Hg Mining Research Articles

Hair can be a good biomarker of occupational exposure to mercury vapor: Simulated experiments and field data analysis

Generally, urine mercury (U-Hg) is widely used for assessment of inorganic mercury (I-Hg) exposure in humans. The reliability of scalp hair as an indicator of mercury vapor exposure is contentious. However, significant correlations were found between hair total mercury (T-Hg) and U-Hg and between hair I-Hg and total gaseous mercury (TGM) in ambient air in our previous studies. Simulated experiments were designed to assess the contribution of direct absorption/adsorption of mercury vapor in the hair. Results indicated that the increases of hair T-Hg concentrations were less than 1 μg/g, which was negligible compared with hair T-Hg concentrations in occupationally exposed workers. The β-mercaptoethanol washing can remove 30% of mercury (Hg) in the exposed hair samples. The inhaled Hg constituted the major fraction (97.4%) of I-Hg exposure for the artisanal Hg mining workers. From the simulated experiments and field data analysis, we can conclude that hair I-Hg can be a useful tool for monitoring occupational exposure to Hg vapor.

Environmental impact of ancient small-scale mercury ore processing at Pšenk on soil (Idrija area, Slovenia)

The Idrija mine was the second largest Hg mine in the world surpassed only by the Almaden mine in Spain. It has been estimated that almost 145,000 tons of Hg was produced during operation (1490–1995) of the mine. In the first decade of Hg mining in Idrija the ore was roasted in piles; after that it was roasted for 150 years, until 1652, in earthen vessels at various sites in the woods around Idrija. Pšenk is one out of 21 localities of ancient roasting sites established on the hills surrounding Idrija and one of the largest localities of roasting vessel fragments. The unique way of roasting very rich Hg ore at this site has resulted in soil contamination and considerable amounts of waste material that potentially leach Hg into the surrounding environment. The main aim of this study was to determine the distribution and the forms of Hg in contaminated soils in order to evaluate potential environmental risk. Detailed soil sampling was performed on 37,800 m2 area to establish the extent of Hg pollution and to investigate Hg transformations and transport characteristics through the 400 a-long period. A total of 156 soil (0–15 cm and 15–30 cm) and SOM (soil organic matter) samples were collected from 73 sampling points. Three soil profiles were sampled to determine vertical distribution of Hg. The main Hg phases were determined by the Hg-thermo-desorption technique. The measured Hg contents in soil samples in the study area vary from 5.5 to almost 9000 mg/kg with a median of 200 mg/kg. In SOM, Hg contents range from 1.4 to 4200 mg/kg with a median of 20 mg/kg. Extremely high Hg contents were found in soil profiles where the metal reaches 37,020 mg/kg. In general, Hg concentrations in all three profiles show a gradual decrease with depth with the minimum values between 140 mg/kg and 1080 mg/kg. The Hg-thermo-desorption curves indicate the presence of Hg in the form of cinnabar and that of Hg bound to organic or mineral soil matter. The distribution of Hg species in soil and SOM samples show almost equal distribution of cinnabar and non-cinnabar Hg compounds. The non-cinnabar fraction shows a little increase with depth, but cinnabar represents a high portion of total Hg (about 40%). Large amounts of potentially mobile and transformable non-cinnabar Hg compounds exist at the roasting site, which are potentially bioavailable.

Mercury pollution in Wuchuan mercury mining area, Guizhou, Southwestern China: The impacts from large scale and artisanal mercury mining

To evaluate the environmental impacts from large scale mercury mining (LSMM) and artisanal mercury mining (AMM), total mercury (THg) and methyl mercury (MeHg) were determined in mine waste, ambient air, stream water and soil samples collected from Wuchuan mercury (Hg) mining area, Guizhou, Southwestern China. Mine wastes from both LSMM and AMM contained high THg concentrations, which are important Hg contamination sources to the local environment. Total gaseous mercury (TGM) concentrations in the ambient air near AMM furnaces were highly elevated, which indicated that AMM retorting is a major source of Hg emission. THg concentrations in the stream water varied from 43 to 2100ng/L, where the elevated values were mainly found in the vicinity of AMM and mine waste heaps of LSMM. Surface soils were seriously contaminated with Hg, and land using types and organic matter played an important role in accumulation and transportation of Hg in soil. The results indicated heavy Hg contaminations in the study area, which were resulted from both LSMM and AMM. The areas impacted by LSMM were concentrated in the historical mining and smelting facilities, while Hg pollution resulted from AMM can be distributed anywhere in the Hg mining area.

