Environmental geochemistry of an active Hg mine in Xunyang,Shaanxi Province,China

The Xunyang Hg mine (XMM) situated in Shaanxi Province is an active Hg mine in China. Gaseous elemental Hg (GEM) concentrations in ambient air were determined to evaluate its distribution pattern as a consequence of the active mining and retorting in the region. Total Hg (HgT) and methylmercury (MeHg) concentrations in riparian soil, sediment and rice grain samples (polished) as well as Hg speciation in surface water samples were measured to show local dispersion of Hg contamination. As expected, elevated concentrations of GEM were found, ranging from 7.4 to 410 ng m⁻³. High concentrations of HgT and MeHg were also obtained in riparian soils, ranged from 5.4 to 120 mg kg⁻¹ and 1.2 to 11 μg kg⁻¹, respectively. Concentrations of HgT and MeHg in sediment samples varied widely from 0.048 to 1600 mg kg⁻¹ and 1.0 to 39 μg kg⁻¹, respectively. Surface water samples showed elevated HgT concentrations, ranging from 6.2 to 23,500 ng L⁻¹, but low MeHg concentrations, ranging from 0.022 to 3.7 ng L⁻¹. Rice samples exhibited high concentrations of 50–200 μg kg⁻¹ in HgT and of 8.2–80 μg kg⁻¹ in MeHg. The spatial distribution patterns of Hg speciation in the local environmental compartments suggest that the XMM is the source of Hg contaminations in the study area.     

Soil mercury distribution in adjacent coniferous and deciduous stands highly impacted by acid rain in the Ore Mountains,Czech Republic

Forests play a primary role in the cycling and storage of mercury (Hg) in terrestrial ecosystems. This study aimed to assess differences in Hg cycling and storage resulting from different vegetation at two adjacent forest stands - beech and spruce. The study site Načetín in the Czech Republic's Black Triangle received high atmospheric loadings of Hg from coal combustion in the second half of the 20th century as documented by peat accumulation rates reaching 100 μg m⁻² y⁻¹. In 2004, the annual litterfall Hg flux was 22.5 μg m⁻² y⁻¹ in the beech stand and 14.5 μg m⁻² y⁻¹ in the spruce stand. Soil concentrations and pools of Hg had a strong positive relation to soil organic matter and concentrations of soil sulfur (S) and nitrogen (N). O-horizon Hg concentrations ranged from 245 to 495 μg kg⁻¹ and were greater in the spruce stand soil, probably as a result of greater dry Hg deposition. Mineral soil Hg concentrations ranged from 51 to 163 μg kg⁻¹ and were greater in the beech stand soil due to its greater capacity to store organic carbon (C). The Hg/C ratio increased with depth from 0.3 in the O-horizon to 3.8 μg g⁻¹ in the C horizon of spruce soil and from 0.7 to 2.7 μg g⁻¹ in beech soil. The Hg/C ratio was greater at all mineral soil depths in the spruce stand. The organic soil Hg pools in beech and spruce stands (6.4 and 5.7 mg m⁻², respectively) were considerably lower than corresponding mineral soil Hg pools (39.1 and 25.8 mg m⁻²). Despite the important role of S in Hg cycling, differences in soil Hg distribution at both stands could not be attributed to differences in soil sulfur speciation.     

Gold mining related mercury contamination in Tongguan,Shaanxi Province,PR China

Elemental Hg–Au amalgamation mining practices are used widely in many developing countries resulting in significant Hg contamination of surrounding ecosystems. The authors examined for the first time Hg contamination in air, water, sediment, soil and crops in the Tongguan Au mining area, China, where elemental Hg has been used to extract Au for many years. Total gaseous Hg (TGM) concentrations in ambient air in the Tongguan area were significantly elevated compared to regional background concentrations. The average TGM concentrations in ambient air in a Au mill reached 18,000 ng m⁻³, which exceeds the maximum allowable occupational standard for TGM of 10,000 ng m⁻³ in China. Both total and methyl-Hg concentrations in stream water, stream sediment, and soil samples collected in the Tongguan area were elevated compared to methyl-Hg reported in artisanal Au mining areas in Suriname and the Amazon River basin. Total Hg concentrations in vegetable and wheat samples ranged from 42 to 640 μg kg⁻¹, all of which significantly exceed the Chinese guidance limit for vegetables (10 μg kg⁻¹) and foodstuffs other than fish (20 μg kg⁻¹). Fortunately, methyl-Hg was not significantly accumulated in the crops sampled in this study, where concentrations varied from 0.2 to 7.7 μg kg⁻¹.     

