Total Hg concentrations in stream and lake sediments: Discerning geospatial patterns and controls across Canada

This article presents an analysis of Geological Survey of Canada (GSC) open-file data for total Hg concentrations (THg) in stream and lake sediments at 142,028 sampling locations. This analysis was done for select survey zones across Canada, with emphasis on discerning THg-relevant geographic, geological, atmospheric and topographic controls. THg was generally highest in areas affected by mining and smelting, followed by areas with high metallogenic source locations. Background levels for THg were elevated in the more populated areas along the south, but dropped toward the remote and coldest locations in the east, north and west. This trend was correlated (R² = 0.74; P < 0.0001) with the 2005 GRAHM projections (Global/Regional Atmospheric Heavy Metals Model) for atmospheric Hg deposition (zones and locations with major geogenic sources and mining activities removed). Mean THg was higher for upland lakes (100.9 ± 0.5 SE, ppb) and streams (71.7 ± 0.6 SE, ppb) than for lowland lakes (94.4 ± 0.86 SE, ppb) and streams (64.2 ± 1.26 SE, ppb). The east-central portion of the Yukon Territory (Selwyn Basin) was analyzed in further detail. Here, THg within the sediments increased with increasing loss-on-ignition and increasing trace-element concentrations, and decreased with an increasing wet-area component per catchment above the sediment sampling locations. The characterization and quantification of these Hg trends is important for modeling and mapping health risks to ecosystems and communities across Canada and elsewhere.     

The distribution of total mercury and methyl mercury in a shallow hypereutrophic lake (Lake Taihu) in two seasons

To understand the geochemical cycle of Hg in hypereutrophic freshwater lake, two sampling campaigns were conducted in Lake Taihu in China during May and September of 2009. The concentrations of unfiltered total Hg (unfTHg) were in the range of 6.8–83 ng L⁻¹ (28 ± 18 ng L⁻¹) in the lake water and total Hg in the sediment was 12–470 ng g⁻¹, both of which are higher than in other background lakes. The concentration of unfTHg in ∼11% of the lake water samples exceeded the second class of the Chinese environmental standards for surface water of 50 ng L⁻¹ (GB 3838-2002), indicating that a high ecological risk is posed by the Hg in Lake Taihu. However, the concentrations of unfiltered total MeHg (unfMeHg) were relatively low in the lake water (0.14 ± 0.05 ng L⁻¹, excluding two samples with 0.81 and 1.0 ng L⁻¹). Lake sediment MeHg varied from 0.2–0.96 ng g⁻¹, with generally low ratios of MeHg/THg of <1%. The low concentrations of TMeHg in the lake water may have resulted from a strong uptake by the high primary productivity and the demethylation of MeHg in oxic conditions. In addition, contrary to the results of previous research conducted in deep-water lakes and reservoirs, the low concentrations of MeHg and low ratio of MeHg/THg in the lake sediment indicates that the net methylation of Hg was not accelerated by the elevated organic matter load created by the eutrophication of Lake Taihu. The results also showed that sediments were a source of THg and MeHg in the water. Higher diffusion fluxes of THg and MeHg may be partly responsible for the higher concentrations of THg in the lake water in May, 2009.     

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.     

Benthic fluxes of mercury species in a lagoon environment (Grado Lagoon,Northern Adriatic Sea,Italy)