Transport and fate of mercury under different hydrologie regimes in polluted stream in mining area

Abstract Seepage from Hg mine wastes and calcines contains high concentrations of mercury (Hg). Hg pollution is a major environmental problem in areas with abandoned mercury mines and retorting units. This study evaluates factors, especially the hydrological and sedimentary variables, governing temporal and spatial variation in levels and state of mercury in streams impacted by Hg contaminated runoff. Samples were taken during different flow regimes in the Wanshan Hg mining area in Guizhou Province, China. In its headwaters the sampled streams/rivers pass by several mine wastes and calcines with high concentration of Hg. Seepage causes serious Hg contamination to the downstream area. Concentrations of Hg in water samples showed significant seasonal variations. Periods of higher flow showed high concentrations of total Hg (THg) in water due to more particles being re-suspended and transported. The concentrations of major anions (e.g., Cl −, F −, NO 3 − and SO 4 2-) were lower during higher flow due to dilution. Due to both sedimentation of particles and dilution from tributaries the concentration of THg decreased from 2100 ng/L to background levels (< 50 ng/L) within 10 km distance downstream. Sedimentation is the main reason for the fast decrease of the concentration, it accounts for 69% and 60% for higher flow and lower flow regimes respectively in the upper part of the stream. Speciation calculation of the dissolved Hg fraction (DHg) (using Visual MINTEQ) showed that Hg(OH) 2 associated with dissolved organic matter is the main form of Hg in dissolved phase in surface waters in Wanshan (over 95%).

Non-point source mercury emission from the Idrija Hg-mine region: GIS mercury emission model

A mercury emission model was developed to estimate non-point source mercury (Hg) emissions occurring over the year from the Idrijca River catchment, draining the area of the world’s second largest Hg mine in Idrija, Slovenia. Site-specific empirical correlations between the measured Hg emission fluxes and the parameters controlling the emission (comprising substrate Hg content, soil temperature, solar radiation and soil moisture) were incorporated into the mercury emission model developed using Geographic Information System technology. In this way, the spatial distribution and significance of the most polluted sites that need to be properly managed was assessed. The modelling results revealed that annually approximately 51 kg of mercury are emitted from contaminated surfaces in the catchment (640 km 2), highlighting that emission from contaminated surfaces contributes significantly to the elevated Hg concentrations in the ambient air of the region. Very variable meteorological conditions in the modelling domain throughout the year resulted in the high seasonal and spatial variations of mercury emission fluxes observed. Moreover, it was found that mercury emission fluxes from surfaces in the Idrija region are 3–4 fold higher than the values commonly used in models representing emissions from global mercuriferous belts. Sensitivity and model uncertainty analysis indicated the importance of knowing not only the amount but also the type of mercury species and their binding in soils in future model development.

The Process of Methylmercury Accumulation in Rice (Oryza sativa L.)

Recent studies have shown that rice consumption can be an important pathway of methylmercury (MeHg) exposure to humans in Hg mining areas and also in certain inland areas of Southwestern China. The seed of rice has the highest ability to accumulate MeHg compared to other tissues. The main objective of this study was to investigate the process of (MeHg) accumulation in rice seed (Oryza sativa L.) by monitoring MeHg levels in specific tissues of rice plants experiencing various levels of Hg multisource pollution during a full rice growing season. Four groups of experimental plantations were utilized, distributed among a rural artisanal Hg production site and a regional background control site. Our results suggest that the newly deposited Hg is more readily transformed to MeHg and accumulated in rice plants than Hg forms with an extended residence time in soil, and soil is the potential source of MeHg in the tissues of rice plants. MeHg in soil was first absorbed by roots and then translocated to the above-ground parts (leaf and stalk). During the full rice growing season only a very small amount of MeHg was retained in the root section. In the premature plant, the majority of MeHg is located in the leaf and stalk; however, most of this MeHg was transferred to seed during the ripening period.