Sorption of inorganic mercury and monomethyl mercury in an iron–humus podzol soil of southern Norway studied by batch experiments

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.     

Weathering versus atmospheric contributions to mercury concentrations in French Guiana soils

This work focuses on two possible sources of Hg in tropical soils, (i) lithogenic Hg from in situ weathering of soil parental material, and (ii) exogenic Hg from natural long-term atmospheric inputs and anthropogenic input from past and present industrial activities. The concentration of lithogenic Hg [Hg]_lithogenic was based on comparison of measured Hg concentration with those of elements resistant to weathering such as Nb, U, Zn, Fe. Exogenic Hg was quantified by subtracting [Hg]_lithogenic from total Hg concentrations. This calculation was applied to 4 French Guiana soil profiles, 3 profiles on the same toposequence (ferralsol, acrisol, hydromorphic soil) and one acrisol close to a Au mine, where elemental Hg is used. In all profiles, [Hg]_lithogenic varied slightly and was always below 40 μg kg⁻¹, whereas [Hg]_exogenic varied considerably and reached 500 μg kg⁻¹. The highest [Hg]_exogenic was calculated for the upper horizon of the acrisol close to Au mining activity, but also in the ferralsol. Concentrations of Hg were insignificant in the compact alterite in acrisols. It was concluded that pedogenesis processes that affect the natural Hg supply, combined with anthropogenic sources, explain the Hg concentrations in these tropical soils.     

X-ray absorption studies of CH3Hg-binding sites in humic substances

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 L_III-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.     

Bonding of methyl mercury to reduced sulfur groups in soil and stream organic matter as determined by x-ray absorption spectroscopy and binding affinity studies

We combined synchrotron-based X-ray absorption near edge structure (XANES) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy and binding affinity studies to determine the coordination, geometry, and strength of methyl mercury, CH₃Hg (II), bonding in soil and stream organic matter. Samples of organic soil (OS), potentially soluble organic substances (PSOS) from the soil, and organic substances from a stream (SOS) draining the soil were taken along a short “hydrological transect.” We determined the sum of concentrations of highly reduced organic S groups (designated Org-S_RED), such as thiol (RSH), disulfane (RSSH), sulfide (RSR), and disulfide (RSSR), using sulfur K-edge XANES. Org-S_RED varied between 27% and 64% of total S in our samples. Hg L_III-edge EXAFS analysis were determined on samples added CH₃Hg (II) to yield CH₃Hg (II)/Org-S_RED ratios in the range 0.01-1.62. At low ratios, Hg was associated to one C atom (the methyl group) at an average distance of 2.03 ± 0.02 Å and to one S atom at an average distance of 2.34 ± 0.03 Å, in the first coordination shell. At calculated CH₃Hg(II)/Org-S_RED ratios above 0.37 in OS, 0.32 in PSOS, and 0.24 in SOS, the organic S sites were saturated by CH₃Hg⁺, and O (and/or N) atoms were found in the first coordination shell of Hg at an average distance of 2.09 ± 0.01 Å. Based on the assumption that RSH (and possibly RSSH) groups take part in the complexation of CH₃Hg⁺, whereas RSSR and RSR groups do not, approximately 17% of total organic S consisted of RSH (+ RSSH) functionalities in the organic soil. Corresponding figures for samples PSOS and SOS were 14% and 9%, respectively. Competitive complexation of CH₃Hg⁺ by halide ions was used to determine the average binding strength of native concentrations of CH₃Hg (II) in the OS sample. Using data for Org-S_RED, calculated surface complexation constants were in the range from 10^16.3 to 10^16.7 for a model RSH site having an acidity constant of mercaptoacetic acid. These values compare favorably with identically defined stability constants (log K₁) for the binding of methyl mercury to thiol groups in well-defined organic compounds.     

