 2002, metallic Hg was found buried in a rural area of Descoberto city, Brazil. The origin of the Hg was a gold mining explotation plant established nearly one century ago. Although a number of studies have been conducted in order to assess the contamination of the area, none of them investigated the presence of methylated Hg in the hydric system. In this work methylmercury (CH3Hg+) was determined using gas chromatography-pyrolysis-atomic fluorescence detection (CG-pyro-AFS) in material from rain sedimentation boxes and stream sediments near the contaminated area. Total Hg concentration (HgT) along with the chemical speciation by thermo-desorption were performed. HgT in material from the sedimentation boxes was found to be very high, up to 41,580 μg kg−1, even in the rainy season, when in general HgT were much lower than in dry season. The samples from the Grama and Rico streams show a range of HgT from 5.8 to 266 μg kg−1. The thermo-desorption analysis showed predominance of Hg2+, possibly linked to organic sulfur, suggested by a good positive correlation between Hg2+, HgT, organic mater (OM) and total S. The CH3Hg+ concentration in stream sediment samples ranged from <0.07 to 1.87 μg kg−1 and in the samples of sedimentation boxes the concentrations were 1.33 and 8.0 μg kg−1 during dry season. The sample with the highest percentage of HgT as Hg2+ (98%) presented also the highest percentage of CH3Hg+ (0.7%). These are high values, showing that care should be taken to avoid the transport of this material to the hydrological system. Further studies on the transfer through the food chain would be very important.  相似文献   

3.
Methylmercury cation (CH3Hg+) is known to have a strong affinity for organic matter in soil, sedimentary, and aquatic environments. The objective of this study is to determine the dominant ligands binding CH3Hg+ in humic acids by evaluating several CH3Hg+-ligand complexation models, using mercury LIII-edge extended X-ray absorption fine structure (EXAFS). The model CH3Hg+ binding ligands examined in this study include thiol (-SH), hydrogen polysulfide (-SSH or -SSSH), sulfide (-S-), disulfide (-SS-), carboxyl (-COOH), and amine (-NH2). Based on the atomic geometry around mercury in each model structure, we distinguished CH3Hg+-binding ligands in two different humic acids (soil and aquatic). We observed CH3Hg+ preferentially binds to thiol ligands. After saturating reactive thiol ligands, the majority of CH3Hg+ binds to carboxyl ligands rather than to amine or other reduced sulfur ligands than thiol. We found no evidence of significant CH3Hg+-sulfide/disulfide or CH3Hg+-hydrogen polysulfide complexes in any samples. When CH3Hg+ binds to a humic ligand, the C-Hg bond in CH3Hg+ remains intact. Some heavy atoms are proximately coordinated around the mercury atom in the sample containing the highest CH3Hg+ levels used in this study.  相似文献   

4.
Mercury vapor (Hg0) emission from plants contributes to the atmospheric Hg cycle. Young barley (Hordeum vulgare L.) plants grown on a hydroponic cultivation medium containing Hg(II) have previously been shown to increase their Hg0 emission significantly by reduction of Hg(II) with endogenous ascorbic acid. Regarding the potential contribution to the Hg cycle from the vast forest-covered areas, it was important to investigate this mechanism in trees. The increase in Hg0 emission from young European beech plants cultivated on a HgCl2 medium exceeded that from controls by ca. tenfold and was proportional to the Hg(II) concentration. From these experiments, a flux of 12.8 μg Hg0/h/m2 was estimated at an exposure of the roots to 20 μM Hg(II). Mercury vapor release from homogenates of Norway spruce needles exceeded that from European beech leaves by a factor of 2.3–4, i.e. in proportion to the reported AA concentrations; the reduction was maximal at alkaline pH which is typical for AA. The 8.4-fold difference in Hg0 release between homogenates from wild-type Arabidopsis thaliana and from its AA-deficient mutant vtc 1-1 also paralleled the reported difference in AA levels of both species. It is concluded that the phytoreduction and vaporization of Hg by AA is an important mechanism as much for Hg detoxification in trees as for Hg emission to the atmosphere. The efficiency of this process seems to result from the optimal coordination of transfer and biochemical transformation of mercuric ions and Hg vapor. There is no evidence for a relevant difference in the mechanisms of biogenic Hg(II) reduction between grass plants and trees.  相似文献   