New Technique for Quantification of Elemental Hg in Mine Wastes and Its Implications for Mercury Evasion Into the Atmosphere

Mercury in the environment is of prime concern to both ecosystem and human health. Determination of the molecular-level speciation of Hg in soils and mine wastes is important for understanding its sequestration, mobility, and availability for methylation. Extended X-ray absorption fine structure (EXAFS) spectroscopy carried out under ambient P-T conditions has been used in a number of past studies to determine Hg speciation in complex mine wastes and associated soils. However, this approach cannot detect elemental (liquid) mercury in Hg-polluted soils and sediments due to the significant structural disorder of liquid Hg at ambient-temperature. A new sample preparation protocol involving slow cooling through the crystallization temperature of Hg(0) (234 K) results in its transformation to crystalline α-Hg(0). The presence and proportion of Hg(0), relative to other crystalline Hg-bearing phases, in samples prepared in this way can be quantified by low-temperature (77 K) EXAFS spectroscopy. Using this approach, we have determined the relative concentrations of liquid Hg(0) in Hg mine wastes from several sites in the California Coast Range and have found that they correlate well with measured fluxes of gaseous Hg released during light and dark exposure of the same samples, with higher evasion ratios from samples containing higher concentrations of liquid Hg(0). Two different linear relationships are observed in plots of the ratio of Hg emission under light and dark conditions vs % Hg(0), corresponding to silica-carbonate- and hot springs-type Hg deposits, with the hot springs-type samples exhibiting higher evasion fluxes than silica-carbonate type samples at similar Hg(0) concentrations. Our findings help explain significant differences in Hg evasion data for different mine sites in the California Coast Range.

Multielemental contents of foodstuffs from the Wanshan (China) mercury mining area and the potential health risks

Potentially harmful element contamination from mining and smelting raises concerns due to possible health risks. For most people, diet is the main route of exposure to potentially harmful elements, so determination of the concentrations of these elements in foodstuffs and assessment of their possible risk for humans via dietary intake is very important. This study was designed to investigate the concentrations of different elements, including Hg, Pb, Cd, Mn and Se in foodstuffs and to estimate the potential health risk of these elements via consumption of polluted foodstuffs in the Wanshan Hg mine area, Guizhou province, SW China. The multielemental concentrations were determined by inductively coupled plasma-mass spectrometry (ICP-MS). The target hazard quotient (THQ) and hazard index (HI) were calculated to evaluate the potential health risk from individual and combined potentially harmful elements due to dietary intake. The average contents of Hg, Pb, Cd, Mn and Se in the most frequently consumed foodstuffs were: 31, 248, 121, 1035 and 32 μg/kg respectively. Among them, Cd and Hg were the most important contributors to potentially harmful elements contamination in Wanshan. Eight of 10 kinds of vegetables were contaminated to various levels by different elements but the samples of rice, pork, radish and potato were below the stipulated limits for toxic elements. In this study, the average dietary intakes of Hg, Pb, Cd, Mn, Se by an adult man of 60 kg living in Wanshan were: 27, 167, 86, 1061, 42 μg/day, respectively. The HIs for multielement dietary intake was 3.11, with the relative contributions of Hg, Pb, Cd, Mn and Se being 22.3%, 24.3%, 45.0%, 3.9% and 4.4%, respectively, which indicated that consumption of food poses a potential health risk. Vegetables were found to be the main source of potentially harmful element dietary intake.