Mercury and methylmercury in riparian soil,sediments, mine-waste calcines,and moss from abandoned Hg mines in east Guizhou province,southwestern China

Concentrations of total Hg and methylmercury (MMHg) in riparian soil, mine-waste calcine, sediment, and moss samples collected from abandoned Hg mines in Wanshan district, Guizhou province, China, were measured to show regional dispersion of Hg-contamination. High total Hg and MMHg concentrations obtained in riparian soils from mined areas, ranged from 5.1 to 790 mg kg⁻¹ and 0.13 to 15 ng g⁻¹, respectively. However, total Hg and MMHg concentrations in the soils collected from control sites were significantly lower varying from 0.1 to 1.2 mg kg⁻¹ and 0.10 to 1.6 ng g⁻¹, respectively. Total Hg and MMHg concentrations in sediments varied from 90 to 930 mg kg⁻¹ and 3.0 to 20 ng g⁻¹, respectively. Total Hg concentrations in mine-waste calcines were highly elevated ranging from 5.7 to 4400 mg kg⁻¹, but MMHg concentrations were generally low ranging from 0.17 to 1.1 ng g⁻¹. Similar to the high Hg concentrations in soil and sediments, moss samples collected from rocks ranged from 1.0 to 95 mg kg⁻¹ in total Hg and from 0.21 to 20 ng g⁻¹ in MMHg. Elevated Hg concentrations in mosses suggest that atmospheric deposition might be an important pathway of Hg to the local terrestrial system. Moreover, the spatial distribution patterns of Hg contamination in the local environment suggest derivation from historic Hg mining sites in the Wanshan area.     

Time and temperature dependency of carbon dioxide triggered metal(loid) mobilization in soil

Assessing the influence of CO₂ on soil and aquifer geochemistry is a task of increasing interest when considering risk assessment for geologic carbon sequestration. Leakage and CO₂ ascent can lead to soil acidification and mobilization of potentially toxic metals and metalloids due to desorption or dissolution reactions. We studied the CO₂ influence on an Fe(III) (oxyhydr)oxide rich, gleyic Fluvisol sampled in close vicinity to a Czech mofette site and compared the short-term CO₂ influence in laboratory experiments with observations on long-term influence at the natural site. Six week batch experiments with/without CO₂ gas flow at 3 different temperatures and monitoring of liquid phase metal(loid) concentrations revealed two main short-term mobilization processes. Within 1 h to 1 d after CO₂ addition, mobilization of weakly adsorbed metal cations occurred due to surface protonation, most pronounced for Mn (2.5–3.3 fold concentration increase, mobilization rates up to 278 ± 18 μg Mn kg_soil⁻¹ d⁻¹) and strongest at low temperatures. However, total metal(loid) mobilization by abiotic desorption was low. After 1–3 d significant Fe mobilization due to microbially-triggered Fe(III) (oxyhydr)oxide dissolution began and continued throughout the experiment (up to 111 ± 24 fold increase or up to 1.9 ± 0.6 mg Fe kg_soil⁻¹ d⁻¹). Rates increased at higher temperature and with a higher content of organic matter. The Fe(III) mineral dissolution was coupled to co-release of incorporated metal(loid)s, shown for As (up to 16 ± 7 fold, 11 ± 8 μg As kg_soil⁻¹ d⁻¹). At high organic matter content, re-immobilization due to resorption reactions could be observed for Cu. The already low pH (4.5–5.0) did not change significantly during Fe(III) reduction due to buffering from sorption and dissolution reactions, but a drop in redox potential (from > +500 mV to minimum +340 ± 20 mV) occurred due to oxygen depletion. We conclude that microbial processes following CO₂ induction into a soil can contribute significantly to metal(loid) mobilization, especially at optimal microbial growth conditions (moderate temperature, high organic carbon content) and should be considered for carbon sequestration monitoring and risk assessment.     

Mercury in sediments from gold and copper exploitation areas in the Camaquã River Basin,Southern Brazil

Mercury concentrations were determined in stream sediments from the Camaquã River Basin, located in the shield region of the state of Rio Grande do Sul, southern Brazil. The resulting geochemical data show that overbank floodplain deposits exhibit higher concentrations than sediments collected from the active channel bed. In addition, higher Hg concentrations were measured in the fine(<63 μm) sediment fraction of the samples. Total Hg concentrations in the fine fraction of active stream sediments from Lavras do Sul County, which have been influenced by past gold mining activities, have decreased during the last five years to values ≤142 ng g⁻¹. However, in a settling pond containing abandoned mine wastes, the Hg concentration of a bulk sample remained exceptionally high (5220 ng g⁻¹). Preliminary speciation results show that Hg⁰ is the predominant species in most of the samples. This was the form of Hg released by the gold amalgamation activities in the area, and appears to be relatively stable under the existing E_h and pH conditions.     

