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.     

Distribution of mercury in chemical fractions of contaminated urban soils of Middle Amur,Russia

The distribution of mercury (Hg) in fractions of urban soils from two industrial cities in the Russian Far East which are subject to varying degrees of Hg contamination was examined. The speciation scheme applied was based on routine chemical extraction methods used in soil investigations. Such an approach enables the Hg data to be brought into correlation with soil basic fractions and the fate of Hg bound to different soil components to be followed. Humic acids and a non-hydrolysable residue (humin), i.e. the soil fractions most refractory to microbiotic and chemical attack, were found to be principal Hg repositories in the soils studied. This pattern was equally observed for slightly, moderately and heavily contaminated soils. Hymatomelanic acids do not appear to be an efficient Hg concentrator. In heavily contaminated soils, Hg concentrations were evident in mobile fractions of fulvic acids as well as in those fractions extracted by H2O and 0.05 M Na2-EDTA pH 3. A portion of Hg extracted by 1 M HCl increased in lower horizons, reflecting relatively weakly bound Hg.     

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.     

Uncertainty assessment of mapping mercury contaminated soils of a rapidly industrializing city in the Yangtze River Delta of China using sequential indicator co-simulation

Accurate characterization of heavy-metal contaminated areas and quantification of the uncertainties inherent in spatial prediction are crucial for risk assessment, soil remediation, and effective management recommendations. Topsoil samples (0–15 cm) (n = 547) were collected from the Zhangjiagang suburbs of China. The sequential indicator co-simulation (SIcS) method was applied for incorporating the soft data derived from soil organic matter (SOM) to simulate Hg concentrations, map Hg contaminated areas, and evaluate the associated uncertainties. High variability of Hg concentrations was observed in the study area. Total Hg concentrations varied from 0.004 to 1.510 mg kg⁻¹ and the coefficient of variation (CV) accounts for 70%. Distribution patterns of Hg were identified as higher Hg concentrations occurred mainly at the southern part of the study area and relatively lower concentrations were found in north. The Hg contaminated areas, identified using the Chinese Environmental Quality Standard for Soils critical values through SIcS, were limited and distributed in the south where the SOM concentration is high, soil pH is low, and paddy soils are the dominant soil types. The spatial correlations between Hg and SOM can be preserved by co-simulation and the realizations generated by SIcS represent the possible spatial patterns of Hg concentrations without a smoothing effect. Once the Hg concentration critical limit is given, SIcS can be used to map Hg contaminated areas and quantitatively assess the uncertainties inherent in the spatial prediction by setting a given critical probability and calculating the joint probability of the obtained areas.     

Energy-dispersive X-ray fluorescence systems as analytical tool for assessment of contaminated soils

To determine the heavy metal content in soil samples at contaminated locations, a static and time consuming procedure is used in most cases. Soil samples are collected and analyzed in the laboratory at high quality and high analytical costs. The demand by government and consultants for a more dynamic approach and by customers requiring performances in which analyses are performed in the field with immediate feedback of the analytical results, is growing. Especially during the follow-up of remediation projects or during the determination of the sampling strategy, field analyses are advisable. For this purpose four types of ED-XRF systems, ranging from portable up to high performance laboratory systems, have been evaluated. The evaluation criteria are based on the performance characteristics for all the ED-XRF systems such as limit of detection, accuracy and the measurement uncertainty on one hand, and also the influence of the sample pretreatment on the obtained results on the other hand. The study proved that the field portable system and the bench top system, placed in a mobile van, can be applied as field techniques, resulting in semi-quantitative analytical results. A limited homogenization of the analyzed sample significantly increases the representativeness of the soil sample. The ED-XRF systems can be differentiated by their limits of detection which are a factor of 10 to 20 higher for the portable system. The accuracy of the results and the measurement uncertainty also improved using the bench top system. Therefore, the selection criteria for applicability of both field systems are based on the required detection level and also the required accuracy of the results.     

Risk assessment of contaminated sediments in river basins--theoretical considerations and pragmatic approach

In order to ensure chemical quality of river basins, measures as required in the Water Framework Directive will also have to address contaminated sediments with subsequent monitoring of their successful application. Financial resources need to be allocated as part of a river basin plan to those contaminated sites that pose the biggest risk to the river basin. In order to differentiate between areas with elevated contaminant levels ("areas of concern") and those sites from which contaminated sediments can become resuspended and transported with the river, affecting the water phase and downstream sites in the catchment ("areas of risk"), the dynamics of sediment and suspended matter need to come into focus. Hydrological data have to be combined with concentration of suspended matter and its contaminant concentration to allow assessment of particle bound contaminant load. Each of these kinds of data, however, are subject to uncertainties--e.g. due to natural variability, heterogeneity of the matrix, challenges during sampling and chemical analyses of the suspended matter. Considering these uncertainties throughout the traceability chains of data collection, use of different lines of evidence and tools like fuzzy logic will increase the confidence of potentially costly management decisions.     

