Distribution and speciation of mercury in soil in the area of an ancient mercury ore roasting site,Frbejžene trate (Idrija area,Slovenia)

In the initial period of mining activities in the Idrija basin (the16^th and the first half of the17^th centuries), Hg ore processing was performed at various small-scale roasting sites in the woods surrounding Idrija, by roasting ore in earthen vessels. The recovery rate of this method was very low; about half of Hg was lost, causing soil contamination and considerable amounts of waste material that could potentially leach Hg into the surrounding environment. The main aims of present geochemical study were to determine the contents, vertical distribution and speciation of Hg in soils at the roasting site at Frbej?ene trate in order to verify the extreme pollution of ancient Hg ore roasting sites in the Idrija area and to establish their significance in the wider spatial contamination of soils and aquatic systems. Soil sampling was performed at the area of the former roasting site. The organic matter-rich surface soil layer (SOM) and underlying mineral soil were sampled at 63 sampling locations. Mercury speciation was performed using Hg thermo-desorption-AAS to distinguish cinnabar from potentially bioavailable forms. The results indicate extremely high Hg concentrations with a maximum of 37,000 mg/kg in SOM and 19,900 mg/kg in mineral soil. The established Hg median in soil was 370 mg/kg and in SOM 96.3 mg/kg. Spatial distributions of Hg in SOM and soil showed very high Hg contents in the central area and decreased rapidly with distance. The results of Hg thermo-desorption measurements indicated the presence of cinnabar (HgS) and Hg bound to organic or mineral soil matter. A significant portion (35–40%) of Hg in the investigated soil and SOM samples was comprised of non-cinnabar compounds, which are potentially bioavailable. It has been shown that soils contain high amounts of potentially transformable non-cinnabar Hg, which is available for surface leaching and runoff into the surrounding environment. Therefore, contaminated soils and roasted residues at the studied area are important for persistent Hg release into the aquatic ecosystem.     

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.     

Anthropogenic metal loads and their sources in stream sediments of the Me?a River catchment area (NE Slovenia)

The Me?a River Valley has been a center of mining, ore processing and iron- and steel-based metallurgical industry for more than 300 a. This paper deals with stream sediments draining this area. Loads of potentially toxic metals and metal-bearing phases were investigated 10 a after the cessation of Pb and Zn mining. Sediments in the upper Me?a River Valley show significant pollution with Pb and Zn as a consequence of mining and ore processing. The highest contents of Pb and Zn were found in the Me?a tributaries, which directly drain mine waste deposits (maximum values: 19,300 mg/kg Pb and 37,900 mg/kg Zn). These results reflect transport of contaminated material from mine waste sites and indicate that the inactive mine and its mine wastes are sources of metal contamination in the surrounding environment. Contents of Cr, Ni, Cu and Co are increased in the lower Me?a River Valley, in the area of Ravne, as a result of the iron and steel industry. The contribution of the Me?a River to the metal-load in the Drava River is evident.Metal-bearing phases, identified in stream sediments by SEM/EDS, are assigned to three areas, according to their source and genesis. The Me?ica mining district source area is characterized by ore minerals of geogenic/technogenic origin (cerussite, sphalerite, smithsonite and galena), the Ravne source area is characterized by technogenic trace metal-bearing Fe-alloys, Fe-oxides and spherical trace metal-oxides and the Me?a and Drava River catchment areas are represented by geogenic metal-bearing accessory and common rock-forming minerals, such as zircon, ilmenite, rutile, sphene, barite and monazite. SEM/EDS analyses of stream sediments agree well with the results of chemical analyses and they prove to be a very useful tool for identification of metal-bearing phases and their characterization according to source and genesis.     