Redox zonation and oscillation in the hyporheic zone of the Ganges-Brahmaputra-Meghna Delta: Implications for the fate of groundwater arsenic during discharge

Riverbank sediment cores and pore waters, shallow well waters, seepage waters and river waters were collected along the Meghna Riverbank in Gazaria Upazila, Bangladesh in Jan. 2006 and Oct.–Nov. 2007 to investigate hydrogeochemical processes controlling the fate of groundwater As during discharge. Redox transition zones from suboxic (0–2 m depth) to reducing (2–5 m depth) then suboxic conditions (5–7 m depth) exist at sites with sandy surficial deposits, as evidenced by depth profiles of pore water (n = 7) and sediment (n = 11; diffuse reflectance, Fe(III)/Fe ratios and Fe(III) concentrations). The sediment As enrichment zone (up to ∼700 mg kg⁻¹) is associated with the suboxic zones mostly between 0 and 2 m depth and less frequently between 5 and 7 m depth. The As enriched zones consist of several 5–10 cm-thick dispersed layers and span a length of ∼5–15 m horizontally from the river shore. Depth profiles of riverbank pore water deployed along a 32 m transect perpendicular to the river shore show elevated levels of dissolved Fe (11.6 ± 11.7 mg L⁻¹) and As (118 ± 91 μg L⁻¹, mostly as arsenite) between 2 and 5 m depth, but lower concentrations between 0 and 2 m depth (0.13 ± 0.19 mg L⁻¹ Fe, 1 ± 1 μg L⁻¹ As) and between 5 and 6 m depth (1.14 ± 0.45 mg L⁻¹ Fe, 28 ± 17 μg L⁻¹ As). Because it would take more than a few hundred years of steady groundwater discharge (∼10 m yr⁻¹) to accumulate hundreds of mg kg⁻¹ of As in the riverbank sediment, it is concluded that groundwater As must have been naturally elevated prior to anthropogenic pumping of the aquifer since the 1970s. Not only does this lend unequivocal support to the argument that As occurrence in the Ganges-Brahmaputra-Meghna Delta groundwater is of geogenic origin, it also calls attention to the fate of this As enriched sediment as it may recycle As into the aquifer.     

Historical mercury trends recorded in sediments from the Laguna del Plata,Córdoba,Argentina

The main carrying phases of mercury (Hg) were analyzed in a 120 cm sediment core taken at the Laguna del Plata (LP), a small lake connected to the main water body of Laguna Mar Chiquita (LMC) during highstands. LMC is considered to be one of the largest saline lakes in the world representing a sensitive climatic indicator due to its frequent lake level variations at millennial and interdecadal scale like the last ones that started early in the 1970s and after 2004. Total particulate Hg (Hg_TP) concentrations vary between ∼13 and ∼131 μg kg⁻¹ indicating a system with low pollution. Selective extractions with ascorbate, HCl and H₂O₂ were performed in the sediments and they revealed that Hg is associated mainly to reactive sulphides in the base of the core, while in the middle and upper part the organic matter seems to be the main Hg-bearing phase. The highest and most important peak was found in sediments accumulated between 1991 and 1995. More than a punctual source of pollution, this peak is likely related to two eruptive events occurred in the Andean Cordillera in this period: the eruption of Hudson volcano in southern Patagonia that occurred in 1991 and the one of the Láscar volcano in northern Chile that occurred in 1993. In both cases, the respective ash plumes were documented to have reached the Laguna del Plata region.     

Dissolved and particulate zinc and nickel in the Yangtze River (China): Distribution,sources and fluxes