EDTA-enhanced phytoremediation of contaminated calcareous soils: heavy metal bioavailability,extractability, and uptake by maize and sesbania

Natural and chemically enhanced phytoextraction potentials of maize (Zea mays L.) and sesbania (Sesbania aculeata Willd.) were explored by growing them on two soils contaminated with heavy metals. The soils, Gujranwala (fine, loamy, mixed, hyperthermic Udic Haplustalf) and Pacca (fine, mixed, hyperthermic Ustollic Camborthid), were amended with varying amounts of ethylenediaminetetraacetic acid (EDTA) chelating agent, at 0, 1.25, 2.5, and 5.0 mM kg^?1 soil to enhance metal solubility. The EDTA was applied in two split applications at 46 and 60 days after sowing (DAS). The plants were harvested at 75 DAS. Addition of EDTA significantly increased the lead (Pb) and cadmium (Cd) concentrations in roots and shoots, uptake, bioconcentration factor, and phytoextraction rate over the control. Furthermore, addition of EDTA also significantly increased the soluble fractions of Pb and Cd in soil over the controls; the maximum increase of Pb and Cd was 13.1-fold and 3.1-fold, respectively, with addition of 5.0 mM EDTA kg^?1soil. Similarly, the maximum Pb and Cd root and shoot concentrations, translocation, bioconcentration, and phytoextraction efficiency were observed at 5.0 mM EDTA kg^?1 soil. The results suggest that both crops can successfully be used for phytoremediation of metal-contaminated calcareous soils.     

Metabolic and bacterial diversity in soils historically contaminated by heavy metals and hydrocarbons

The aim of this study was to characterize soils contaminated by different levels of heavy metals and hydrocarbons (Madonna Dell'Acqua, Pisa, Italy). The soils were chemically and biochemically analysed by measuring the standard chemical properties and some enzyme activities related to microbial activity (dehydrogenase activity) and the soil carbon cycle (total and extracellular beta-glucosidase activities). The metabolic capacities of soil microorganisms to degrade hydrocarbons through catechol 2,3-dioxygenase were also described. The microbial diversity of contaminated and uncontaminated soils was estimated by denaturing gradient gel electrophoresis (DGGE) of amplified 16S rDNA sequences. The PCR/single-strand conformation polymorphism (PCR/SSCP) method was used to estimate the genetic diversity of PAH-degrading genes in both contaminated and uncontaminated soils. A greater bacterial diversity and lower catechol 2,3-dioxygenase activity was detected in unpolluted soils. The complexity of the microbial community (Shannon and Simpson indices) as well as the dehydrogenase soil activity negatively correlated with contamination levels. The greatest PAH-degrading gene diversity and the most intense catechol 2,3-dioxygenase activity were found in the soils with the highest levels of hydrocarbons. Heavy metals and hydrocarbon pollution has caused a genetic and metabolic alteration in microbial communities, corresponding to a reduction in microbial activity. A multi-technique approach combining traditional biochemical methods with molecular-based techniques, along with some methodological improvements, may represent an important tool to expand our knowledge of the role of microbial diversity in contaminated soil.     

Young northern pike,yellow perch and crayfish as bioindicators in a mercury contaminated watercourse

Young-of-the-year and yearling northern pike (Esox lucius), yearling yellow perch (Perca flavescens) and adult crayfish (Orconectes virilis) were collected in the mercury-contaminated Wabigoon/English/Winnipeg River System, Ontario, and analyzed for total mercury. Analysis of mercury concentrations in these organisms produced consistent geographical trends; i.e. mercury concentrations in biota downstream of Dryden > English River system > Winnipeg River system > control sites. In the Wabigoon River system the bioavailability of mercury increases with distance downstream of the historical point source. Mercury concentrations in the biota studied were highly correlated with mercury concentrations in fish species which are of sport and commercial interest. The locations where young fish obtain their bodyburdens are known typically within 100 m. The biota studied compare favourably with the criteria proposed by Phillips (1980) as prerequisites for biological indicators. The wide distribution of young pike, perch and crayfish in North America, Europe and Asia may enhance their appeal as biomonitors.The views expressed are those of the authors and do not necessarily reflect the views of the Ontario Ministry of the Environment. No endorsement should be inferred.     