Potentially harmful elements in rice paddy fields in mercury hot spots in Guizhou, China

► Levels of Hg, Pb, Cd, Cu, Zn and As in soils from rice paddy fields were assessed. ► The two different regions were assessed, one impacted by mercury mining, one in a heavy industry area. ► In the mercury impacted regions soils had elevated levels of Zn and Cd in addition to Hg. ► In the coal impacted area soils had elevated levels of As and Hg. Levels of the chalcophile metals Hg, Pb, Cd, Cu and Zn and the metalloid As in soils from rice paddy fields were assessed in two regions impacted by different industrial activities in Guizhou province, China. The two study areas (Wanshan and Qingzhen) have previously received attention in the international literature due to heavy Hg pollution, though levels of other potentially harmful elements have not previously been reported. The regions were selected as representing two important, but categorically different metal(loid) contaminated areas in China: Wanshan has been a major region for Hg production while Qingzhen is an important region for a large range of various heavy industries based on coal as an energy source. Within a limited distance of the Hg mine tailings in Wanshan the rice paddy fields are heavily contaminated by Hg (median concentration 25 μg g −1 , maximum 119 μg g −1 ) and moderately contaminated by Zn and Cd (median concentrations of 86 and 0.9 μg g −1 , respectively). Zinc and Cd levels correlate well with Hg contamination, which indicates a similar source and mechanism of transport and accumulation. Other studies have concluded that the main sources of Hg contamination in Wanshan are the numerous Hg mine tailings. This is likely as these metals are all geochemically associated with the mineral cinnabar (HgS). The other chalcophile elements (Pb, Cu and As) are nevertheless found at background levels only. In Qingzhen the soils were found to contain elevated levels of As and Hg (median concentrations of 38 and 0.3 μg g −1 , respectively). These are elements that are known to be more associated with coal and released during coal combustion.

A regional mass balance of methylmercury in San Francisco Bay, California, USA

The San Francisco Bay (California, USA) is a water body listed as impaired because of Hg contamination in sport fish for human consumption, as well as possible effects on resident wildlife. A legacy of Hg mining in local watersheds and Hg used in Au mining in the Sierra Nevada (USA) has contributed to contamination seen in the bay, with additional more recent and ongoing inputs from various sources. Methylmercury is the species of Hg most directly responsible for contamination in biota, so better understanding of its sources, loads, and processes was sought to identify the best means to reduce impacts. A regional scale model of San Francisco Bay was developed to characterize major methylmercury inputs and processes. The model was used to evaluate the potential impact of uncertainties in estimates for methylmercury loading pathways and environmental processes, identify major data gaps, and explore management prospects for reducing methylmercury contamination. External loading pathways considered in the mass balance include methylmercury loads entering via atmospheric deposition to the bay surface, and discharges from the Sacramento/San Joaquin Delta, local watersheds, municipal wastewater, and fringing wetlands. Internal processes considered include exchange between bed and suspended sediments and the water column, in situ production and demethylation, biological uptake, and losses via hydrologic transport to the ocean through the Golden Gate. In situ sediment methylation and demethylation were dominant sources and losses determining ambient steady-state concentrations in the model, with changes in external loads and export causing smaller changes. Better information on methylation and demethylation is thus most critical to improving understanding of methylmercury balances and management.

Atmospheric distribution and deposition of mercury in the Idrija Hg mine region, Slovenia

The atmospheric distribution and deposition of Hg in the area of the former Idrija Hg-mine, Slovenia, were investigated. Mapping of air Hg 0 concentrations was performed to assess the spatial distribution and major sources of mercury to the atmosphere in the area. In addition, analyses of mercury speciation in the air over Idrija were performed during a 4-day sampling campaign in September 2006 to better understand the fate and transformation of Hg in the atmosphere of this specific mercury polluted site. The speciation results were then compared to the results of mercury speciation in the wet and throughfall deposition sampled on a precipitation event basis from October 2006 to September 2007. The Hg 0 concentration in air was mostly below 10 ng m −3, with the highest concentration in the area of the former smelter complex exceeding 5000 ng m −3. Mercury-bearing airborne particles (TPM) seem to dominate the atmospheric Hg deposition, which revealed noticeable variations between precipitation events (11–76 ng m −2 day −1), mostly as a function of the amount of precipitation. Hg in precipitation was largely (∼50%) associated with the particulate phase (THg P). No correlation was found between the THg P and the dissolved phases (THg D), suggesting that particulate phase Hg is mostly the result of dry deposition. In the throughfall, significantly higher (2–10 fold) Hg concentrations than in associated event precipitation were observed, mostly due to Hg in the particulate phase (∼70% THg). As shown by SEM/EDXS microscopy, an important amount of mercury in the precipitation and throughfall samples is due to the presence of cinnabar particles as a result of the aeolian erosion of cinnabar-containing surfaces in the area.