The role of the major biogeochemical processes in Hg cycling at the sediment–water interface was investigated in the Grado Lagoon (Northern Adriatic Sea). This wetland system has been extensively contaminated from the Idrija Hg Mine (Slovenia) through the Isonzo River suspended load carried by tidal fluxes. Three approaches were used to study the sediment–water exchange of total Hg (THg), methylmercury (MeHg), reactive Hg (RHg) and dissolved gaseous Hg (DGHg): (1) estimation of diffusive fluxes from porewater and overlying water concentrations, (2) measurements of benthic fluxes using a deployed light benthic chamber in situ and (3) measurements of benthic fluxes during oxic–anoxic transition with a laboratory incubation experiment. The THg solid phase, ranging between 9.5 and 14.4 μg g⁻¹, showed slight variability with depth and time. Conversely, MeHg contents were highest (up to 21.9 ng g⁻¹) at the surface; they tended to decrease to nearly zero concentration with depth, thus suggesting that MeHg production and accumulation occur predominantly just below the sediment–water interface. Porewater MeHg concentrations (0.9–7.9 ng L⁻¹, 0.15–15% of THg) varied seasonally; higher contents were observed in the warmer period. The MeHg diffusive fluxes (up to 17 ng m⁻² day⁻¹) were similar to those in the nearby Gulf of Trieste [Covelli, S., Horvat, M., Faganeli, J., Brambati, A., 1999. Porewater distribution and benthic flux of mercury and methylmercury in the Gulf of Trieste (Northern Adriatic Sea). Estuar. Coast. Shelf Sci. 48, 415–428], although the lagoon sediments contained four-fold higher THg concentrations. Conversely, the THg diffusive fluxes in the lagoon (up to 110 ng m⁻² day⁻¹) were one- to two-fold higher than those previously estimated for the Gulf of Trieste. The diurnal MeHg benthic fluxes were highest in summer at both sites (41,000 and 33,000 ng m⁻² day⁻¹ at the fishfarm and in the open lagoon, respectively), thus indicating the influence of temperature on microbial processes. The diurnal variations of dissolved THg and especially MeHg were positively correlated with O₂ and inversely with DIC, suggesting an important influence of benthic photosynthetic activities on lagoon benthic Hg cycling, possibly through the production of organic matter promptly available for methylation. The results from the dark chamber incubated in the laboratory showed that the regeneration of dissolved THg was slightly affected by the oxic–anoxic transition. Conversely, the benthic flux of MeHg was up to 15-fold higher in sediments overlain by O₂ depleted waters. In the anoxic phase, the MeHg fluxes proceeded in parallel with Fe fluxes and the methylated form reached approximately 100% of dissolved THg. The MeHg is mostly released into overlying water (mean recycling efficiency of 89%) until the occurrence of sulphide inhibition, due to scavenging of the available Hg substrate for methylation. The results suggest that sediments in the Grado Lagoon, especially during anoxic events, should be considered as a primary source of MeHg for the water column.     

Distribution of Hg in mangrove trees and its implication for Hg enrichment in the mangrove ecosystem

The aim of this study was to evaluate Hg distribution in mangrove plants and changes of Hg content during leaf aging; the contribution of litterfall to Hg enrichment in mangrove ecosystems is also discussed. Contents of total Hg (THg) and methylmercury (MeHg) in mangrove plants and sediments were determined. Contents of THg and MeHg in the sediments were 225 ± 157 ng/g and 0.800 ± 0.600 ng/g. Concentrations of THg and MeHg in the mangrove plants were 1760 ± 1885 ng/g and 0.721 ± 0.470 ng/g (dry weight), respectively, which were much higher than those in terrestrial plants. Enrichment of THg in mangrove plants was different, following the order Rhizophra apiculata > Rhizophora stylosa > Kandelia candel > Aegiceras corniculatum > Avicennia marina; while MeHg contents in mangrove plants decreased in the order of R. stylosa > K. candel > A. corniculatum > R. apiculata > A. marina. There were obvious interspecies differences, regional differences, individual differences and tissue differences between THg and MeHg contents of mangrove plants, all of which were closely related to the environmental and the physiological characteristics of mangrove plants. In juvenile leaves, mature leaves and leaf litter, THg contents ranged 55.3-1760 ng/g, 204-1800 ng/g, and 385-2130 ng/g (dry weight), respectively; MeHg contents ranged 0.17-2.39 ng/g, 0.01-1.28 ng/g, and 0.13-1.47 ng/g (dry weight), respectively. Except for A. corniculatum and Bruguier gymnorrhiza, THg content of mature leaves was always higher than that in juvenile leaves, but MeHg showed a contrasting trend. THg content of litter leaves was between that of juvenile leaves and mature leaves, while MeHg content was generally lower than that of juvenile leaves and mature leaves. In the mangrove ecosystem, Hg enrichment contributed by the litterfall decreased in the order of K. candel > A. corniculatum > A. marina.     