Measurement of total antimony and antimony species in mine contaminated soils by ICPMS and HPLC-ICPMS

This paper describes the measurement of total antimony and antimony species in "real world" mine contaminated sediments using ICPMS and HPLC-ICPMS. Low and high temperature microwave extraction procedures (90 degrees C and 150 degrees C, respectively) using a range of nitric-hydrochloric acid combinations were examined as to their efficacy to extract antimony from six mine contaminated soils and a certified reference material. The use of the higher temperature with nitric-hydrochloric acid (1:2 (v/v)) was suitable to release antimony from sediments and the certified reference material, NIST 2710 Montana soil. Antimony concentrations obtained using this acid mixture were similar to those obtained using a more aggressive extraction with nitric, hydrochloric, perchloric and hydrofluoric acid mixture. A 25 mM citric acid solution at 90 degrees C for 15 min extracted 47-78% of antimony from soils. A Hamilton PRP X-100 anion exchange column with 20 mM EDTA mobile phase, pH 4.5, flow rate 1.5 mL min(-1) and column temperature of 50 degrees C was used to separate antimony species. Column recoveries ranged from 78-104%. The predominant form of antimony was Sb(5+). Little conversion of Sb(5+) occurred (<5%) during extraction, however, significant conversion of Sb(3+) occurred (approximately 36%). The extraction of antimony species with citric acid should be useful in the determination of inorganic antimony available to plants, as plants commonly excrete carboxylic acids, including citric acid, into their rhizospheres to mobilise trace elements for nutritional purposes.     

Remediation aspect of microbial changes of plant rhizosphere in mercury contaminated soil

Phytoremediation, an approach that uses plants to remediate contaminated soil through degradation, stabilization or accumulation, may provide an efficient solution to some mercury contamination problems. This paper presents growth chamber experiments that tested the ability of plant species to stabilize mercury in soil. Several indigenous herbaceous species and Salix viminalis were grown in soil collected from a mercury-contaminated site in southern Poland. The uptake and distribution of mercury by these plants were investigated, and the growth and vitality of the plants through a part of one vegetative cycle were assessed. The highest concentrations of mercury were found at the roots, but translocation to the aerial part also occurred. Most of the plant species tested displayed good growth on mercury contaminated soil and sustained a rich microbial population in the rhizosphere. The microbial populations of root-free soil and rhizosphere soil from all species were also examined. An inverse correlation between the number of sulfur amino acid decomposing bacteria and root mercury content was observed. These results indicate the potential for using some species of plants to treat mercury contaminated soil through stabilization rather than extraction. The present investigation proposes a practical cost-effective temporary solution for phytostabilization of soil with moderate mercury contamination as well as the basis for plant selection.     

Use of biological monitoring in the assessment of effects of mining wastes on aquatic ecosystems of the alligator rivers region,tropical Northern Australia

The primary objective of the biological monitoring program of the ARRRI is to develop techniques and procedures to monitor and assess effects of the mining and processing of ores on aquatic ecosystems of the Region. Studies have been made in a seasonal tributary (Magela Creek) of the East Alligator River near the Ranger Uranium Mine, and in the upper South Alligator River (SAR) near the Coronation Hill gold, platinum and palladium prospect. Ranger and Coronation Hill are enclosed by Kakadu National Park, environmental safeguards for which require the minimization of impairment of water quality in the aquatic ecosystems. Present studies on Magela Creek are designed to verify the adequacy of release standards, based on biological tests, in protecting the aquatic environment during and after releases of waste-water from Ranger during the Wet season. Detection of short-term effects will be sought by either creekside orin situ monitoring methods. The detection and assessment of any longer-term impacts, however, will rely chiefly on comparisons of post-release data with those of historical baselines. Such baseline information is provided by studies on the structure of macroinvertebrate and fish communities and/or on concentrations of elements in organisms in those communities, in Magela Creek and SAR catchments.     

Non-radiological contaminants from uranium mining and milling at Ranger,Jabiru, Northern Territory,Australia

Protection from the hazards from radioactivity is of prime importance in the management of uranium mine and mill wastes. Such wastes also contain non-radiological contaminants (heavy metals, acids and neutralising agents) which give rise to potential long-term health and environmental hazards and short-term hazards to the aquatic ecosystem, e.g. as a result of release of waste water. This study seeks to identify non-radiological contaminants (elements) transferred to waste water at the Ranger uranium mine/mill complex at Jabiru, which are likely to hazardous to the aquatic environment. The two principal sources of contaminants are:

1. ore and waste rock mobilised from mining; and
2. process reagents used in the milling and mineral extraction process.

These substances may or may not already be present in the natural environment but may lead to deleterious effects on the aquatic environment if increased above threshold levels. Rhenium, derived from the ore body, was found to be significantly enriched in waste water from Ranger, indicating its suitability as an indicator element for water originating from the mining and milling process, but only uranium, likewise derived from the ore, and magnesium, manganese and sulfur (as sulfate) from the milling process were found to be significant environmental contaminants.     