5.
Aqueous production and water-air exchange of elemental mercury (Hg0) are important features of the environmental cycling of Hg. We investigated Hg0 cycling in ten Arctic Alaskan lakes that spanned a wide range in physicochemical characteristics. Dissolved gaseous Hg (DGM, dominated by Hg0) varied from 40 to 430 fM and averaged 200 fM. All surface waters were supersaturated relative to the atmosphere. DGM averaged 3 ± 2% of dissolved (i.e., filter passing) dissolved total mercury (DTM) and 15 ± 6% of dissolved labile Hg (DLM). In-lake DGM profiles generally followed the vertical distribution of light, indicating photoreduction of Hg(II) complexes as a source of Hg0. Additionally, DGM correlated linearly with DLM (r2 = 0.82, p < 0.0001) in the lake surface, signifying that Hg complexes (mostly organic Hg associations) in dissolved phase are photoreducible and contribute to production of DGM. Further, a positive relation between DGM/DTM and both Ka (light attenuation coefficient; r2 = 0.73, p < 0.02) and DOC (r2 = 0.60, p = 0.02) suggests that solar radiation and dissolved organic matter control DGM production and its cycling. An average rate of DGM formation (0.6 ± 0.2% of DTM d−1; range, 0.20.8) was estimated by assuming steady state with the evasional rate. In-lake DGM formation occurs at lower rates in waters with greater suspended particulate matter and dissolved organic carbon (DOC), pointing to the significant role of organic matter plays in controlling DGM formation in these aquatic systems. Estimated evasional fluxes of Hg0 (average, 140 ± 50 pmol m−2 d−1; range, 60-200) were comparable to those of temperate lakes (e.g., Wisconsin, Michigan). In arctic lakes, the rate of evasion during ice-free periods (7 ± 3 nmol m−2 yr−1) is similar to the atmospheric input of Hg (wet + dry) to the lakes based on levels in summertime precipitation but not including additional sources, e.g., springtime depletion.  相似文献   

6.
Age-dated sediment cores from 4 remote lakes across California were analyzed for total Hg (HgT) concentration as a function of pre- and post-industrialization. Particle size, magnetic susceptibility and organic C and N, were measured to determine if the Hg concentration in sediment cores could be related to atmospheric deposition and/or watershed processes. Results indicate that (a) for each lake modern (1970–2004) HgT lake sediment concentrations have increased by an average factor of 5 times more than historic (pre-1850) HgT concentrations; (b) the ratio of modern to pre-industrial lake sediment HgT for these lakes are higher than estimated for other locations where atmospheric deposition is presumed to be the main source of Hg; (c) 2 of the 4 studied lakes demonstrated significant relationships between HgT concentrations and percentage organic material (r2 = 0.68 and p < 0.01; r2 = 0.67 and p < 0.01) whereas the other two indicated no significant relationship (r2 = 0.05 and p = 0.51; r2 = 0.12 and p = 0.36).  相似文献   

7.
Cadmium (Cd) is a toxic trace element and due to human activities soils and waters are contaminated by Cd both on a local and global scale. It is widely accepted that chemical interactions with functional groups of natural organic matter (NOM) is vital for the bioavailability and mobility of trace elements. In this study the binding strength of cadmium (Cd) to soil organic matter (SOM) was determined in an organic (49% organic C) soil as a function of reaction time, pH and Cd concentration. In experiments conducted at native Cd concentrations in soil (0.23 μg g−1 dry soil), halides (Cl, Br) were used as competing ligands to functional groups in SOM. The concentration of Cd in the aqueous phase was determined by isotope-dilution (ID) inductively-coupled-plasma-mass-spectrometry (ICP-MS), and the activity of Cd2+ was calculated from the well-established Cd-halide constants. At higher Cd loading (500-54,000 μg g−1), the Cd2+ activity was directly determined by an ion-selective electrode (ISE). On the basis of results from extended X-ray absorption fine structure (EXAFS) spectroscopy, a model with one thiolate group (RS−) was used to describe the complexation (Cd2+ + RS− ? CdSR+; log KCdSR) at native Cd concentrations. The concentration of thiols (RSH; 0.047 mol kg−1 C) was independently determined by X-ray absorption near-edge structure (XANES) spectroscopy. Log KCdSR values of 11.2-11.6 (pKa for RSH = 9.96), determined in the pH range 3.1-4.6, compare favorably with stability constants for the association between Cd and well-defined thiolates like glutathione. In the concentration range 500-54,000 μg Cd g−1, a model consisting of one thiolate and one carboxylate (RCOO−) gave the best fit to data, indicating an increasing role for RCOOH groups as RSH groups become saturated. The determined log KCdOOCR of 3.2 (Cd2+ +  RCOO− ? CdOOCR+; log KCdOOCR; pKa for RCOOH = 4.5) is in accordance with stability constants determined for the association between Cd and well-defined carboxylates. Given a concentration of reduced sulfur groups of 0.2% or higher in NOM, we conclude that the complexation to organic RSH groups may control the speciation of Cd in soils, and most likely also in surface waters, with a total concentration less than 5 mg Cd g−1 organic C.  相似文献   