Mercury pollution in two gold mining areas of the Brazilian Amazon

Gold has been exploited intensively in the Brazilian Amazon during the past fifteen years using garimpo methods (small-scale gold mining). In this study, two gold mining areas were investigated, the municipalities of Pocone and Alta Floresta located in the state of Mato Grosso. Central Brazil. The elemental mercury (Hg) used in amalgamating the gold, the final stage of the ore dressing process, has caused abnormal Hg concentrations in waterways. This has occurred principally in the Amazon region, where most of the ore prospected is alluvial. Background levels of metals were determined by analyzing sediments and soils located upstream of the anthropogenic inputs and unaffected by mining activities. The study aimed to evaluate the pollution level in sediments and soils, taking into account drainage waters directly affected by gold mining. ‘Geoaccumulation indexes’ (Igeo) of Hg in sediments from both study areas were used to assesses the pollution level in the aquatic environment. The geoaccumulation indexes of Hg in sediments of the Bento Gomes River in Pocone indicate a relatively high degree of pollution at some sites, even reaching class 4 (1.85 mg/kg). However, when the river reaches the Pantanal swamp, Hg concentrations drop considerably to 0.30 mg/kg. This drop seems to be due to accumulation of metals in the sediments of a lake (sampling site PG-24), which retains most of the sediments transported by the Bento Gomes River. Accumulation of metals in the lake also occurred for Cu, Pb, Zn, Fe and Mn. In the region of Alta Floresta, total Hg concentrations in sediments of the Teles Pires River were studied in the grain size fractions < 74 μm and > 74 μm. Hg concentrations in bottom sediments of this river were higher than those found in the Pocone region, with increases of 1.5 to 30 times the background, and thus reaching an Igeo up to class 5.     

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.     

Mercury speciation in tailings of the Idrija mercury mine

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 (Hg⁰) sorbed to mineral matrix components such as dolomite and Fe-oxyhydroxides became the predominant Hg binding form in addition to unbound Hg⁰ 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 Hg⁰ 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 Hg⁰ is higher than that of older tailings bearing mostly immobile cinnabar.     

50-year record and solid state speciation of mercury in natural and contaminated reservoir sediment

Contaminated fluvial sediments represent both temporary sinks for river-borne pollutants and potential sources in case of natural and/or anthropogenic resuspension. Reservoir lakes play a very important role in sediment dynamics of watersheds and may offer great opportunities to study historical records of river-borne particles and associated elements transported in the past. The fate and potential environmental impact of Hg depends on its abundance, its carrier phases and its chemical speciation. Historical Hg records and solid state Hg speciation were compared in sediments from two contrasting reservoirs of the Lot River (France) upstream and downstream from a major polymetallic pollution (e.g. Cd, Zn) source. Natural (geochemical background) and anthropogenic Hg concentrations and their relationships with predominant carrier phases were determined. The results reveal important historical Hg contamination (up to 35 mg kg⁻¹) of the downstream sediment, reflecting the historical evolution of industrial activity at the point source, i.e. former coal mining, Zn ore treatment and post-industrial remediation work. Single chemical extractions (ascorbate, H₂O₂, KOH) suggest that at both sites most (∼75%) of the Hg is bound to organic and/or reactive sulphide phases. Organo-chelated (KOH-extracted) Hg, representing an important fraction in the uncontaminated sediment, shows similar concentrations (∼0.02 mg kg⁻¹) at both sites and may be mainly attributed to natural inputs and/or processes. Although, total Hg concentrations in recent surface sediments at both sites are still very different, similar mono-methylmercury concentrations (up to 4 μg kg⁻¹) and vertical distributions were observed, suggesting comparable methylation-demethylation processes. High mono-methylmercury concentrations (4–15 μg kg⁻¹) in 10–40 a-old, sulphide-rich, contaminated sediment suggest long-term persistence of mono-methylmercury. Beyond historical records of total concentrations, the studied reservoir sediments provided new insights in solid state speciation and carrier phases of natural and anthropogenic Hg. In case of sediment resuspension, the major part of the Hg historically stored in the Lot River sediments will be accessible to biogeochemical recycling in the downstream fluvial-estuarine environment.     

Toxic metal contamination in the lateral lakes of the Coeur d'Alene River valley, Idaho

 The 11 lateral lakes of Coeur d'Alene River valley in northern Idaho have received heavy metal contamination from over a century of upstream mining. The lateral lakes lie within the flood plain of the Coeur d'Alene River, and in their bottom sediments is preserved a stratigraphic record of the upstream mining operations. To characterize the contaminated sediments in the lateral lakes, sampling techniques, including the Livingston piston corer and the Huttenen freeze box, have been developed by Quaternary geologists to preserve the vertical stratigraphy in the samples. From 26 cm to over 55 cm of undisturbed tailing sediments, commonly with “varve-like” features, have been found in each of the lateral lakes, with maximum concentrations by weight of lead at 3.8%, zinc at 3.4%, arsenic at 340 mg/kg, cadmium at 120 mg/kg and mercury at 7 mg/kg. The contamination in the lakes appears to be restricted to the shallow subsurface and heavy metal concentrations generally drop to background levels within a meter of depth. Received: 22 May 1998 · Accepted: 21 September 1998     