Mercury distribution, partitioning and speciation in coastal vs. inland High Arctic snow

Atmospheric mercury deposition on snow at springtime has been reported in polar regions, potentially posing a threat to coastal and inland ecosystems receiving meltwaters. However, the post-depositional fate of Hg in snow is not well known, and no data are available on Hg partitioning in polar snow. During snowmelt, we conducted a survey of Hg concentrations, partitioning and speciation in surface snow and at depth, over sea ice and over land along a 100 km transect across Cornwallis Island, NU, Canada. Total Hg concentrations [THg] in surface snow were low (less than 20 pmol L⁻¹) and were significantly higher in marine vs. inland environments. Particulate Hg in surface snow represented up to 90% of total Hg over sea ice and up to 59% over land. At depth, [THg] at the snow/sea ice interface (up to 300 pmol L⁻¹) were two orders of magnitude higher than at the snow/lake ice interface (ca. 2.5 pmol L⁻¹). Integrated snow columns, sampled over sea-ice and over land, showed that particulate Hg was mostly bound to particles ranging from 0.45 to 2.7 μm. Moreover, melting snowpacks over sea ice and over lake ice contribute to increase [THg] at the water/ice interfaces. This study indicates that, at the onset of snowmelt, most of the Hg in snow is in particulate form, particularly over sea ice. Low Hg levels in surface snow suggest that Hg deposited through early spring deposition events is partly lost to the atmosphere from the snowpack before snowmelt. The sea ice/snow interface may constitute a site for Hg accumulation, however. Further understanding of the cycling of mercury at the sea ice/snow and sea ice/seawater interfaces is thus warranted to fully understand how mercury enters the arctic food webs.     

Mercury speciation in soils of the industrialised Thur River catchment (Alsace,France)

Methylmercury (MeHg) and total Hg (THg) concentrations in soil profiles were monitored in the Thur River basin (Alsace, France), where a chlor-alkali plant has been located in the city of Vieux-Thann since the 1930s. Three soil types were studied according to their characteristics and location in the catchment: industrial soil, grassland soil and alluvial soil. Contamination of MeHg and THg in soil was important in the vicinity of the plant, especially in industrial and alluvial soil. Concentrations of MeHg reached 27 ng g⁻¹ and 29,000 ng g⁻¹ for THg, exceeding the predictable no effect concentration. Significant ecotoxicological risk exists in this area and remedial actions on several soil types are suggested. In each type of soil, MeHg concentrations were highest in topsoil, which decreased with depth. Concentrations of MeHg were negatively correlated with soil organic matter and total S, particularly when MeHg concentrations exceeded 8 ng g⁻¹. Under these conditions, MeHg concentrations in soil seemed to be influenced by THg, soil organic matter and total S concentrations. It was found that high MeHg/THg ratios (near 2%) in soil were mainly related to the combined soil environmental conditions such as low THg concentrations, low organic C/N ratios (<11) and relatively low pH (5–5.5). Nevertheless, even when the MeHg/THg ratio was low (∼0.04%), MeHg and THg concentrations were elevated, up to 13 ng g⁻¹ and to 29,000 ng g⁻¹, respectively. Thus, both THg and MeHg concentrations should be taken into account to assess potential environmental risks of Hg.     

