Mateja Gosar

Mercury speciation in tailings of the Idrija mercury mine

Abstract Five hundred years of mercury (Hg) mining activity in Idrija, Slovenia caused widespread Hg contamination. Besides Hg emissions from the ore smelter, tailings have been found to be the major source of river sediment contamination. In the present study, solid phase binding forms and the aqueous mobility of Hg have been investigated in tailings of the Idrija Hg mine by means of a pyrolysis technique and aqueous Hg speciation. Results show that Hg binding forms differ with the age of the tailings due to the processing of different ores with different roasting techniques. In older tailings, the predominant Hg species is cinnabar (HgS), due to incomplete roasting, whereas in tailings of the 20th century the amount of cinnabar in the material decreased due to a higher efficiency of the roasting process and the increasing use of ores bearing native Hg. In younger tailings, metallic Hg (Hg 0 ) sorbed to mineral matrix components such as dolomite and Fe-oxyhydroxides became the predominant Hg binding form in addition to unbound Hg 0 and traces of HgO. Leaching tests show that in younger tailings high amounts of soluble Hg exist in reactive form. In older tailings most of the soluble Hg occurs bound to soluble complexes. It might be assumed that in the long term, matrix-bound Hg 0 could be bound to humic acids derived from soils covering the tailings. This means that, despite the lower total Hg concentrations found in the younger tailings, the long-term risk potential of its mobile matrix-bound Hg 0 is higher than that of older tailings bearing mostly immobile cinnabar.

Mercury in the Idrijca River sediments as a reflection of mining and smelting activities of the Idrija mercury mine

Abstract Stream and flood plain sediments along the valley of the Idrijca River were systematically sampled. Upstream of the mercury mining town of Idrija, the Hg in stream sediment varies around 2 mg/kg. Mecury contents in the region from Idrija downstream to the town of Spodnja Idrija are from 100 to 1, 000 mg/kg. Downstream from Spodnja Idrija, sediments contain lower Hg (from 5 to 300 mg/kg). Recent overbank sediments are enriched relative to the stream sediments downstream of Idrija. River flood plain sediments that represent an accumulation of polluted sediments have Hg contents of 100 to 200 mg/kg.

Distribution of mercury in the atmosphere over Idrija, Slovenia

Idrija mine, the second largest mercury mine in the world, was in use since 1490. More than 107 000 tons of Hg were produced in its five centuries of history until 1990 when production was reduced to a few hundred kilos per year. The average recovery rate of mercury has been estimated to 73%; much of the remaining 27% was dissipated into the environment. In spite of present minimal levels of production, and only a few days of smelter operation per year, a real time survey with a mercury Zeeman analyser in a car showed relatively high mercury concentrations in the air. Amounts of 300--4000 ng Hg m-3 have been found around both the major sources of mercury vapour, the smelter and mine ventilation shaft -- while the amounts at the Old Place, at the City Museum, and near the Nikova-Idrijca confluence are of the order of 50 ng m-3. Polluted air will be transported from those sources to a degree which depends on the weather conditions, mainly the direction and intensity of the wind. The high mercury contents in the air are not only due to anthropogenic sources (smelter and the ventilation shaft, dumps and smelter slag used in construction), but may also partly be natural as in the Pront area, where the outcropping bedrock contains native mercury.

Mercury in river sediments, floodplains and plants growing thereon in the drainage area of the Idrija mine, Slovenia

half a millennium of mercury production at Idrija is reflected in increased mercury contents in all of its environmental segments. Stream sediments have been monitored along the Idrijca and Soca rivers (70 km) every 5 years since 1991. It has been discovered that there was no decrease in mercury concentration in stream sediments during the last 15 years. upstream from the town of Idrija, mercury concentrations in active river sediments vary from 1 to 10 mg/kg dry weight (average 3.3 mg/kg). From Idrija to Spodnja Idrija mercury concentrations increase extremely and vary greatly. The average in this area amounts to 603 mg/kg with individual contents up to 4121 mg/kg. From Spodnja Idrija to the Idrijca-Soca confluence the average is 213 mg/kg, while the average in the Soca river sediments is 57 mg/kg. Floodplain soils and samples of averaged meadow forage and plantain (Plantago lanceolata) were collected on river terraces at two localities in the lower course of the Idrijca. It has been determined that floodplains along the Idrijca River are strongly enriched with mercury. The average concentration of hg in the upper 20 cm of the floodplain at IdB location is 157.7 and at TEm location it is 294.8 mg/kg. Samples of averaged meadow forage and plantain contain from 0.055 to 0.220 mg hg/kg. In comparison to the plant samples from Idrija in the 1970s, these contents are relatively low. however, regarding mercury contents in plants in non-polluted soils the contents on the Idrijca River terraces are considerably higher than the background.