Dissolved and particulate Zn and Ni concentrations were determined at 76 locations along the Yangtze River basin from the headwaters to the estuary during flood and dry seasons. Spatial and temporal variations of Zn and Ni were investigated and six major source zones were identified. The Three Gorges Dam (TGD) blocked most of the suspended loads and extremely low concentration of Zn and Ni were observed downstream of the dam. Dissolved (ranging from 0.062 to 8.0 μg L⁻¹) and particulate (ranging from 12 to 110 mg kg⁻¹) Ni showed similar levels of concentrations during flood and dry seasons, whereas dissolved (ranging from 0.43 to 49 μg L⁻¹) and particulate (ranging from 54 to 1100 mg kg⁻¹) Zn were slightly and much lower in the flood season than dry season, respectively. This was attributed to the increased water discharge during the flood season causing a dilution effect and sediment resuspension. In the flood season, average concentrations of Zn and Ni were higher in the main channel than in tributaries, due to soil erosion and mining activities providing the dominant inputs. The situation was opposite in the dry season, attributed to the contribution of municipal sewage, industrial activities, and waste disposal. During the flood season, dissolved Zn and Ni concentrations were negatively correlated with pH. Water and suspended particulate matter (SPM) from the upper reaches, middle reaches, and lower reaches of the Yangtze River were characterized by their Zn and Ni concentrations. The Panzhihua, Nanling and Tongling mining areas were considered as the most important source zones of particulate Zn and Ni. The Chongqing region, Wuhan region and the Yangtze River Delta provided most of the dissolved Zn and Ni inputs into the river. Annual net flux of Zn (10–72 × 10⁵ kg a⁻¹) and Ni (5.0–19 × 10⁵ kg a⁻¹) in each source zone were estimated according to their respective influent and effluent fluxes. Contributions of the source zones to Zn and Ni transport decreased from the upper reaches to the lower reaches.     

Mercury in the Lot–Garonne River system (France): Sources,fluxes and anthropogenic component

Dissolved and particulate Hg fluxes in the Lot–Garonne–Gironde fluvial-estuarine system were obtained from observation of daily discharge and suspended particulate matter (SPM) concentrations. In addition to the measurements of the total dissolved (<0.45 μm) and particulate Hg (>0.45 μm), called HgT_D and HgT_P respectively, the dissolved inorganic Hg species (HgR_D) were determined monthly. Geochemical background values for HgT_P in sediments and SPM were similar to crustal values and to typical concentrations in SPM of non-contaminated river systems, respectively. The Riou Mort watershed already known as the origin of important historical polymetallic (e.g., Cd, Zn) pollution was identified as an important Hg point source. In the downstream Lot River, Hg concentrations were clearly higher than those in other moderately contaminated systems. The mean relative contribution of HgR_D to HgT_D in the Lot River and in the Garonne River was close to 25% and 50%, respectively, and showed no correlation with water discharge or SPM concentration. Depending on the origin and nature of SPM, HgT_P concentrations were correlated or not with particulate organic C (POC). Maximum HgT_P concentrations were measured in samples containing low POC concentrations and were attributed to sediment resuspension. In contrast, high POC concentrations (6–17%) during algal blooms were associated with low/moderate HgT_P concentrations (<0.5 mg kg⁻¹) at different sites, suggesting that Hg concentrations in fluvial phytoplankton may be limited by bioavailability of dissolved Hg and/or physiologically controlled Hg accumulation. Mercury was mostly (up to 98%) transported in the particulate phase with estimated annual Hg fluxes at the outlet of the Lot River system ranging from 35 to 530 kg a⁻¹ for the past decade. The minimum anthropogenic component (58–84% of total Hg fluxes) could not be explained by present Riou Mort point source contributions, suggesting important Hg release from contaminated sediment as a major source and from downstream point sources (e.g., coal-fired power plants and/or metal processing industries). HgT_P concentrations and fluxes were strongly related to hydrologic variations and were clearly increased by riverbed dredging during lock construction. Therefore, the estimated Hg stocks in the Lot River sediment (5–13 tons) represent an important potential Hg source for the downstream fluvial-estuarine system.     

50-year record and solid state speciation of mercury in natural and contaminated reservoir sediment