Sources of mercury to San Francisco Bay surface sediment as revealed by mercury stable isotopes

Mercury (Hg) concentrations and isotopic compositions were examined in shallow-water surface sediment (0–2 cm) from San Francisco (SF) Bay to determine the extent to which historic Hg mining contributes to current Hg contamination in SF Bay, and to assess the use of Hg isotopes to trace sources of contamination in estuaries. Inter-tidal and wetland sediment had total Hg (Hg T) concentrations ranging from 161 to 1529 ng/g with no simple gradients of spatial variation. In contrast, inter-tidal and wetland sediment displayed a geographic gradient of δ 202Hg values, ranging from −0.30‰ in the southern-most part of SF Bay (draining the New Almaden Hg District) to −0.99‰ in the northern-most part of SF Bay near the Sacramento–San Joaquin River Delta. Similar to SF Bay inter-tidal sediment, surface sediment from the Alviso Slough channel draining into South SF Bay had a δ 202Hg value of −0.29‰, while surface sediment from the Cosumnes River and Sacramento–San Joaquin River Delta draining into north SF Bay had lower average δ 202Hg values of −0.90‰ and −0.75‰, respectively. This isotopic trend suggests that Hg-contaminated sediment from the New Almaden Hg District mixes with Hg-contaminated sediment from a low δ 202Hg source north of SF Bay. Tailings and thermally decomposed ore (calcine) from the New Idria Hg mine in the California Coast Range had average δ 202Hg values of −0.37 and +0.03‰, respectively, showing that Hg calcination fractionates Hg isotopes resulting in Hg contamination from Hg(II) mine waste products with higher δ 202Hg values than metallic Hg(0) produced from Hg mines. Thus, there is evidence for at least two distinct isotopic signals for Hg contamination in SF Bay: Hg associated with calcine waste materials at Hg mines in the Coast Range, such as New Almaden and New Idria; and Hg(0) produced from these mines and used in placer gold mines and/or in other industrial processes in the Sierra Nevada region and SF Bay area.

Human co-exposure to mercury vapor and methylmercury in artisanal mercury mining areas, Guizhou, China

Mercury (Hg) concentrations were determined in human urine and hair samples from Gouxi (GX, n=25) and Laowuchang (LWC, n=18), Tongren, Guizhou, China, to evaluate human exposure from artisanal Hg mining. Geometric means of urinary Hg (U-Hg) were 216 and 560μgg−1 Creatinine (μgg−1 Cr) for artisanal mining workers from GX and LWC, respectively, and clinical symptoms (finger tremor) were observed in three workers. The means of hair Me-Hg concentrations were 4.26μgg−1 (1.87–10.6μgg−1) and 4.55μgg−1 (2.29–9.55μgg−1) for the population in GX and LWC, respectively. Significant relationship was found between estimated rice Me-Hg intake and hair Me-Hg levels (r=0.73, p<0.001). Co-exposure to Hg vapor and Me-Hg may pose health risks for the study population.

Pre-Colombian Mercury Pollution Associated with the Smelting of Argentiferous Ores in the Bolivian Andes

The development of the mercury (Hg) amalgamation process in the mid-sixteenth century triggered the onset of large-scale Hg mining in both the Old and New Worlds. However, ancient Hg emissions associated with amalgamation and earlier mining efforts remain poorly constrained. Using a geochemical time-series generated from lake sediments near Cerro Rico de Potosí, once the world's largest silver deposit, we demonstrate that pre-Colonial smelting of Andean silver ores generated substantial Hg emissions as early as the twelfth century. Peak sediment Hg concentrations and fluxes are associated with smelting and exceed background values by approximately 20-fold and 22-fold, respectively. The sediment inventory of this early Hg pollution more than doubles that associated with extensive amalgamation following Spanish control of the mine (1574-1900 AD). Global measurements of [Hg] from economic ores sampled world-wide indicate that the phenomenon of Hg enrichment in non-ferrous ores is widespread. The results presented here imply that indigenous smelting constitutes a previously unrecognized source of early Hg pollution, given naturally elevated [Hg] in economic silver deposits.