Heavy metal contamination in overbank sediments of the Geul river (East Belgium): Its relation to former Pb-Zn mining activities

Overbank sediments of the Geul River (East Belgium) are highly contaminated by the heavy metals Pb, Zn, and Cd due to former Pb-Zn mining activities in the drainage basin. Geochemical variations in vertical overbank sediment profiles sampled 1 km north of the mine tailings of Plombiéres allow metal fluxes back to the 17th century to be reconstructed. The vertical profiles are subdivided into three major units corresponding to different industrial periods based on sedimentological criteria as well as on the distribution of contaminants. Alluvial sediments with the highest heavy metal concentrations correspond to the major period of mining activity of the 19th century. The fact that Zn mining at the La Calamine open mine started before large-scale mining of the PbS-ZnS subsurface exploitations is reflected in the vertical profiles by an increase in Zn content before a marked increase in Pb and Cu. The regional extent of contamination in the alluvial deposits was evaluated on the basis of the geochemical analysis of sediments at depths of the 0–20 cm and 80–100 cm. Most of the upper samples are extremely contaminated. Significant local variations in heavy metal concentration in the lower samples are interpreted in terms of which overbank sediment horizon has been sampled at a depth of 80–100 cm. This indicates that blind sampling of overbank sediments to characterize the degree of contamination in shallow boreholes can give very erratic results.     

Transportation and evolution of trace element bearing phases in stream sediments in a mining – Influenced basin (Upper Isle River,France)

Arsenic-bearing stream sediments enter the Upper Isle River, an Au mining-influenced basin (France), by the discharge of mining sites, tailings runoff and weathering of mineralized veins in granites and gneiss. Some fresh ochreous As-rich deposits on the river banks and in floodplains are identified as additional As-rich point sources (As between 0.07 and 6.5 wt.%). The <63 μm fraction of stream sediments contains elevated As bulk concentrations, ranging from 160 to 890 mg/kg, compared to the geochemical background (70 mg/kg on average). It is also enriched in Cd, Hg and W. Spatial variations of these trace elements show 3 significant increases corresponding to the 3 drained mining districts. They decrease down river but are still enriched 30 km downstream of the mining districts due to downstream transportation. Three types of trace element-bearing phases have been identified as: (i) detrital primary sulfides, with high in situ As percentages (up to 43.7 wt.%). They also carry significant amounts of W according to the differences in chemical compositions of the total and light <63 μm fractions. These sulfide particles do not show any sign of alteration in the oxygenated stream sediments; (ii) Secondary Fe–Mn oxyhydroxides,some with very high in situ As₂O₅ concentrations (up to 59.8 wt.%) and with about 40% of the total Cd composition. They occur as fresh precipitates in the river banks and floodplains and as discrete particles in stream sediments and (iii) Al–Si fine-grained phases. Their major element composition is highly variable with in situ As₂O₅ concentrations ranging between 430 and 5020 mg/kg. This type of solid phase is also the major carrier of Hg.     

陕西潼关金矿区太峪河底泥重金属元素的含量及污染评价

通过对潼关金矿区太峪河和太峪水库底泥中重金属元素总量的调查,探讨了金矿开发活动中重金属元素对河流底泥的污染程度。研究结果表明,除As外,河流底泥中重金属元素的含量与尾矿渣中重金属元素的含量变化一致,表明其主要来源于尾矿渣,但又明显高于尾矿渣。在同一地点河流底泥中重金属元素的含量平均高出河水中的1048.61～666030.08倍,呈显著富集。以邻近地区不受工矿活动影响的河流底泥重金属元素的含量均值作为评价参比值,太峪河底泥受到了Hg、Pb、Cd、Cu、Zn元素的极度污染,单项污染超标倍数及综合污染指数法评价结果表明,Hg、Pb、Cd平均污染超标倍数达366.90、217.42和149.97,是底泥中最主要的污染元素。河流底泥重金属元素的综合污染指数高达278.97,表明河流的复合污染亦呈极度状态。太峪河底泥受重金属元素极度污染的现实提示,矿区的环境防治工作已刻不容缓。     