Gaseous mercury emissions from urban surfaces: Controls and spatiotemporal trends

The spatial and temporal variability of Hg emissions from urban paved surfaces was assessed through repeated measurements under varying environmental conditions at six sample sites in Toronto, Ontario, Canada. The results show significant spatial variability of the Hg emissions with median values ranging from below detection limit to 5.2 ng/m²/h. Two of the sites consistently had higher Hg emissions (on several occasions >20 ng/m²/h) than the other 4, which were equivalently low (maximum emission: 2.1 ng/m²/h). A surrogate measure of the pavement Hg concentrations was obtained during each day of sampling through the collection of street dust. The median street dust concentration also showed significant spatial variability (ranging from 9.6 to 44.5 ng/g). Regression analysis showed that the spatial variability of the Hg emissions was significantly related to the street dust concentrations. Controlled experiments using Hg amended street dust confirmed the relationship between Hg surface concentration and emission magnitude. Within a given sample site, Hg emissions varied temporally and multiple regression analysis showed that within-site variability was significantly influenced by changes in solar radiation with only a minor effect from surface temperature. Controlled experiments using shade cloths confirmed that solar radiation can have a large influence on the magnitude of Hg emissions within a given site. The emissions measured in Toronto were contextualized through comparison sampling in Austin, Texas. The Hg emissions measured in Austin were within the range detected in Toronto and also showed significant correlation with Hg street dust concentrations between sites. To provide a holistic assessment of Hg emissions from urban environments, samples were also collected from other common urban surfaces (soil, roofs, and windows). Soils consistently had higher emissions than all the other surfaces (7.3 ng/m²/h, n = 39).     

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.     

Distribution,behavior, and transport of inorganic and methylmercury in a high gradient stream

Concentrations of Hg remain elevated in physical and biological media of the South River (Virginia, USA), despite the cessation of the industrial use of Hg in its watershed nearly six decades ago, and physical characteristics that would not seem to favor Hg(II)-methylation. A 3-a study of inorganic Hg (IHg) and methylmercury (MeHg) was conducted in physical media (soil, sediment, surface water, porewater and soil/sediment extracts) to identify non-point sources, transport mechanisms, and potential controls on Hg(II)-methylation. Data collected from surface water and sediment indicate that the majority of the non-point sources of IHg to the South River are within the first 14 km downstream from the historic point source. Partitioning data indicate that particle bound IHg is introduced in this reach, releasing dissolved and colloidal bound IHg, which is transported downstream. Extraction experiments revealed that floodplain soils released a higher fraction of their IHg content in aqueous extractions than fine-grained sediment (FGS). Based on ultrafiltration [<5000 nominal molecular weight cutoff (NMWC)] the majority of soil IHg released was colloidal in nature, providing evidence for the continued evolution of IHg for Hg(II)-methylation from soil. Strong seasonal patterns in MeHg concentrations were observed in surface water and sediment. The highest concentrations of MeHg in surface water were observed at moderate temperatures, suggesting that other factors limit net Hg(II)-methylation. Seasonal changes in sediment organic content and the fraction of 1 N KOH-extractable THg were also observed and may be important factors in controlling net Hg(II)-methylation rates. Sulfate concentrations in surface water are low and the evidence suggests that Fe reduction may be an important Hg(II)-methylation process. The highest sediment MeHg concentrations were observed in habitats with large amounts of FGS, which are more prevalent in the upper half of the study area due to the lower hydrologic gradient and agricultural impacts. Past and present land use practices and other geomorphologic controls contribute to the erosion of banks and accumulation of fine-grained sediment in this section of the river, acting as sources of IHg.     

Fractionation,distribution and transport of mercury in rivers and tributaries around Wanshan Hg mining district,Guizhou Province,Southwestern China: Part 2 – Methylmercury

Water samples were collected during normal flow (2007) and during a drought period (2008) from five rivers and tributaries draining the Wanshan Hg mining district, Guizhou, China. Unfiltered methylmercury (MeHg) as well as particulate and dissolved fractions of MeHg (P-MeHg, D-MeHg) were measured to assess the spatial and temporal variation of MeHg contamination in the local river system. Most locations (about 80%) displayed higher MeHg concentrations during drought period than during normal discharge conditions. Concentrations of MeHg during the drought period ranged from <0.035 to 11 ng L⁻¹ (geometric mean: 0.43), while during normal flow the concentrations ranged from <0.035 to only 3.4 ng L⁻¹ (geometric mean: 0.21). Concentrations of MeHg were positively correlated with total Hg (THg) concentrations (R² = 0.20–0.58, P < 0.001) and inversely related to distance from the calcines, during both sampling periods (R² = 0.34 and 0.23, P < 0.001, for low and normal flow, respectively) indicating that calcines may be important sources of MeHg to the downstream environment. Approximately 39% of MeHg was bound to particulates and the rest was transported in the dissolved phase along stretches of the entire river, which was different from THg, as this was mainly transported bound to particulates (commonly more than 80%).     