Contaminated fluvial sediments represent both temporary sinks for river-borne pollutants and potential sources in case of natural and/or anthropogenic resuspension. Reservoir lakes play a very important role in sediment dynamics of watersheds and may offer great opportunities to study historical records of river-borne particles and associated elements transported in the past. The fate and potential environmental impact of Hg depends on its abundance, its carrier phases and its chemical speciation. Historical Hg records and solid state Hg speciation were compared in sediments from two contrasting reservoirs of the Lot River (France) upstream and downstream from a major polymetallic pollution (e.g. Cd, Zn) source. Natural (geochemical background) and anthropogenic Hg concentrations and their relationships with predominant carrier phases were determined. The results reveal important historical Hg contamination (up to 35 mg kg⁻¹) of the downstream sediment, reflecting the historical evolution of industrial activity at the point source, i.e. former coal mining, Zn ore treatment and post-industrial remediation work. Single chemical extractions (ascorbate, H₂O₂, KOH) suggest that at both sites most (∼75%) of the Hg is bound to organic and/or reactive sulphide phases. Organo-chelated (KOH-extracted) Hg, representing an important fraction in the uncontaminated sediment, shows similar concentrations (∼0.02 mg kg⁻¹) at both sites and may be mainly attributed to natural inputs and/or processes. Although, total Hg concentrations in recent surface sediments at both sites are still very different, similar mono-methylmercury concentrations (up to 4 μg kg⁻¹) and vertical distributions were observed, suggesting comparable methylation-demethylation processes. High mono-methylmercury concentrations (4–15 μg kg⁻¹) in 10–40 a-old, sulphide-rich, contaminated sediment suggest long-term persistence of mono-methylmercury. Beyond historical records of total concentrations, the studied reservoir sediments provided new insights in solid state speciation and carrier phases of natural and anthropogenic Hg. In case of sediment resuspension, the major part of the Hg historically stored in the Lot River sediments will be accessible to biogeochemical recycling in the downstream fluvial-estuarine environment.     

Mercury gas emissions from La Soufrière Volcano, Guadeloupe Island (Lesser Antilles)

Quantifying mercury (Hg) emissions from active volcanoes is of particular interest for better constraining the global cycle and environmental impact of this highly toxic element. Here we report on the abundance of total gaseous (TGM = Hg⁰_(g) + Hg^II_(g)) and particulate (Hg_(p)) mercury in the summit gas emissions of La Soufrière andesitic volcano (Guadeloupe island, Lesser Antilles), where enhanced degassing of mixed hydrothermal-magmatic volatiles has been occurring since 1992 from the Southern summit crater. We demonstrate that Hg in volcanic plume occurs predominantly as gaseous mercury, with a mean TGM/Hg_(p) mass ratio of ~ 63. Combining the mean TGM/H₂S mass ratio of the volcanic plume (~ 3.2 × 10^− 6), measured close to the source vent, with the H₂S plume flux (~ 0.7 t d^− 1), determined simultaneously, allows us to estimate a gaseous mercury emission rate of 0.8 kg yr^− 1 from La Soufrière summit dome. Somewhat lower TGM/S_tot mass ratio in fumarolic gases from the source vent (4.4 × 10^− 7) suggests that plume chemical composition is not well represented by the emission source (fumaroles) due to chemical processes prior to (or upon) discharge. Current mercury emission from La Soufrìere volcano represents a very small contribution to the estimated global volcanic budget for this element.     

Use of biomarkers indices in a sediment core to evaluate potential pollution sources in a subtropical reservoir in Brazil

The presence of PAHs, n-alkanes, pristane, and phytanes in core sediment from the Vossoroca reservoir (Parana, southern Brazil) was investigated. The total concentration of the 16 PAHs varied from 15.5 to 1646 μg kg⁻¹. Naphthalene was present in all layers (3.34–74.0 μg kg⁻¹). The most abundant and dominant n-alkanes were n-C₁₅ and n-C₃₆, with average concentrations of 198.1 ± 46.8 and 522.9 ± 167.7 μg kg⁻¹, respectively. Lighter n-alkanes were distributed more evenly through the layers and showed less variation, specially n-C₉, n-C₁₂, and n-C₁₈, with average concentrations of 14.6 ± 3.0, 31.6 ± 1.9, and 95.0 ± 5.2 μg kg⁻¹, respectively; heavier n-alkanes were more unevenly distributed.     

Total mercury and monomethylmercury in water, sediments, and hydrophytes from the rivers, estuary, and bay along the Bohai Sea coast, northeastern China