Speciation and quantification of Hg in sediments contaminated by artisanal gold mining in the Gualaxo do Norte River,Minas Gerais,SE, Brazil

The Iron Quadrangle in SE Brazil was, in the eighteenth century, one of the most important Au producing regions of Brazil. In this region, gold is produced, even today, by artisanal methods that use Hg to increase the extraction efficiency with no control of Hg release to water systems and the atmosphere. In this context, the Gualaxo do Norte River is of particular interest; its springs are located in the Doce River basin, an important Brazilian basin that supplies water for 3.5 million people. The main goal of this work was to quantify and speciate the Hg in the sediments of the Gualaxo do Norte River using a direct mercury analyzer and gas chromatography-pyrolysis-atomic fluorescence detection system. Statistical analyses consisted of principal component analysis, aiming to assess interactions among elements and species and to group the variables in factors affecting the properties of sediment. The results show that total Hg (THg) and methylmercury (CH₃Hg⁺) concentrations in samples ranged from 209 to 1207 μg kg^?1 and from 0.07 to 1.00 μg kg^?1, respectively (methylation percentages from 0.01 to 0.27%). Thermal desorption analysis showed that mercury is mainly present in the oxidized form, and correlation analyses pointed to a relationship between THg and MnO, indicating that manganese can oxidize and/or adsorb Hg. Together, MO and CH₃Hg⁺ are important parameters in the third principal component, indicating the influence of OM on the methylation process. This first investigation on Hg methylation in this small-scale gold mining area points to the possibility of Hg bioaccumulation and to the need of better understanding the biogeochemical cycle of Hg in this area. Samples were collected in 2012, prior to the 2015 Fundão Dam disaster. The results are also a record of the characteristics of the sediment prior to that event.     

Lichen biomonitoring of mercury emission and deposition in mining,geothermal and volcanic areas of Italy

Natural emissions of Hg are attracting increased interest both for their environmental implications and for possible applications in the exploration of mineral, petroleum and geothermal fields. However, daily and seasonal fluctuations in concentrations of Hg in the atmosphere, caused by meteorological and environmental variables, has made it very difficult to assess Hg anomalies by conventional analytical procedures. Some species of widespread foliose lichens from an abandoned cinnabar mining and smelting area (Mt. Amiata), geothermal fields (Larderello, Bagnore and Piancastagnaio, Central Italy), and active volcanic areas (Mt. Etna and Vulcano, Southern Italy) seem to be very suitable biomonitors of gaseous Hg; especially as lichen thalli have an Hg content which reflects average values measured in air samples. We discuss the advantages of quantitative biological monitoring by lichens with respect to conventional air sampling in large-scale monitoring.     

Fractionation and elemental association of Zn, Cd and Pb in soils contaminated by Zn minings using a continuous-flow sequential extraction

Fractionation and elemental association of Zn, Cd, and Pb in soils near Zn mining areas were studied using a continuous-flow sequential extraction approach. The recently developed sequential extraction procedure not only gave fractional distribution data for evaluation of the mobility or potential environmental impact of the metals, but also the extraction profiles (extractograms) which were used for study of elemental association. In addition, the elemental atomic ratio plot extractogram can be used to demonstrate the degree of anthropogenic contamination. Seventy-nine soil samples were collected in the vicinity of a Zn mine and were fractionated into 4 phases i.e. exchangeable (F1), acid soluble (F2), reducible (F3) and oxidizable (F4) phases. Most samples were contaminated with Zn, Cd and Pb. The reducible phase is the most abundant fraction for Zn and Pb (>50%) while Cd is concentrated in the first 3 extraction steps. The distribution patterns of Cd were obviously affected by soil pH. 55% of Cd appears predominantly in the F1 fraction for acidic soils while in neutral and alkaline soils, it was mostly (70%) found in the F2 + F3 fractions. The extractograms obtained from the continuous-flow extraction system revealed close association between Zn, Cd, Pb and Fe in the acid soluble phase, Cd-Pb and Zn-Fe in the reducible phase for contaminated soils. A correlation study of the 3 metals using a correlation coefficient was also performed to compare the results with the elemental association revealed by the extractograms. Atomic ratio plot extractograms of Zn/Fe, Cd/Fe and Pb/Fe in the reducible phase, where contaminated metals are predominant, can be used to evaluate the degree of anthropogenic contamination. From the elemental atomic ratio plot, it is obvious that the contaminants Cd and Pb are mostly adsorbed on the surface of Fe oxides. Zn, which is present in an approximately 1 ratio 1 ratio with Fe in contaminated soils, does not show a similar trend to that found for Cd and Pb.