Speciation of methylmercury in rice grown from a mercury mining area

Monomethylmercury (CH 3Hg + and its complexes; MeHg hereafter) is a known developmental neurotoxin. Recent studies have shown that rice ( Oryza sativa L.) grain grown from mercury (Hg) mining areas may contain elevated MeHg concentrations, raising concerns over the health of local residents who consume rice on a daily basis. An analytical method employing high performance liquid chromatography (HPLC) – inductively coupled plasma mass spectrometry (ICP-MS) following enzymatic hydrolysis was developed to analyze the speciation of MeHg in uncooked and cooked white rice grain grown from the vicinity of a Hg mine in China. The results revealed that the MeHg in the uncooked rice is present almost exclusively as CH 3Hg- l-cysteinate (CH 3HgCys), a complex that is thought to be responsible for the transfer of MeHg across the blood–brain and placental barriers. Although cooking does not change the total Hg or total MeHg concentration in rice, no CH 3HgCys is measurable after cooking, suggesting that most, if not all, of the CH 3HgCys is converted to other forms of MeHg, the identity and toxicity of which remain elusive.

Mercury in San Francisco Bay forage fish

In the San Francisco Estuary, management actions including tidal marsh restoration could change fish mercury (Hg) concentrations. From 2005 to 2007, small forage fish were collected and analyzed to identify spatial and interannual variation in biotic methylmercury (MeHg) exposure. The average whole body total Hg concentration was 0.052 μg g −1 (wet-weight) for 457 composite samples representing 13 fish species. MeHg constituted 94% of total Hg. At a given length, Hg concentrations were higher in nearshore mudflat and wetland species ( Clevelandia ios, Menidia audens, and Ilypnus gilberti), compared to species that move offshore (e.g., Atherinops affinis and Lepidogobius lepidus). Gut content analysis indicated similar diets between Atherinops affinis and Menidia audens, when sampled at the same locations. Hg concentrations were higher in sites closest to the Guadalupe River, which drains a watershed impacted by historic Hg mining. Results demonstrate that despite differences among years and fish species, nearshore forage fish exhibit consistent Hg spatial gradients.

In Vitro Studies Evaluating Leaching of Mercury from Mine Waste Calcine Using Simulated Human Body Fluids

In vitro bioaccessibility (IVBA) studies were carried out on samples of mercury (Hg) mine-waste calcine (roasted Hg ore) by leaching with simulated human body fluids. The objective was to estimate potential human exposure to Hg due to inhalation of airborne calcine particulates and hand-to-mouth ingestion of Hg-bearing calcines. Mine waste calcines collected from Hg mines at Almadén, Spain, and Terlingua, Texas, contain Hg sulfide, elemental Hg, and soluble Hg compounds, which constitute primary ore or compounds formed during Hg retorting. Elevated leachate Hg concentrations were found during calcine leaching using a simulated gastric fluid (as much as 6200 μg of Hg leached/g sample). Elevated Hg concentrations were also found in calcine leachates using a simulated lung fluid (as much as 9200 μg of Hg leached/g), serum-based fluid (as much as 1600 μg of Hg leached/g), and water of pH 5 (as much as 880 μg of Hg leached/g). The leaching capacity of Hg is controlled by calcine mineralogy; thus, calcines containing soluble Hg compounds contain higher leachate Hg concentrations. Results indicate that ingestion or inhalation of Hg mine-waste calcine may lead to increased Hg concentrations in the human body, especially through the ingestion pathway.