Mercury contamination in aquatic environments is of worldwide concern because of its high biomagnification factor in food chains and long-range transport. The rivers, estuary and the bay along the northwestern Bohai Sea coast, northeastern China have been heavily contaminated by Hg due to long-term Zn smelting and chlor-alkali production. This work investigated the distributions of total Hg (THg) and monomethylmercury (MMHg) in the water, sediment and hydrophytes from this area. Concentrations of THg in sediment (0.5–64 mg kg⁻¹) and water (39–2700 ng L⁻¹) were elevated by 1–3 orders of magnitude compared to background concentrations, which induced high concentrations of MMHg in these media. The highest concentration of MMHg in sediment reached 35 μg kg⁻¹, which was comparable to that in the Hg mining area, Wanshan, China, and the highest MMHg concentration of 3.0 ng L⁻¹ in the water sample exceeded the MMHg Chinese drinking water guideline of 1.0 ng L⁻¹. Concentrations of THg in a sediment profile from Jinzhou Bay were found to be consistent with annual Hg emission flux from a local Zn smelter (r = 0.74, p < 0.01), indicating that Hg contamination was mainly caused by Zn smelting locally. For some freshwater hydrophytes, concentrations of THg and MMHg ranged from 5.2 to 100 μg kg⁻¹ and 0.15 to 12 μg kg⁻¹, respectively. Compared to sediment, concentrations of THg in hydrophytes were 2–3 orders of magnitude lower but MMHg was comparable or higher, indicating that the bioaccumulation in plants was distinct for the two Hg species studied. The data suggest that a significant load of Hg has been released into the northwestern coastal region of the Bohai Sea.     

Effects of acid-sulfate weathering and cyanide-containing gold tailings on the transport and fate of mercury and other metals in Gossan Creek: Murray Brook mine,New Brunswick,Canada

Gossan Creek, a headwater stream in the SE Upsalquitch River watershed in New Brunswick, Canada, contains elevated concentrations of total Hg (Hg_T up to 60 μg/L). Aqueous geochemical investigations of the shallow groundwater at the headwaters of the creek confirm that the source of Hg is a contaminated groundwater plume (neutral pH with Hg and Cl concentrations up to 150 μg/L and 20 mg/L, respectively), originating from the Murray Brook mine tailings, that discharges at the headwaters of the creek. The discharge area of the contaminant plume was partially delineated based on elevated pH and Cl concentrations in the groundwater. The local groundwater outside of the plume contains much lower concentrations of Hg and Cl (<0.1 μg/L and 3.8 mg/L, respectively) and displays the chemical characteristics of an acid-sulfate weathering system, with low pH (4.1–5.5) and elevated concentrations of Cu, Zn, Pb and SO₄ (up to 5400 μg Cu/L, 8700 μg Zn/L, 70 μg Pb/L and 330 mg SO₄/L), derived from oxidation of sulfide minerals in the Murray Brook volcanogenic massive sulfide deposit and surrounding bedrock. The Hg_T mass loads measured at various hydrologic control points along the stream system indicate that 95–99% of the dissolved Hg_T is attenuated in the first 3–4 km from the source. Analyses of creek bed sediments for Au, Ag, Cu, Zn, Pb and Hg indicate that these metals have partitioned strongly to the sediments. Mineralogical investigations of the contaminated sediments using analytical scanning electron microscopy (SEM), transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM), reveal discrete particles (<1–2 μm) of metacinnabar (HgS), mixed Au–Ag–Hg amalgam, Cu sulfide and Ag sulfide.     

Identification of contamination in a lake sediment core using Hg and Pb isotopic compositions,Lake Ballinger,Washington, USA

Concentrations and isotopic compositions of Hg and Pb were measured in a sediment core collected from Lake Ballinger, near Seattle, Washington, USA. Lake Ballinger has been affected by input of metal contaminants emitted from the Tacoma smelter, which operated from 1887 to 1986 and was located about 53 km south of the lake. Concentrations and loadings of Hg and Pb in Lake Ballinger increased by as much as three orders of magnitude during the period of smelting as compared to the pre-smelting period. Concentrations and loadings of Hg and Pb then decreased by about 55% and 75%, respectively, after smelting ended. Isotopic compositions of Hg changed considerably during the period of smelting (δ²⁰²Hg = −2.29‰ to −0.38‰, mean −1.23‰, n = 9) compared to the pre-smelting period (δ²⁰²Hg = −2.91‰ to −2.50‰, mean −2.75‰, n = 4). Variations were also observed in ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁷Pb isotopic compositions during these periods. Data for Δ¹⁹⁹Hg and Δ²⁰¹Hg indicate mass independent fractionation (MIF) of Hg isotopes in Lake Ballinger sediment during the smelting and post-smelting period and suggest MIF in the ore smelted, during the smelting process, or chemical modification at some point in the past. Negative values for Δ¹⁹⁹Hg and Δ²⁰¹Hg for the pre-smelting period are similar to those previously reported for soil, peat, and lichen, likely suggesting some component of atmospheric Hg. Variations in the concentrations and isotopic compositions of Hg and Pb were useful in tracing contaminant sources and the understanding of the depositional history of sedimentation in Lake Ballinger.