Comparison of elemental contents in earthworm cast and soil from a mercury-contaminated site (Idrija area, Slovenia).

The aim of this paper was to test the new sampling media-earthworm casts in a highly contaminated area. The investigation was carried out at the ancient Hg ore roasting site Pšenk in the surroundings of Idrija, where extremely high Hg contents in soils and SOM were determined in previous investigations. 32 earthworm cast samples were collected in the research grid 30 × 30 m in order to compare the Hg contents and spatial distribution in earthworm casts to the values and distributions in SOM and soil (0-15 cm). Extremely elevated Hg concentrations were determined in earthworm casts from the studied area ranging from 5.4 to 4330 mg/kg with the median of 31 mg/kg. The Hg values in casts are somewhat lower than in soil (6.3-8600 mg/kg) and slightly higher compared to soil organic matter (SOM) (1.5-4200 mg/kg). Strong correlation (r²=0.75) between Hg contents in casts and soil was found, while correlation between casts and SOM was positive but weaker (r²=0.35). Spatial distribution of Hg in earthworm casts show the highest concentrations in the central part of investigated area, similar to the distribution in soil. Hg contents rapidly decrease from the center toward the margins of the studied area, where they reach values of less than 50mg/kg. It was shown that Hg contents and dispersion in casts are comparable to those in soil, which indicates that at investigated area soil contamination is strongly reflected in contamination of earthworm casts.

Assessment of Metal Pollution Sources by SEM/EDS Analysis of Solid Particles in Snow: A Case Study of Žerjav, Slovenia

Solid particles in snow deposits, sampled in mining and Pb-processing area of Žerjav, Slovenia, have been investigated using scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDS). Identified particles were classified as geogenic-anthropogenic, anthropogenic, and secondary weathering products. Geogenic-anthropogenic particles were represented by scarce Zn- and Pb-bearing ore minerals, originating from mine waste deposit. The most important anthropogenic metal-bearing particles in snow were Pb-, Sb- and Sn-bearing oxides and sulphides. The morphology of these particles showed that they formed at temperatures above their melting points. They were most abundant in snow sampled closest to the Pb-processing plant and least abundant in snow taken farthest from the plant, thus indicating that Pb processing was their predominant source between the last snowfall and the time of sampling. SEM/EDS analysis showed that Sb and Sn contents in these anthropogenic phases were higher and more variable than in natural Pb-bearing ore minerals. The most important secondary weathering products were Pb- and Zn-containing Fe-oxy-hydroxides whose elemental composition and morphology indicated that they mostly resulted from oxidation of metal-bearing sulphides emitted from the Pb-processing plant. This study demonstrated the importance of single particle analysis using SEM/EDS for differentiation between various sources of metals in the environment.

Chemical and morphological characteristics of solid metal-bearing phases deposited in snow and stream sediment as indicators of their origin.

Detailed scanning electron microscopy/energy dispersive spectroscopy of metal-bearing particles in snow deposits and stream sediment from a steelworks area was performed. Identified metal-bearing phases were apportioned according to their chemical and morphological characteristics to anthropogenic phases and secondary weathering products. Anthropogenic metal-bearing phases are the most abundant in both media and are represented by various irregular ferrous oxides, ferrous alloys, spherical ferrous oxides, and ferrous silicates with variable contents of Cr, Mn, Ni, V, W, and Mo. Secondary weathering products are Al silicates, Fe oxy-hydroxides, and Fe oxy-hydroxy sulfates with minor contents of transition metals, resulting from weathering of anthropogenic phases and Pb–Zn ore minerals from a closed Pb–Zn mine located upstream from the study area. Comparison of anthropogenic metal-bearing phases in both media showed agreement in their compositions and morphologies and indicated their sources are high-temperature processes in steel production. It also showed that spherical metal-bearing phases were transported by the same transport medium, which is the atmosphere, while other phases were transported into stream sediment mostly by other pathways, such as precipitation runoff over contaminated surfaces.

