David Kocman

Global Biogeochemical Implications of Mercury Discharges from Rivers and Sediment Burial

Rivers are an important source of mercury (Hg) to marine ecosystems. Based on an analysis of compiled observations, we estimate global present-day Hg discharges from rivers to ocean margins are 27 ± 13 Mmol a(-1) (5500 ± 2700 Mg a(-1)), of which 28% reaches the open ocean and the rest is deposited to ocean margin sediments. Globally, the source of Hg to the open ocean from rivers amounts to 30% of atmospheric inputs. This is larger than previously estimated due to accounting for elevated concentrations in Asian rivers and variability in offshore transport across different types of estuaries. Riverine inputs of Hg to the North Atlantic have decreased several-fold since the 1970s while inputs to the North Pacific have increased. These trends have large effects on Hg concentrations at ocean margins but are too small in the open ocean to explain observed declines of seawater concentrations in the North Atlantic or increases in the North Pacific. Burial of Hg in ocean margin sediments represents a major sink in the global Hg biogeochemical cycle that has not been previously considered. We find that including this sink in a fully coupled global biogeochemical box model helps to balance the large anthropogenic release of Hg from commercial products recently added to global inventories. It also implies that legacy anthropogenic Hg can be removed from active environmental cycling on a faster time scale (centuries instead of millennia). Natural environmental Hg levels are lower than previously estimated, implying a relatively larger impact from human activity.

Mercury fractionation in contaminated soils from the Idrija mercury mine region

Mercury (Hg) fractionation was investigated in contaminated soil in the Idrija Hg-mine region, Slovenia. The main aim of this study was to test and apply sequential extraction and quantification of different Hg phases in order to estimate the mobility and potential bioavailability of Hg in contaminated soils. Separation of Hg phases was performed by means of a selective sequential extraction procedure complemented by volatilization of elemental mercury (Hg0). The influence of temperature, moisture and storage on Hg0 volatilization was also investigated. The total Hg concentrations varied between 8.4 and 415 mg kg(-1) and were up to 40-fold higher than the maximum permissible set by Slovenian legislation. Fractionation measurements indicated cinnabar as the predominant Hg fraction, followed by Hg0. Accumulation of cinnabar predominantly occurred in coarse grained flood plain sediments, where on average it constituted more than 80% of total Hg. In contrast non-cinnabar fractions were found to be enriched in areas where fine grained material was deposited, reaching up to 60% of total Hg. The strong positive correlation (R2 = 0.71-0.99) among non-cinnabar fractions suggested that these fractions predominantly control the mobility and potential bioavailability of Hg. Sample pretreatment before fractionation influenced the partition of Hg between different fractions, and therefore fractionation in fresh, nontreated samples is suggested. In addition, the specificity of the extraction steps needs further attention, as it was shown that some extraction steps, such as the organo-chelating Hg fraction, do not provide meaningful results. This further suggests that protocols for mercury fractionation need further harmonization in order to improve the comparability of the results and their use in risk assessment. Volatile mercury fluxes averaged between 0.04 and 6.5 ng g(-1) h(-1). Good agreement (R2 = 0.81-0.95) was found between the non-cinnabar fractions and evaporation of Hg0. Both the temperature and sample moisture had significant effects on mercury volatilization. The results in this study were obtained at 70 degrees C, which may be somewhat high, in particular for bacterial activity which may also play an important role in Hg volatilization. Therefore it is strongly suggested that further optimisation of the protocol to assess Hg volatilization from soil is required.