8.
Carboxyl groups are abundant in natural organic molecules (NOM) and play a major role in their reactivity. The structural environments of carboxyl groups in IHSS soil and river humic samples were investigated using 2D NMR (heteronuclear and homonuclear correlation) spectroscopy. Based on the 1H-13C heteronuclear multiple-bond correlation (HMBC) spectroscopy results, the carboxyl environments in NOM were categorized as Type I (unsubstituted and alkyl-substituted aliphatic/alicyclic), Type II (functionalized carbon substituted), Type IIIa, b (heteroatom and olefin substituted), and Type IVa, b (5-membered heterocyclic aromatic and 6-membered aromatic). The most intense signal in the HMBC spectra comes from the Type I carboxyl groups, including the 2JCH and 3JCH couplings of unsubstituted aliphatic and alicyclic acids, though this spectral region also includes the 3JCH couplings of Type II and III structures. Type II and III carboxyls have small but detectable 2JCH correlations in all NOM samples except for the Suwannee River humic acid. Signals from carboxyls bonded to 5-membered aromatic heterocyclic fragments (Type IVa) are observed in the soil HA and Suwannee River FA, while correlations to 6-membered aromatics (Type IVb) are only observed in Suwannee River HA. In general, aromatic carboxylic acids may be present at concentrations lower than previously imagined in these samples. Vibrational spectroscopy results for these NOM samples, described in an accompanying paper [Hay M. B. and Myneni S. C. B. (2007) Structural environments of carboxyl groups in natural organic molecules from terrestrial systems. Part 1: Infrared spectroscopy. Geochim. Cosmochim. Acta (in press)], suggest that Type II and Type III carboxylic acids with α substituents (e.g., -OH, -OR, or -CO2H) constitute the majority of carboxyl structures in all humic substances examined. Furoic and salicylic acid structures (Type IV) are also feasible fragments, albeit as minor constituents. The vibrational spectroscopy results also suggest that much of the “Type I” signal observed in the HMBC spectrum is due to carboxylic acid esters and possibly α-substituted alicyclic acids.  相似文献   