Mercury contamination due to zinc smelting and chlor-alkali production in NE China

Zinc smelting and chlor-alkali production are major sources of Hg contamination to the environment, potentially leading to serious impacts on the health of the local population. Huludao, NE China has been heavily contaminated by Hg due to long-term Zn smelting and chlor-alkali production. The aim of this work was to determine Hg accumulation in the aquatic and terrestrial environment, as well as in the human population of Huludao. The investigation included: (a) Hg accumulation in sediments, Spirogyra algae, crucian carp and shrimp, (b) Hg distribution in soil, vegetables and corn, and (c) assessment of potential health effects of Hg exposure associated with total Hg (T-Hg) concentrations in human hair. Measured T-Hg concentrations in sediments of Wuli River ranged from 0.15 to 15.4 mg kg⁻¹, with the maximum Hg concentration in sediment exceeding the background levels in Liaoning Province by 438 times. The maximum T-Hg levels in Spirogyra, crucian carp and shrimp were 13.6, 0.36, and 0.44 mg kg⁻¹, respectively. Total-Hg concentrations in hair of the human population varied from 0.05 to 3.25 mg kg⁻¹ (average 0.43 mg kg⁻¹). However, the frequency of paraesthesia to most inhabitants in Huludao was estimated to be lower than 5%, with only one person rated at 50%. The results indicated minimal adverse health effects of Hg exposure to the inhabitants of Huludao, despite the serious Hg contamination of the environment.     

Mercury and other metal and metalloid soil contamination near a Pb/Zn smelter in east Hunan province, China

The spatial distributions of contaminant metals (Hg, Pb, Zn, Cd, Cu) and a metalloid (As) in vegetable plots and paddy fields located near a large scale Pb/Zn smelter in Hunan province, China, were investigated. Soil located 4 km from the smelter was severely contaminated, with maximum concentrations of Hg, Pb, Zn, Cd, Cu and As as high as 2.89, 1200, 3350, 41.1, 157 and 93 mg kg⁻¹, respectively. Concentrations of soil metal and As decreased with distance in the dominant wind direction. Single-factor assessment indicated pollution levels of Hg, Pb, Zn and Cd were most severe, while pollution levels for Cu and As were less severe. Results from a potential ecological risk assessment indicated high risk associated with the soil within a 4 km radius, with the contribution for each contaminant calculated as follows: Cd (70.0%), Hg (19.4%), Pb (4.8%), As (3.0%), Cu (1.7%) and Zn (1.1%). The forest soil in the nearby city park was also affected by the atmospheric depositions from smelting activities. Soil profiles demonstrated the pollutants were mostly accumulated in the upper 20 cm layer. Contamination of the topsoil with Hg, Pb, Zn, Cd, Cu and As indicated remediation should be considered.     

A comparison of winter mercury accumulation at forested and no-canopy sites measured with different snow sampling techniques