Contribution of contaminated sites to the global mercury budget

Global mercury emission inventories include anthropogenic emissions, contributing via current use or presence of mercury in a variety of products and processes, as well as natural source emissions. These inventories neglect the contribution of areas contaminated with mercury from historical accumulation, which surround mines or production plants associated with mercury production or use. Although recent studies have shown that releases of mercury from these historical sites can be significant, a database of the global distribution of mercury contaminated sites does not exist, nor are there means of scaling up such releases to estimate fluxes on a regional and global basis. Therefore, here we estimated for the first time the contribution of mercury releases from contaminated sites to the global mercury budget. A geo-referenced database was built, comprising over 3000 mercury contaminated sites associated with mercury mining, precious metal processing, non-ferrous metal production and various polluted industrial sites. In the assessment, mercury releases from these sites to both the atmosphere as well as the hydrosphere were considered based on data available for selected case studies, their number, the reported extent of contamination and geographical location. Annual average global emissions of mercury from identified contaminated sites amount to 198 (137-260) Mgyr(-1). Of that, 82 (70-95)Mgyr(-1) contribute to atmospheric releases, while 116 (67-165) Mgyr(-1) is estimated to be transported away from these sites by hydrological processes. Although these estimates are associated with large uncertainties, our current understanding of mercury releases from contaminated sites indicates that these releases can also be of paramount importance on the global perspective. This is especially important as it is known that these sites represent a long-term source of releases if not managed properly. Therefore, the information presented here is needed by governments and NGOs in order to re-focus resources in making decisions regarding mitigation and remediation strategies on a global level.

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.

XANES speciation of mercury in three mining districts – Almadén, Asturias (Spain), Idria (Slovenia)

The mobility, bioavailability and toxicity of mercury in the environment strongly depend on the chemical species in which it is present in soil, sediments, water or air. In mining districts, differences in mobility and bioavailability of mercury mainly arise from the different type of mineralization and ore processing. In this work, synchrotron-based X-ray absorption near-edge spectroscopy (XANES) has been taken advantage of to study the speciation of mercury in geological samples from three of the largest European mercury mining districts: Almadén (Spain), Idria (Slovenia) and Asturias (Spain). XANES has been complemented with a single extraction protocol for the determination of Hg mobility. Ore, calcines, dump material, soil, sediment and suspended particles from the three sites have been considered in the study. In the three sites, rather insoluble sulfide compounds (cinnabar and metacinnabar) were found to predominate. Minor amounts of more soluble mercury compounds (chlorides and sulfates) were also identified in some samples. Single extraction procedures have put forward a strong dependence of the mobility with the concentration of chlorides and sulfates. Differences in efficiency of roasting furnaces from the three sites have been found.

Human mercury exposure and effects in Europe.

The effects of human exposure to mercury (Hg) and its compounds in Europe have been the focus of numerous studies that differed in their design, including recruiting different population groups at different levels of exposure and using different protocols and recruitment strategies. The objective of the present study was to review current studies of Hg exposure in Europe, taking into account the potential routes of Hg exposure, actual Hg exposure levels assessed by different biomarkers, and the effects of Hg to Europeans. All published studies from 2000 onward were reviewed, and exposure and effects studies were compared with known Hg levels in environmental compartments by mapping the various population groups studied and taking into account known sources of Hg. A study of the spatial distribution trends confirmed that the highest exposure levels to Hg, mostly as methylmercury (MeHg), are found in coastal populations, which consume more fish than inland populations. Fewer studies addressed exposure to elemental Hg through inhalation of Hg in air and inorganic Hg in food, particularly in highly contaminated areas. Overall, at the currently low exposure levels of Hg prevalently found in Europe, further studies are needed to confirm the risk to European populations, taking into consideration exposure to various Hg compounds and mixtures of stressors with similar end-points, nutritional status, and a detailed understanding of Hg in fish present in European markets.

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 worlds 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.

Toward an assessment of the global inventory of present-day mercury releases to freshwater environments

Aquatic ecosystems are an essential component of the biogeochemical cycle of mercury (Hg), as inorganic Hg can be converted to toxic methylmercury (MeHg) in these environments and reemissions of elemental Hg rival anthropogenic Hg releases on a global scale. Quantification of effluent Hg releases to aquatic systems globally has focused on discharges to the global oceans, rather than contributions to freshwater systems that affect local exposures and risks associated with MeHg. Here we produce a first-estimate of sector-specific, spatially resolved global aquatic Hg discharges to freshwater systems. We compare our release estimates to atmospheric sources that have been quantified elsewhere. By analyzing available quantitative and qualitative information, we estimate that present-day global Hg releases to freshwater environments (rivers and lakes) associated with anthropogenic activities have a lower bound of ~1000 Mg·a−1. Artisanal and small-scale gold mining (ASGM) represents the single largest source, followed by disposal of mercury-containing products and domestic waste water, metal production, and releases from industrial installations such as chlor-alkali plants and oil refineries. In addition to these direct anthropogenic inputs, diffuse inputs from land management activities and remobilization of Hg previously accumulated in terrestrial ecosystems are likely comparable in magnitude. Aquatic discharges of Hg are greatly understudied and further constraining associated data gaps is crucial for reducing the uncertainties in the global biogeochemical Hg budget.