9.
We present here the first mercury speciation study in the water column of the Southern Ocean, using a high-resolution south-to-north section (27 stations from 65.50°S to 44.00°S) with up to 15 depths (0-4440 m) between Antarctica and Tasmania (Australia) along the 140°E meridian. In addition, in order to explore the role of sea ice in Hg cycling, a study of mercury speciation in the “snow-sea ice-seawater” continuum was conducted at a coastal site, near the Australian Casey station (66.40°S; 101.14°E). In the open ocean waters, total Hg (HgT) concentrations varied from 0.63 to 2.76 pmol L−1 with “transient-type” vertical profiles and a latitudinal distribution suggesting an atmospheric mercury source south of the Southern Polar Front (SPF) and a surface removal north of the Subantartic Front (SAF). Slightly higher mean HgT concentrations (1.35 ± 0.39 pmol L−1) were measured in Antarctic Bottom Water (AABW) compared to Antarctic Intermediate water (AAIW) (1.15 ± 0.22 pmol L−1). Labile Hg (HgR) concentrations varied from 0.01 to 2.28 pmol L−1, with a distribution showing that the HgT enrichment south of the SPF consisted mainly of HgR (67 ± 23%), whereas, in contrast, the percentage was half that in surface waters north of PFZ (33 ± 23%). Methylated mercury species (MeHgT) concentrations ranged from 0.02 to 0.86 pmol L−1. All vertical MeHgT profiles exhibited roughly the same pattern, with low concentrations observed in the surface layer and increasing concentrations with depth up to an intermediate depth maximum. As for HgT, low mean MeHgT concentrations were associated with AAIW, and higher ones with AABW. The maximum of MeHgT concentration at each station was systematically observed within the oxygen minimum zone, with a statistically significant MeHgTvs Apparent Oxygen Utilization (AOU) relationship (p < 0.001). The proportion of HgT as methylated species was lower than 5% in the surface waters, around 50% in deep waters below 1000 m, reaching a maximum of 78% south of the SPF. At Casey coastal station HgT and HgR concentrations found in the “snow-sea ice-seawater” continuum were one order of magnitude higher than those measured in open ocean waters. The distribution of HgT there suggests an atmospheric Hg deposition with snow and a fractionation process during sea ice formation, which excludes Hg from the ice with a parallel Hg enrichment of brine, probably concurring with the Hg enrichment of AABW observed in the open ocean waters. Contrastingly, MeHgT concentrations in the sea ice environment were in the same range as in the open ocean waters, remaining below 0.45 pmol L−1. The MeHgT vertical profile through the continuum suggests different sources, including atmosphere, seawater and methylation in basal ice. Whereas HgT concentrations in the water samples collected between the Antarctic continent and Tasmania are comparable to recent measurements made in the other parts of the World Ocean (e.g., Soerensen et al., 2010), the Hg species distribution suggests distinct features in the Southern Ocean Hg cycle: (i) a net atmospheric Hg deposition on surface water near the ice edge, (ii) the Hg enrichment in brine during sea ice formation, and (iii) a net methylation of Hg south of the SPF.  相似文献   

10.
Concentrations of atmospheric Hg species, elemental Hg (Hg°), reactive gaseous Hg (RGM), and fine particulate Hg (Hg-PM2.5) were measured at a coastal site near Weeks Bay, Alabama from April to August, 2005 and January to May, 2006. Mean concentrations of the species were 1.6 ± 0.3 ng m−3, 4.0 ± 7.5 pg m−3 and 2.7 ± 3.4 pg m−3, respectively. A strong diel pattern was observed for RGM (midday maximum concentrations were up to 92.7 pg m−3), but not for Hg° or Hg-PM2.5. Elevated RGM concentrations (>25 pg m−3) in April and May of 2005 correlated with elevated average daytime O3 concentrations (>55 ppbv) and high light intensity (>500 W m−2). These conditions generally corresponded with mixed continental-Gulf and exclusively continental air mass trajectories. Generally lower, but still elevated, RGM peaks observed in August, 2005 and January–March, 2006 correlated significantly (p < 0.05) with peaks in SO2 concentration and corresponded to periods of high light intensity and lower average daytime O3 concentrations. During these times air masses were dominated by trajectories that originated over the continent. Elevated RGM concentrations likely resulted from photochemical oxidation of Hg° by atmospheric oxidants. This process may have been enhanced in and by the near-shore environment relative to inland sites. The marine boundary layer itself was not found to be a significant source of RGM.  相似文献   

11.
《Applied Geochemistry》1999,14(3):395-407
An ultrafiltration procedure has been developed to study the interaction between organic C and Hg species in natural waters, and a pilot study was conducted in the surface waters of the Florida Everglades. Compared to total Hg, CH3Hg shows different distribution patterns in the suspended particulate, colloidal, and truly dissolved phases. Colloidal forms (0.22 μm, 3 kDa) contain the majority of the total dissolved Hg, while the amount found in the truly dissolved fraction (<3 kDa) is small (about 10%). However, CH3Hg, which shows strong binding capability with low molecular-weight dissolved organic C, is present almost entirely in the lower molecular-weight fraction of the colloids and in the truly dissolved fraction. Quantitative CH3Hg data correlate well with those for dissolved organic C, an indication that the organic matter present in the system plays an important role in the fate and transport of organomercury. Distribution coefficients between water and the different-sized fractions of the dissolved organic C were determined for both total Hg and CH3Hg. Results for total Hg were in general agreement with other reports resulting from studies of molecular size distributions of total Hg in freshwater systems. This is, to the best of our knowledge, the first report of such distribution profiles for CH3Hg between different-sized fractions of dissolved organic C in natural waters.  相似文献   