Atmospheric mercury (Hg) is delivered to ecosystems via rain, snow, cloud/fog, and dry deposition. The importance of snow, especially snow that has passed through the forest canopy (throughfall), in delivering Hg to terrestrial ecosystems has received little attention in the literature. The snowpack is a dynamic system that links atmospheric deposition and ecosystem cycling through deposition and emission of deposited Hg. To examine the magnitude of Hg delivery via snowfall, and to illuminate processes affecting Hg flux to catchments during winter (cold season), Hg in snow in no-canopy areas and under forest canopies measured with four collection methods were compared: (1) Hg in wet precipitation as measured by the Mercury Deposition Network (MDN) for the site in Acadia National Park, Maine, USA, (2) event throughfall (collected after snowfall cessation for accumulations of >8 cm), (3) season-long throughfall collected using the same apparatus for event sampling but deployed for the entire cold season, and (4) snowpack sampling. Estimates (mean ± SE) of Hg deposition using these methods during the 91-day cold season in 2004–2005 at conifer sites showed that season-long throughfall Hg flux (1.80 μg/m²) < snowpack Hg (2.38 ± 0.68 μg/m²) < event throughfall flux (5.63 ± 0.38 μg/m²). Mercury deposition at the MDN site (0.91 μg/m²) was similar to that measured at other no-canopy sites in the area using the other methods, but was 3.4 times less than was measured under conifer canopies using the event sampling regime. This indicates that snow accumulated under the forest canopy received Hg from the overstory or exhibited less re-emission of Hg deposited in snow relative to open areas. The soil surface of field-scale plots were sprayed with a natural rain water sample that contained an Hg tracer (²⁰²Hg) just prior to the first snowfall to explore whether some snowpack Hg might be explained from soil emissions. The appearance of the ²⁰²Hg tracer in the snowpack (0–64% of the total Hg mass in the snowpack) suggests that movement of Hg from the soil into the snowpack is possible. However, as with any tracer study the ²⁰²Hg tracer may not precisely represent the reactivity and mobility of natural Hg in soils.     

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.     

Mercury in the Southern Ocean

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 (Hg_T) 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 Hg_T 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 (Hg_R) concentrations varied from 0.01 to 2.28 pmol L⁻¹, with a distribution showing that the Hg_T enrichment south of the SPF consisted mainly of Hg_R (67 ± 23%), whereas, in contrast, the percentage was half that in surface waters north of PFZ (33 ± 23%). Methylated mercury species (MeHg_T) concentrations ranged from 0.02 to 0.86 pmol L⁻¹. All vertical MeHg_T 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 Hg_T, low mean MeHg_T concentrations were associated with AAIW, and higher ones with AABW. The maximum of MeHg_T concentration at each station was systematically observed within the oxygen minimum zone, with a statistically significant MeHg_Tvs Apparent Oxygen Utilization (AOU) relationship (p < 0.001). The proportion of Hg_T 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 Hg_T and Hg_R 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 Hg_T 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, MeHg_T 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 MeHg_T vertical profile through the continuum suggests different sources, including atmosphere, seawater and methylation in basal ice. Whereas Hg_T 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.     

Impact of mining activities on soils and sediments at the historical mining area in Podljubelj,NW Slovenia

The abandoned Hg mine in Podljubelj was in operation with interceptions from 1557 to 1902. The entire operating period yielded about 110 000 tons of ore, from which 360 tons of Hg was produced. The objective of the research project was to establish the contents and spatial distribution of Hg in soils and stream sediments in the vicinity of the mine. On an area of 88 ha the soil was sampled in a 100 × 100 m grid. Two soil horizons (0–5 cm and 20–30 cm) were sampled in order to distinguish between geogenic and anthropogenic Hg sources. It was established that on an area of about 9 ha Hg content in soil exceeds The New Dutchlist action value for Hg (10 mg/kg). Total Hg concentrations in soil samples vary between 0.17 and 719 mg/kg, with a mean of 3.0 mg/kg. Mercury contents in stream sediments range from 0.065 to 1.4 mg/kg, with a mean of 0.64 mg/kg. The highest determined value in soils was found in the area around the former roasting furnace, where the ore was processed. Increased Hg concentrations were also found on the mine waste dump (108 mg/kg). Mercury contents in soils generally decrease with soil profile depth and with the distance from the mine and from the roasting furnace location. Mercury also appears in higher concentrations along the road that runs through the valley, which results from the use of Hg-bearing ore residues in road construction. The average enrichment factor (EF) of Hg in topsoil with respect to subsoil is 3.3. Calculated enrichment factors show higher values also for Cd (3.2), Pb (2.7), Ca (2.4) and P (1.9). The average enrichment factor of Hg in topsoil with regard to the established Slovenian soil averages (EF_slo) is 19. EF_slo of other determined chemical elements do not exceed 3.0.     