Mercury emissions in equilibrium: a novel approach for the quantification of mercury emissions from contaminated soils.

Mercury emissions from soil samples with different mercury contents have been estimated using a closed circuit array. The samples were collected from the Almaden mercury mining district. The emissions confirmed that temperature and light radiation favour mercury desorption due to the increase in the mercury vapour pressure. An additional positive factor could be the photocatalytic reduction of soluble Hg2+ to volatile Hg0 at the soil surface. A physicochemical model based on mass transfer and equilibrium was developed and was used to reproduce the mercury emissions at the laboratory scale. The use of this model allowed us to obtain the unknown mass transfer coefficient (KL) and adsorption parameters required to quantify the possible gaseous mercury fluxes from these contaminated soils. Experimental results indicate that an equilibrium between the solid and gas phases was established. The proposed kinetic model reproduced perfectly the experimental data, with KL found to be proportional to the inverse of temperature and independent of the radiation. The concentration of mercury in the gas phase was mainly dependent on the soluble mercury content (HgS). Equilibrium data were fitted by Langmuir and Freundlich models and the best fit was obtained using the multi-layer model attending to the convex shape of the curves, which is characteristic of non-porous or possibly macroporous materials having a low adsorption energy. The Freundlich constant (KF) was also fitted as a polynomial function with temperature and this gave a straight line for the light radiation and a second grade equation for dark conditions. Once the parameters had been obtained, the Hg emission fluxes from contaminated soils were estimated and the values were between two and three orders of magnitude higher than those published in the literature for non-contaminated soils.

Exposure to mercury in susceptible population groups living in the former mercury mining town of Idrija, Slovenia.

Abstract 500 years of mercury (Hg) mining in the town of Idrija has caused severe pollution in Idrija and its surroundings. Following the closure of the mine in 1995, the environment remains contaminated with Hg. Sources of elemental‐, inorganic‐ and methyl Hg exposure were identified, potential environmental level of exposure to Hg was evaluated and actual internal exposure to Hg was assessed in selected susceptible population groups comprising school‐age children and pregnant women living in Idrija and in control groups from rural and urban environments. The study of pregnant women (n=31) was conducted between 2003 and 2008, and the study of school‐age children (n=176) in 2008. Potential interaction of Hg with selenium (Se) in plasma was assessed in both study populations, while in pregnant women antioxidative enzyme activity (glutathione peroxidase, superoxide dismutase and catalase) in erythrocytes of maternal and cord blood was also assessed. Actual exposure to Hg as indicated by levels of Hg in childrens blood (geometric mean (GM) 0.92 &mgr;g/L), mothers blood (GM 1.86 &mgr;g/L), childrens urine (GM 1.08 &mgr;g/g crea.), mothers urine (GM 2.51 &mgr;g/L), childrens hair (GM 241 ng/g) and mothers hair (GM 251 ng/g) was higher in the two study groups from Idrija than in the control groups from rural areas, but was still at the level of a “normal” population and reflects mainly exposure to elemental Hg (Hg°) from dental amalgam and, to a certain extent atmospheric Hg°. Furthermore, the internal doses of Hg received during pregnancy did not decrease the bioavailability of Se. Based on observation in children, the increase in Se protein expression is suggested to be a consequence of moderately elevated exposure to Hg°. The observed changes in activity of antioxidative enzymes, as biomarkers of oxidative stress, appear to be mainly associated with pregnancy per se and not with an increased exposure to Hg. In view of the continuing increased potential for Hg exposure and the low number of pregnant women studied, the results warrant a further longitudinal study of a larger group of pregnant women residing in the area of the former mercury mine. HighlightsEstimated environmental Hg exposure in the town of Idrija still poses a potential risk to susceptible groups of inhabitants.Actual internal exposure reflects mainly exposure to Hg° from dental amalgam and, to a certain extent atmospheric Hg°.The internal doses of Hg received in the Idrija children and pregnant women did not decrease the bioavailability of Se.Changes in activity of antioxidative enzymes were not associated with exposure to Hg in the town of Idrija.