Mercury contamination and its potential health effects in a lead-zinc mining area in the karst region of Guangxi, China

Mercury contamination of the environment is of worldwide concern because of its global presence and its potent neurotoxicity. Mining, smelting and the electronics industry are the main sources of Hg pollution. However, few studies have been performed to investigate systemic Hg contamination in metal mining regions. In this study, concentrations of Hg in air, farmland soil, and crops were measured in a Pb-Zn mining area in the karst region of Guangxi, China. Key factors that could affect Hg distribution, such as the fate of waste ore and waste residue, were analyzed. Geo-statistical methods were adopted to analyze the characteristics of spatial structure and distribution of Hg. The results show that Hg contamination in this region is serious. The total mercury (T-Hg) content is far higher than the Level II Limit Value of Chinese Soil Standards of 0.30 mg kg⁻¹, showing obvious directional characteristics from WNW to ESE. Highest Hg concentrations were found in the WNW portion of the study area. The contamination of paddy soil is higher than that in dry farmland soil. The vertical distribution of T-Hg and its decrease with depth suggest that the important sources are waste water irrigation and the improper disposal of the waste ore and waste rock. The T-Hg concentrations in the agricultural products examined exceed the Chinese tolerance value (0.02 mg kg⁻¹ for rice and 0.01 mg kg⁻¹ for vegetables), indicating the seriousness of the problem. The ecological environment and the safety of food grown in this mining area are being affected, with the result that human health is possibly being affected.     

Mercury contamination in Marano Lagoon (Northern Adriatic sea,Italy): Source identification by analyses of Hg phases

Total Hg concentrations and Hg speciation were determined in bottom sediments of Marano lagoon to investigate the consequences of Hg phases on fish farms and shellfish cultivation areas. Mercury phases were separated into cinnabar (HgS) and non-cinnabar compounds, via a thermo-desorption technique, in surface and core sediments; both of which had been contaminated by industrial wastes and mining activity residues. The former are due to an industrial complex, which has been producing cellulose, chlor-alkali and textile artificial fibres since 1940. Processing and seepage wastewaters, which were historically discharged into the Aussa-Corno river system and therefore into the lagoon, have been significantly reduced since 1984 due to the construction of wastewater treatment facilities. The second source is the Isonzo River, which has been the largest contributor of Hg into the northern Adriatic Sea since the 16th century due to Hg mining at the Idrija mine (western Slovenia). Red cinnabar (HgS) derived from the mining area is mostly stable and insoluble under current environmental conditions. In contrast, organically bound Hg, such as Hg bound to humic acids, has the potential to be transformed into bioavailable Hg compounds (for example, methylmercury). The presence of the two Hg forms permitted each Hg source to be quantified. It also allowed the areas with the highest risk of Hg contamination from Hg-rich sediment to be identified; thus potentially avoiding the transfer of Hg from the sediment into the water column and eventually into living biota. The results show that Hg Enrichment Factors in bottom sediments exceed values of 10 and cinnabar dominates the central sector near the main tidal channel where tidal flux is more effective. Non-cinnabar compounds were found to be enriched in fine grained material and organic matter. In fact, up to 98% of total Hg at the Aussa-Corno river mouth and in the inner margin of the basin occurred in an organic form. This evidence, combined with the high contents of total Hg (4.1–6.6 μg g⁻¹ and EF > 10) measured in surface sediments, suggest that Hg in Marano lagoon is involved in biogeochemical transformations (e.g., methylation).     

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 pollution from artisanal mercury mining in Tongren, Guizhou, China

Concentrations of total Hg (T-Hg) were measured in mine waste, stream water, soil and moss samples collected from the Tongren area, Guizhou, China to identify potential Hg contamination to local environments, which has resulted from artisanal Hg mining. Mine waste contained high T-Hg concentrations, ranging from 1.8 to 900 mg/kg. High concentrations of Hg were also found in the leachates of mine waste, confirming that mine waste contains significant water-soluble Hg compounds. Total Hg distribution patterns in soil profiles showed that top soil is contaminated with Hg, which has been derived from atmospheric deposition. Data suggest that organic matter plays an important role in the binding and transport of Hg in soil. Elevated T-Hg concentrations (5.9–44 mg/kg) in moss samples suggest that atmospheric deposition is the dominant source of Hg to local terrestrial ecosystems. Concentrations of T-Hg were highly elevated in stream water samples, varying from 92 to 2300 ng/L. Particulate Hg in water constituted a large proportion of the T-Hg and played a major role in Hg transport. Methyl–Hg (Me–Hg) concentrations in the water samples was as high as 7.9 ng/L. Data indicate that Hg contamination is dominantly from artisanal Hg mining in the study area, but the extent of Hg contamination is dependent on the mining history and the scale of artisanal Hg mining.     