12.
《Applied Geochemistry》1999,14(2):147-158
This study evaluates several southern Appalachian Piedmont mining districts for Hg contamination in surface waters and determines potential relationships between Hg discharged from historical mining operations and site-specific physical factors. Water samples were collected from 3 fluvial systems that drain areas where Hg was used to amalgamate Au from ore during the 19th century. Each of the fluvial systems exhibit similar physical characteristics such as climate, vegetation, and rock type. Total Hg (HgT) determinations were made using cold vapour atomic fluorescence spectroscopy techniques. Concentrations of HgT in the southern Appalachian Piedmont range from 1–3 ng l−1 in waters of the Arbacoochee, Alabama, and South Mountains, North Carolina, Mining Districts to 13 ng l−1 in waters of the Dahlonega Mining District in Georgia. The correlation between HgT and total suspended solids (TSS) at the southern Appalachian sites was good with a coefficient of determination (r2) of 0.82. A clear trend between environmentally-available Fe (FeE) and HgT (r2=0.86) was also evident. The correlation between HgT and FeE most likely reflects similarities in the mechanisms that control the aqueous concentrations of both metals (i.e., the particle-reactive nature of the two elements), allowing for the sorption of Hg onto Fe-oxyhydroxides. Hence, increased loads of TSS from erosional events are probably responsible for higher stream water HgT concentrations. Vegetation at these sites, which is heavy due to the warm, humid climate of the SE, may help reduce the total amount of Hg released from contaminated mining sites to the rivers by controlling erosion, hence, decreasing the input of contaminated particles into streams and rivers.These southern Appalachian mining sites used Hg amalgamation techniques similar to those used in other precious metals mining districts, such as the highly contaminated Comstock Au–Ag district in Nevada, yet HgT concentrations are orders of magnitude lower; This difference in concentration between the southern Appalachian districts and the Comstock district may correlate to the relative amounts of Hg that were used in each. However, other variables were evaluated to determine if physio-chemical differences such as climate could influence HgT concentrations in surface waters of the two areas.  相似文献   

13.
The objective of this work was to study sorption–desorption and/or precipitation–dissolution processes of Hg(II) compounds considering an eventual contact of soils with Hg-bearing wastes. In addition, this study contributes new data about Hg(II) chemistry in alkaline systems. Saline and alkaline soils with low organic matter (<1 %) and high clay content (60–70 %) were obtained near a chlor-alkali plant. Batch techniques were used to perform the experiments using 0.1 M NaNO3 solutions. Total Hg(II) concentrations ranged from 6.2 × 10?8 to 6.3 × 10?3 M. Sorption of Hg(II) was evaluated at two concentration ranges: (a) 6.2 × 10?8 to 1.1 × 10?4 M, and (b) 6.4 × 10?4 to 6.3 × 10?3 M. At low Hg(II) concentrations, adsorption occurred with a maximum sorption capacity ranging from 4 to 5 mmol/kg. At high Hg(II) concentrations, sorption–precipitation reactions occurred and maximum sorption capacity ranged from 17 to 31 mmol/kg. The distribution of Hg(II) hydrolysis products showed that Hg(OH)2 was the predominant species under soil conditions. According to sorption experiments, X-ray diffraction and chemical speciation modelling, the presence of Hg(OH)2 in the interlayer of the interstratified clay minerals can be proposed. Hg(OH)2 was partially desorbed by repeated equilibrations in 0.1 M NaNO3 solution. Desorption ranged from 0.1 to 0.9 mmol/kg for soils treated with 5.8 × 10?5 M Hg(II), whereas 2.1–3.8 mmol/kg was desorbed from soils treated with 6.3 × 10?3 M Hg(II). Formation of soluble Hg(II) complexes was limited by low organic matter content, whereas neutral Hg(OH)2 was retained by adsorption on clay mineral surfaces.  相似文献   