U-Th signatures of agricultural soil at the European continental scale (GEMAS): Distribution, weathering patterns and processes controlling their concentrations

Agricultural soil (Ap-horizon, 0-20cm) samples were collected in Europe (33 countries, 5.6millionkm2) as part of the GEMAS (GEochemical Mapping of Agricultural and grazing land Soil) soil-mapping project. The GEMAS survey area includes diverse groups of soil parent materials with varying geological history, a wide range of climate zones, and landscapes. The soil data have been used to provide a general view of U and Th mobility at the continental scale, using aqua regia and MMI® extractions. The U-Th distribution pattern is closely related to the compositional variation of the geological bedrock on which the soil is developed and human impact on the environment has not concealed these genuine geochemical features. Results from both extraction methods (aqua regia and MMI®) used in this study support this general picture. Ternary plots of several soil parameters have been used to evaluate chemical weathering trends. In the aqua regia extraction, some relative Th enrichment-U loss is related to the influence of alkaline and schist bedrocks, due to weathering processes. Whereas U enrichment-Th loss characterizes soils developed on alkaline and mafic bedrock end-members on one hand and calcareous rock, with a concomitant Sc depletion (used as proxy for mafic lithologies), on the other hand. This reflects weathering processes sensu latu, and their role in U retention in related soils. Contrary to that, the large U enrichment relative to Th in the MMI® extraction and the absence of end-member parent material influence explaining the enrichment indicates that lithology is not the cause of such enrichment. Comparison of U and Th to the soil geological parent material evidenced i) higher capability of U to be weathered in soils and higher resistance of Th to weathering processes and its enrichment in soils; and, ii) the MMI® extraction results show a greater affinity of U than Th for the bearing phases like clays and organic matter. The comparison of geological units with U anomalies in agricultural soil at the country scale (France) enables better understanding of U sources in the surficial environment and can be a useful tool in risk assessments.

GEMAS: CNS concentrations and C/N ratios in European agricultural soil

A reliable overview of measured concentrations of TC, TN and TS, TOC/TN ratios, and their regional distribution patterns in agricultural soil at the continental scale and based on measured data has been missing - despite much previous work on local and the European scales. Detection and mapping of natural (ambient) background element concentrations and variability in Europe was the focus of this work. While total C and S data had been presented in the GEMAS atlas already, this work delivers more precise (lower limit of determination) and fully quantitative data, and for the first time high-quality TN data. Samples were collected from the uppermost 20cm of ploughed soil (Ap horizon) at 2108 sites with an even sampling density of one site per 2500km2 for one individual land-use class (agricultural) across Europe (33 countries). Laboratory-independent quality control from sampling to analysis guaranteed very good data reliability and accuracy. Total carbon concentrations ranged from 0.37 to 46.3wt% (median: 2.20wt%) and TOC from 0.40 to 46.0wt% (median: 1.80wt%). Total nitrogen ranged from 0.018 to 2.64wt% (median: 0.169wt%) and TS from 0.008 to 9.74wt% (median: 0.034wt%), all with large variations in most countries. The TOC/TN ratios ranged from 1.8 to 252 (median: 10.1), with the largest variation in Spain and the smallest in some eastern European countries. Distinct and repetitive patterns emerge at the European scale, reflecting mostly geogenic and longer-term climatic influence responsible for the spatial distribution of TC, TN and TS. Different processes become visible at the continental scale when examining TC, TN and TS concentrations in agricultural soil Europe-wide. This facilitates large-scale land-use management and allows specific areas (subregional to local) to be identified that may require more detailed research.

Calcite precipitates in Slovenian bottled waters

Storage of bottled waters in varying ambient conditions affects its characteristics. Different storage conditions cause changes in the initial chemical composition of bottled water which lead to the occurrence of precipitates with various morphologies. In order to assess the relationship between water composition, storage conditions and precipitate morphology, a study of four brands of Slovenian bottled water stored in PET bottles was carried out. Chemical analyses of the main ions and measurements of the physical properties of water samples were performed before and after storage of water samples at different ambient conditions. SEM/EDS analysis of precipitates was performed after elapsed storage time. The results show that the presence of Mg2+, SO42−, SiO2, Al, Mn and other impurities such as K+, Na+, Ba and Sr in the water controlled precipitate morphology by inhibiting crystal growth and leading to elongated rhombohedral calcite crystal forms which exhibit furrowed surfaces and calcite rosettes. Different storage conditions, however, affected the number of crystallization nuclei and size of calcite crystals. Hollow calcite spheres composed of cleavage rhombohedrons formed in the water with variable storage conditions by a combination of evaporation and precipitation of water droplets during high temperatures or by the bubble templating method.