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.     

Influence of nutritional status on some toxic and essential elements in the blood of women exposed to vehicular pollution in Ile-Ife, Nigeria

Blood levels of the elements Cu, Zn, Se, As, Cd, Hg, and Pb have been determined in 62 Nigerian women who were occupationally exposed to vehicular pollution. Mercury was determined using a direct mercury analyzer, while all the other elements were determined by an inductively coupled plasma mass spectrometer system. The mean values for all the toxic elements were all within the recommended desirable/tolerable limits, except for Se (0.44 μg/mL, compared with <0.2 μg/mL recommended by the WHO). More than 98 % of the subjects had blood selenium levels higher than this recommended limit. For As, Hg, and Pb, the corresponding figures of subjects with blood levels above the recommended limits were 4, 8, and 19.3 %, respectively. When the subjects were grouped according to their body mass indexes as normal, underweight, overweight, and obese, analysis of variance shows that mean blood levels of Cu, As, and, to some extent Hg were significantly different in the four nutritional status groups. Blood Hg level correlates significantly with blood As in all the groups, except in obese subjects. Also, a significant correlation between age and blood Hg was observed only in normal subjects and between age and blood Pb only in obese subjects. These results suggest that nutritional status could influence both elemental levels and the interactions between trace elements in the blood of female subjects. Nutrition is therefore a factor to consider in efforts to modify human susceptibility to toxic elements.     

Mercury in the Mediterranean,part I: spatial and temporal trends

The present paper provides an overview of mercury studies performed in the Mediterranean Sea region in the framework of several research projects funded by the European Commission and on-going national programmes carried out during the last 15 years. These studies investigated the temporal and spatial distribution of mercury species in air, in the water column and sediments, and the transport mechanisms connecting them. It was found that atmospheric concentrations of Hg compounds, particularly oxidised Hg species observed at five coastal sites in the Mediterranean Sea Basin, are significantly higher compared with those recorded at five coastal sites distributed across N Europe, most probably due to natural emissions. Hg levels in water are comparable to other oceans. Anthropogenic and natural point sources show locally limited enrichments, while natural diffusive sources influence Hg speciation over larger areas. Results and statistic comparison of mercury species concentrations within Mediterranean compartments will be presented and discussed.     

Development,Calibration and Verification of a 1-D Flow Model for a Looped River Network

This paper presents the development, calibration and verification of a looped river network model. After introducing the governing equations, the established numerical model is calibrated employing measurements conducted on the Danube River and its two main tributaries in Serbia, the Sava and Tisa rivers. The calibration is done by altering the Strickler’s coefficient using three different approaches, assigning a constant value of the coefficient in a cross section, setting the coefficient as a function of discharge and, finally, connecting the Strickler’s coefficient to local depth. The verification is conducted by comparing the computed results, for all three of the considered methods, with measurements for the time interval from January 1st to December 31st of the year 2006. Careful examination of the obtained results helped to select the most suitable calibration method for future reference. The selected approach gave better agreement of computed and measured values, has a clear physical explanation and enables faster and easier calibration.     

Conceptual Frameworks and Methods for Advancing Invasion Ecology

Invasion ecology has much advanced since its early beginnings. Nevertheless, explanation, prediction, and management of biological invasions remain difficult. We argue that progress in invasion research can be accelerated by, first, pointing out difficulties this field is currently facing and, second, looking for measures to overcome them. We see basic and applied research in invasion ecology confronted with difficulties arising from (A) societal issues, e.g., disparate perceptions of invasive species; (B) the peculiarity of the invasion process, e.g., its complexity and context dependency; and (C) the scientific methodology, e.g., imprecise hypotheses. To overcome these difficulties, we propose three key measures: (1) a checklist for definitions to encourage explicit definitions; (2) implementation of a hierarchy of hypotheses (HoH), where general hypotheses branch into specific and precisely testable hypotheses; and (3) platforms for improved communication. These measures may significantly increase conceptual clarity and enhance communication, thus advancing invasion ecology.     

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.     

Mercury emission and dispersion models from soils contaminated by cinnabar mining and metallurgy

The laboratory flux measurement system (LFMS) and dispersion models were used to investigate the kinetics of mercury emission flux (MEF) from contaminated soils. Representative soil samples with respect to total Hg concentration (26-9770 μg g(-1)) surrounding a decommissioned mercury-mining area (Las Cuevas Mine), and a former mercury smelter (Cerco Metalúrgico de Almadenejos), in the Almadén mercury mining district (South Central Spain), were collected. Altogether, 14 samples were analyzed to determine the variation in mercury emission flux (MEF) versus distance from the sources, regulating two major environmental parameters comprising soil temperature and solar radiation. In addition, the fraction of the water-soluble mercury in these samples was determined in order to assess how MEF from soil is related to the mercury in the aqueous soil phase. Measured MEFs ranged from less than 140 to over 10,000 ng m(-2) h(-1), with the highest emissions from contaminated soils adjacent to point sources. A significant decrease of MEF was then observed with increasing distance from these sites. Strong positive effects of both temperature and solar radiation on MEF was observed. Moreover, MEF was found to occur more easily in soils with higher proportions of soluble mercury compared to soils where cinnabar prevails. Based on the calculated Hg emission rates and with the support of geographical information system (GIS) tools and ISC AERMOD software, dispersion models for atmospheric mercury were implemented. In this way, the gaseous mercury plume generated by the soil-originated emissions at different seasons was modeled. Modeling efforts revealed that much higher emissions and larger mercury plumes are generated in dry and warm periods (summer), while the plume is smaller and associated with lower concentrations of atmospheric mercury during colder periods with higher wind activity (fall). Based on the calculated emissions and the model implementation, yearly emissions from the "Cerco Metalúrgico de Almadenejos" decommissioned metallurgical precinct were estimated at 16.4 kg Hg y(-1), with significant differences between seasons.     

A compilation of field surveys on gaseous elemental mercury (GEM) from contrasting environmental settings in Europe,South America,South Africa and China: separating fads from facts

Mercury is transported globally in the atmosphere mostly in gaseous elemental form (GEM, \( {\text{Hg}}_{\text{gas}}^{0} \) ), but still few worldwide studies taking into account different and contrasted environmental settings are available in a single publication. This work presents and discusses data from Argentina, Bolivia, Bosnia and Herzegovina, Brazil, Chile, China, Croatia, Finland, Italy, Russia, South Africa, Spain, Slovenia and Venezuela. We classified the information in four groups: (1) mining districts where this contaminant poses or has posed a risk for human populations and/or ecosystems; (2) cities, where the concentration of atmospheric mercury could be higher than normal due to the burning of fossil fuels and industrial activities; (3) areas with natural emissions from volcanoes; and (4) pristine areas where no anthropogenic influence was apparent. All the surveys were performed using portable LUMEX RA-915 series atomic absorption spectrometers. The results for cities fall within a low GEM concentration range that rarely exceeds 30 ng m^?3, that is, 6.6 times lower than the restrictive ATSDR threshold (200 ng m^?3) for chronic exposure to this pollutant. We also observed this behavior in the former mercury mining districts, where few data were above 200 ng m^?3. We noted that high concentrations of GEM are localized phenomena that fade away in short distances. However, this does not imply that they do not pose a risk for those working in close proximity to the source. This is the case of the artisanal gold miners that heat the Au–Hg amalgam to vaporize mercury. In this respect, while GEM can be truly regarded as a hazard, because of possible physical–chemical transformations into other species, it is only under these localized conditions, implying exposure to high GEM concentrations, which it becomes a direct risk for humans.