Bioaccumulation of Methylmercury versus Inorganic Mercury in Rice (Oryza sativa L.) Grain

Mercury (Hg) bioaccumulation in aquatic food webs has been much studied, motivated from high Hg levels found in many fish species important for human consumption. Hg bioaccumulation in terrestrial food chains have received little attention and assumed to be of minor importance. However, recent studies showed that rice can be an important pathway of methylmercury (MeHg) exposure to inhabitants in Hg mining areas in China. In this study, 59 sampling sites (including 32 sites from "heavily polluted area", 19 from "less-impacted area" and 8 from "control sites") were selected in a Hg mining area in China and both inorganic Hg (IHg) and MeHg were determined in rice grain (brown rice) and soil samples to evaluate Hg bioaccumulation in rice grain. Bio-Accumulation Factors (BAFs) for IHg ranged from 0.00014 to 0.51 and from 0.71 to 50 for MeHg. BAFs for MeHg were on average more than 800 times higher than those for IHg (maximum: 40,000 times). This study, for the first time, showed that rice grain is an intensive bioaccumulator of MeHg, but not of IHg, which may be trapped by the roots.

Fractionation, distribution and transport of mercury in rivers and tributaries around Wanshan Hg mining district, Guizhou province, southwestern China: Part 1 – Total mercury

The Wanshan Hg mining area in Guizhou, China, was one of the world’s largest Hg producing regions. Numerous mine-waste and calcines still remain, leaching Hg to local rivers and streams and potentially impacting the local population. Several studies have been published on local environmental impacts of these mining and retorting residues, but a comprehensive, regional survey on the distribution of Hg in the rivers in the region, as presented in this paper, has not previously been conducted. This study focuses on the regional distribution and temporal variation of aqueous Hg fractions in the five main watercourses draining the Wanshan Hg mining and retorting area, covering more than 700 km2. Three sampling campaigns were carried out in 2007 and 2008, covering high flow, normal flow and low flow periods. Total (THg), particulate (PHg), dissolved (DHg) and reactive (RHg) Hg fractions were determined. All rivers had the highest Hg concentrations at sample sites about 100–500 m downstream of the mine wastes. Total Hg concentrations ranged from extremely high (up to 12,000 ng L−1) at the sample site just 100 m below mine wastes, to quite low in tributary streams (1.9 ng L−1, about 14 km downstream of the mine wastes). Total Hg and PHg concentrations were usually highest during high flow periods in the Hg-contaminated areas (i.e. THg ⩾ 50 ng L−1), while in the less-impacted downstream areas (with THg < 50 ng L−1) the Hg concentrations were usually lowest during high flow periods. Although highly elevated concentrations of Hg in water samples were found just downstream of the mine wastes, the concentrations decreased sharply to well below 50 ng L−1 (US EPA Hg concentration standard for protection of fresh water), within only 6–8 km downstream. Concentrations of THg were highly dominated by and correlated with PHg (R2 = 0.996–0.999, P < 0.001); PHg constituted more than 80% of THg in Hg-contaminated areas, and could account for 99.6% of the THg close to the mine wastes.

Tracing Mercury Contamination Sources in Sediments Using Mercury Isotope Compositions

Mercury (Hg) isotope ratios were determined in two sediment cores collected from two adjacent reservoirs in Guizhou, China, including Hongfeng Reservoir and Baihua Reservoir. Hg isotope compositions were also analyzed in a soil sample collected from the catchment of Hongfeng Reservoir and three cinnabar samples collected from the Wanshan Hg mine. Baihua Reservoir was contaminated with runoff from Guizhou Organic Chemical Plant (GOCP) when metallic Hg was used as a catalyst to produce acetic acid. Hongfeng Reservoir, located upstream of Baihua, receives Hg from runoff and atmospheric deposition. We demonstrated that delta(202)Hg values relative to NIST 3133 of sediment in Baihua Reservoir ranging from -0.60 to -1.10 per thousand were distinctively different from those in Hongfeng Reservoir varying from -1.67 to -2.02 per thousand. While sediments from both Baihua and Hongfeng Reservoirs were characterized by mass dependent variation (MDF), only Hongfeng Reservoir sediments were characterized by mass independent variation (MIF). Moreover, by using a binary mixing model, we demonstrated the major source of Hg in sediment of Hongfeng Reservoir was from runoff due to soil erosion, which was consistent with the conclusion obtained from a previous Hg balance study. This study demonstrates Hg isotope data are valuable tracers for determining Hg contamination sources in sediments.