14.
Zusammenfassung Die röntgenographische Neubestimmung der Kristallstruktur des kubischen Quecksilberminerals Eglestonit [a o=16,036(3) Å, RaumgruppeIa3d-O h 10 ,R=0,039 für 185 beobachtete Reflexe] führte auf den Zellinhalt Hg96Cl48O32. Die Anordnung des Quecksilbers in Hg2-Gruppen weist auf eine reine Hg(I)-Verbindung hin, was mit dieser Formel in Widerspruch steht. Aufgrund der H2O-Bestimmung von synthetischem Eglestonit und in Übereinstimmung mit einem kurzen O–O-Abstand, welcher eine Wasserstoffbrücke anzeigt, muß man annehmen, daß die Elementarzelle zusätzlich 16 röntgenographisch nicht nachweisbare H-Atome enthält. Die chemische Formel lautet folglich [Hg2]3Cl3O2H. Eglestonit kann aus Kalomel durch Hydrothermalbehandlung in alkalischem Medium synthetisiert werden.
Reexamination of the mercury mineral eglestonite: Crystal structure, chemical composition, and synthesis
Summary The reexamination of the crystal structure of the cubic mercury mineral eglestonite [a o=16.036(3) Å, space groupIa3d-O h 10 ,R=0.039 for 185 observed X-ray reflections] has led to a cell content of Hg96Cl48O32. The arrangement of mercury in Hg2-groups indicates a pure Hg(I) compound in contradiction to this formula. Based on the H2O determination of synthetic eglestonite and in agreement with the observation of a short O–O distance as characteristic for a hydrogen bond, one must assume that the unit cell also contains 16 H-atoms which cannot be specifically located by X-ray methods. The chemical formula therefore reads [Hg2]3Cl3O2H. Eglestonite can be synthesized by hydrothermal treatment of calomel in alkaline media.

Mit 3 Abbildungen  相似文献   

15.
Wanshan mercury mine is the largest cinnabar deposit in Guizhou, China. Few effective methods had been achieved to remedy Hg heavily contaminated field soils. In this paper, a modified EK method with approaching cathodes (AC-EK) and an I−/I2 lixiviant was described to remedy mercury-contaminated field soils near Wanshan mercury mine. Paddy Soil I and Paddy Soil II were sampled and contained 576.73 ± 45.50 and 491.35 ± 4.73 mg/kg Hg, respectively. Although they contained 6.9 and 9.4% organic matter respectively, more than 92 and 89% Hg were removed by AC-EK within 5 days. Removal ratio increased by 0.21 and 0.68 times using EK process with ACs over that with one single cathode (SC-EK). AC-EK method saved nearly 26.4–28.1% electric power as compared to SC-EK method. As an I−/I2 lixiviant solution was used to solubilize HgS(HgO) during EK process, the bonding of Hg to organic functional S groups should be less important than the binding to inner sites of organic matter in soil. The relationship between EK remediation effect and soil organic matter content was fitted to a linear model. It turned out that when soil OM increased by 1.0%, EK removal ratio (%) of Hg would decrease by 2.63%.  相似文献   

16.
WHAM, incorporating Humic Ion Binding Model VI, was used to analyse published data describing the binding of Hg(II) and methylmercury (CH3Hg) by isolated humic substances. For Hg(II), the data covered wide ranges of pH and levels of metal binding, whereas for CH3Hg the range of metal binding was relatively narrow. Data were fitted by adjustment of a single model parameter, log KMA, the intrinsic equilibrium constant characterising, in the standard version of the model, the binding of metal ions and their first hydrolysis products to humic carboxylic acid groups. Other model parameters, including those characterising the tendency of metal ions to interact with “softer” ligand atoms (N and S), were held at their default values. The importance of the first hydrolysis products in binding was considered, and also the possible influence of competition by residual Fe(III), bound to the humic matter.  相似文献   