Arsenic and antimony contamination of waters,stream sediments and soils in the vicinity of abandoned antimony mines in the Western Carpathians,Slovakia

Environmental contamination with As and Sb caused by past mining activities at Sb mines is a significant problem in Slovakia. This study is focused on the environmental effects of the 5 abandoned Sb mines on water, stream sediment and soil since the mines are situated in the close vicinity of residential areas. Samples of mine wastes, various types of waters, stream sediments, soils, and leachates of the mine wastes, stream sediments and selected soils were analyzed for As and Sb to evaluate their geochemical dispersion from the mines. Mine wastes collected at the mine sites contained up to 5166 mg/kg As and 9861 mg/kg Sb. Arsenic in mine wastes was associated mostly with Fe oxides, whereas Sb was present frequently in the form of individual Sb, Sb(Fe) and Fe(Sb) oxides. Waters of different types such as groundwater, surface waters and mine waters, all contained elevated concentrations of As and Sb, reaching up to 2150 μg/L As and 9300 μg/L Sb, and had circum-neutral pH values because of the buffering capacity of abundant Ca- and Mg-carbonates. The concentrations of Sb in several household wells are a cause for concern, exceeding the Sb drinking water limit of 5 μg/L by as much as 25 times. Some attenuation of the As and Sb concentrations in mine and impoundment waters was expected because of the deposition of metalloids onto hydrous ferric oxides built up below adit entrances and impoundment discharges. These HFOs contained >20 wt.% As and 1.5 wt.% Sb. Stream sediments and soils have also been contaminated by As and Sb with the peak concentrations generally found near open adits and mine wastes. In addition to the discharged waters from open adits, the significant source of As and Sb contamination are waste-rock dumps and tailings impoundments. Leachates from mine wastes contained as much as 8400 μg/L As and 4060 μg/L Sb, suggesting that the mine wastes would have a great potential to contaminate the downstream environment. Moreover, the results of water leaching tests showed that Sb was released from the solids more efficiently than As under oxidizing conditions. This might partly explain the predominance of Sb over As in most water samples.     

Mineralogy and the release of trace elements from slag from the Hegeler Zinc smelter,Illinois (USA)

Slag from the former Hegeler Zn-smelting facility in Illinois (USA) is mainly composed of spinifex Ca-rich plagioclase, fine-grained dendritic or coarse-grained subhedral to anhedral clinopyroxenes, euhedral to subhedral spinels, spherical blebs of Fe sulfides, silicate glass, and less commonly fayalitic olivine. Mullite and quartz were also identified in one sample as representing remnants of the furnace lining. Secondary phases such as goethite, hematite and gypsum are significant in some samples and reflect surficial weathering of the dump piles or represent byproducts of roasting. A relatively rare Zn-rich material contains anhedral willemite, subhedral gahnite, massive zincite, hardystonite and a Zn sulfate (brianyoungite), among other phases, and likely represents the molten content of the smelting furnace before Zn extraction. The bulk major-element chemistry of most slag samples is dominated by SiO₂, Al₂O₃, Fe₂O₃ and CaO. The bulk composition of the slag suggests a high viscosity of the melt and the mineralogy suggests a high silica content of the melt. Bulk slag trace-element chemistry shows that the dominant metal is Zn with >28.4 wt.% in the Zn-rich material and between 212 and 14,900 mg/kg in the other slags. The concentrations of other trace elements reach the following: 45 mg/kg As, 1170 mg/kg Ba, 191 mg/kg Cd, 242 mg/kg Co, 103 mg/kg Cr, 6360 mg/kg Cu, 107 mg/kg Ni, and 711 mg/kg Pb.     