Rate of formation and dissolution of mercury sulfide nanoparticles: The dual role of natural organic matter

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 (Hg_aq) 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.     

Source Identification of Florida Bay's Methylmercury Problem: Mainland Runoff Versus Atmospheric Deposition and <Emphasis Type="Italic">In situ</Emphasis> Production

The first advisory to limit consumption of Florida Bay fish due to mercury was issued in 1995. Studies done by others in the late 1990s found elevated water column concentrations of both total Hg (THg) and methylmercury (MeHg) in creeks discharging from the Everglades, which had its own recognized mercury problem. To investigate the significance of allochthonous MeHg discharging from the upstream freshwater Everglades, we collected surface water and sediment along two transects from 2000 to 2002. Concentrations of THg and MeHg, ranging from 0.36 ng THg/L to 5.98 ng THg/L and from <0.02 ng MeHg/L to 1.79 ng MeHg/L, were elevated in the mangrove transition zone when compared both to upstream canals and the open waters of Florida Bay. Sediment concentrations ranged from 5.8 ng THg/g to 145.6 ng THg/g and from 0.05 ng MeHg/g to 5.4 ng MeHg/g, with MeHg as a percentage of THg occasionally elevated in the open bay. Methylation assays indicated that sediments from Florida Bay have the potential to methylate Hg. Assessment of mass loading suggests that canals delivering stormwater from the northern Everglades are not as large a source as direct atmospheric deposition and in situ methylation, especially within the mangrove transition zone.     

Methylation of Hg downstream from the Bonanza Hg mine,Oregon

Speciation of Hg and conversion to methyl-Hg were evaluated in stream sediment, stream water, and aquatic snails collected downstream from the Bonanza Hg mine, Oregon. Total production from the Bonanza mine was >1360 t of Hg, during mining from the late 1800s to 1960, ranking it as an intermediate sized Hg mine on an international scale. The primary objective of this study was to evaluate the distribution, transport, and methylation of Hg downstream from a Hg mine in a coastal temperate climatic zone. Data shown here for methyl-Hg, a neurotoxin hazardous to humans, are the first reported for sediment and water from this area. Stream sediment collected from Foster Creek flowing downstream from the Bonanza mine contained elevated Hg concentrations that ranged from 590 to 71,000 ng/g, all of which (except the most distal sample) exceeded the probable effect concentration (PEC) of 1060 ng/g, the Hg concentration above which harmful effects are likely to be observed in sediment-dwelling organisms. Concentrations of methyl-Hg in stream sediment collected from Foster Creek varied from 11 to 62 ng/g and were highly elevated compared to regional baseline concentrations (0.11–0.82 ng/g) established in this study. Methyl-Hg concentrations in stream sediment collected in this study showed a significant correlation with total organic C (TOC, R² = 0.62), generally indicating increased methyl-Hg formation with increasing TOC in sediment. Isotopic-tracer methods indicated that several samples of Foster Creek sediment exhibited high rates of Hg-methylation. Concentrations of Hg in water collected downstream from the mine varied from 17 to 270 ng/L and were also elevated compared to baselines, but all were below the 770 ng/L Hg standard recommended by the USEPA to protect against chronic effects to aquatic wildlife. Concentrations of methyl-Hg in the water collected from Foster Creek ranged from 0.17 to 1.8 ng/L, which were elevated compared to regional baseline sites upstream and downstream from the mine that varied from <0.02 to 0.22 ng/L. Aquatic snails collected downstream from the mine were elevated in Hg indicating significant bioavailability and uptake of Hg by these snails. Results for sediment and water indicated significant methyl-Hg formation in the ecosystem downstream from the Bonanza mine, which is enhanced by the temperate climate, high precipitation in the area, and high organic matter.