17.
Hg in hydrothermal systems is generally thought to be transported as Hg-S complexes. However, the abundance of Hg0vap, in geothermal emissions suggests that Hg0eq, is present in the liquid phase of geothermal systems. Calculations for reducing fluids (HS? dominant over SO=4) in equilibrium with cinnabar indicate that Hg0eq, can be quite abundant relative to other species at temperatures above 200°C. Increasing pH and temperature, and decreasing total S, ionic strength, and pO2 all promote the abundance of Hg0eq. When a vapor phase develops from a geothermal liquid, Hg partitions strongly into the vapor as Hg0vap. Vapor transport at shallow level then results in the formation of Hg halos around shallow aquifers as well as in a flux of Hg to the atmosphere. Hg deposition may occur in response to mixing with oxidizing or acidic water, turning Hg0eq, into Hg++, with subsequent cinnabar precipitation. When pyrite is the stable Fe-sulfide, cinnabar solubility is at its lowest, so cinnabar + pyrite assemblages are common. Cinnabar + hematite ± pyrite can precipitate from more oxidized or S-poor water. Hg0liq, can occur as a primary mineral, in coexistence with all common Fe-sulfides and oxides. Cinnabar ± Hg0liq cannot coexist with pyrrhotite or magnetite at temperatures between 100° and 250°C. Evidence from Hg deposits indicates that many formed from dilute hydrothermal fluids in which Hg probably occurred as Hg0eq. In S-rich systems, Hg may occur as Hg-S complexes, and in saline waters it can occur as Hg-Cl complexes.  相似文献   

18.
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 200 nm aggregates consisting of 1-2 nm HgS(s) subunits that are more structurally disordered than metacinnabar in the presence of 2 × 10−9 to 8 × 10−6 M 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.  相似文献   

19.
In order to examine the transportation and deposition mechanisms of Hg, we investigated the ore and hydrothermal alteration minerals and solid organic matters from Itomuka mercury mine located in the eastern part of central Hokkaido. In addition to the ore minerals, native mercury and cinnabar, quartz, marcasite, alunite, kaolinite, and minor amounts of pyrite and smectite were identified in the Hg ore by powder X‐ray diffraction (XRD) analysis. This mineral assemblage of acid sulfate alteration was likely developed under the conditions of low temperature (≤100°C) and low pH (≤2) in the steam‐heated environment. The H2SO4 was produced above the water table by the oxidation of H2S separated from deep, near‐neutral fluids by boiling. The dominance of native mercury over cinnabar in Hg ore indicates that the greater part of mineralized Hg was transported as Hg0 in aqueous solution and vapor with low sulfur fugacity. The solid organic matters found in the Hg ore were analyzed with SEM‐EDS, micro‐XRD, and micro‐Fourier transform infrared (FTIR) spectroscopy, and these results suggest that the organic matters contributed to keeping the low fO2 of the Hg‐bearing fluid and transportation of Hg as Hg0 in S‐poor condition. Because the solubility of Hg in acidic fluid is low, neutral to alkaline fluid seems to have leached Hg from the basement sedimentary rocks of Hidaka Group which also supplied the organic matters to the fluid. The oxidation and cooling of Hg‐bearing solution and vapor triggered the deposition of liquid Hg as a primary phase.  相似文献   

20.
Mass independent fractionation (MIF) of stable isotopes associated with terrestrial geochemical processes was first observed in the 1980s for oxygen and in the 1990s for sulfur isotopes. Recently mercury (Hg) was added to this shortlist when positive odd Hg isotope anomalies were observed in biological tissues. Experimental work identified photoreduction of aquatic inorganic divalent HgII and photodegradation of monomethylmercury species as plausible MIF inducing reactions. Observations of continental receptors of atmospheric Hg deposition such as peat, lichens, soils and, indirectly, coal have shown predominantly negative MIF. This has led to the suggestion that atmospheric Hg has negative MIF signatures and that these are the compliment of positive Hg MIF in the aquatic environment. Recent observations on atmospheric vapor phase Hg0 and HgII in wet precipitation reveal zero and positive Hg MIF respectively and are in contradiction with a simple aquatic HgII photoreduction scenario as the origin for global Hg MIF observations.This study presents a synthesis of all terrestrial Hg MIF observations, and these are integrated in a one-dimensional coupled continent-ocean-atmosphere model of the global Hg cycle. The model illustrates how Hg MIF signatures propagate through the various Earth surface reservoirs. The scenario in which marine photoreduction is the main MIF inducing process results in negative atmospheric Δ199Hg and positive ocean Δ199Hg of −0.5‰ and +0.25‰, yet does not explain atmospheric Hg0 and HgII wet precipitation observations. Alternative model scenarios that presume in-cloud aerosol HgII photoreduction and continental HgII photoreduction at soil, snow and vegetation surfaces to display MIF are necessary to explain the ensemble of natural observations. The model based approach is a first step in understanding Hg MIF at a global scale and the eventual incorporation of Hg stable isotope information in detailed global mercury chemistry and transport models.  相似文献   

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