Sources of mercury to San Francisco Bay surface sediment as revealed by mercury stable isotopes

Mercury (Hg) concentrations and isotopic compositions were examined in shallow-water surface sediment (0-2 cm) from San Francisco (SF) Bay to determine the extent to which historic Hg mining contributes to current Hg contamination in SF Bay, and to assess the use of Hg isotopes to trace sources of contamination in estuaries. Inter-tidal and wetland sediment had total Hg (Hg_T) concentrations ranging from 161 to 1529 ng/g with no simple gradients of spatial variation. In contrast, inter-tidal and wetland sediment displayed a geographic gradient of δ²⁰²Hg values, ranging from −0.30‰ in the southern-most part of SF Bay (draining the New Almaden Hg District) to −0.99‰ in the northern-most part of SF Bay near the Sacramento-San Joaquin River Delta. Similar to SF Bay inter-tidal sediment, surface sediment from the Alviso Slough channel draining into South SF Bay had a δ²⁰²Hg value of −0.29‰, while surface sediment from the Cosumnes River and Sacramento-San Joaquin River Delta draining into north SF Bay had lower average δ²⁰²Hg values of −0.90‰ and −0.75‰, respectively. This isotopic trend suggests that Hg-contaminated sediment from the New Almaden Hg District mixes with Hg-contaminated sediment from a low δ²⁰²Hg source north of SF Bay. Tailings and thermally decomposed ore (calcine) from the New Idria Hg mine in the California Coast Range had average δ²⁰²Hg values of −0.37 and +0.03‰, respectively, showing that Hg calcination fractionates Hg isotopes resulting in Hg contamination from Hg(II) mine waste products with higher δ²⁰²Hg values than metallic Hg(0) produced from Hg mines. Thus, there is evidence for at least two distinct isotopic signals for Hg contamination in SF Bay: Hg associated with calcine waste materials at Hg mines in the Coast Range, such as New Almaden and New Idria; and Hg(0) produced from these mines and used in placer gold mines and/or in other industrial processes in the Sierra Nevada region and SF Bay area.     

珠江三角洲第四纪沉积物Cd元素的分布特征及成因

根据珠江三角洲平原区44个钻孔揭示的第四系,对晚更新世以来沉积物的地球化学特征进行了系统分析,结合沉积物粒度,探讨了珠江三角洲平原区第四纪沉积物Cd的分布特征、高含量来源及迁移富集规律。研究结果表明：①珠江三角洲第四纪沉积物的Cd含量地区差异较大,西江、北江冲积区为主要富集区,而潭江和东江冲积区为背景区。②物质来源、沉积物粒度、沉积环境与有机质含量共同影响了珠江三角洲第四纪沉积物Cd的含量分布,西江、北江冲积区受控于富Cd的泥盆系、石炭系砂页岩,而东江、潭江冲积区主要由贫Cd的燕山期花岗岩等限定;沉积物平均粒径（φ值）与Cd含量存在显著正相关关系;另外,温暖湿润、海陆交互作用强烈的沉积环境与富含有机质的地区有利于Cd的聚积富集。③西江、北江流域相对富Cd岩石风化的产物,特别是具高强度Cd含量的铅锌多金属矿区,是西江、北江冲积区Cd高含量的主要来源。④珠江三角洲第四纪沉积物Cd的高含量区分成西江、北江西北部和东南濒海两大片区,究其原因,前者由区域发育的铅锌多金属矿控制,后者则受海陆交互作用沉积环境的影响。     

Ordinary kriging and indicator kriging in the cartography of trace elements contamination in São Domingos mining site (Alentejo, Portugal)

The abandoned pyrite mine of São Domingos, in the southeast Portugal is still an acid mine drainage generator and a source for trace elements pollution. This study aims to evaluate and map the soils and sediments chemical pollution. With this purpose three test sites located in the vicinities of the mine were sampled for soils, sediments and mining waste materials. The samples were analysed for pH, organic carbon, iron oxides and total content of As, Cu, Cr, Hg, Pb, Sb, U, Zn, Mn, S, Fe Al, Ca, K, Mg and P. The hyperspectral image of the test sites was acquired using the aero transported sensor HymapTM. Chemical analysis and hyperspectral images data were processed to estimate the contamination maps by multivariate data analysis, ordinary kriging, cokriging and indicator kriging methodologies.The test sites located downstream the mine open pit, are highly contaminated mainly in As, Hg, Pb and Sb, but no contamination was found in the third test site, upstream the mining site. The acid mining drainage seems to be the main spreading agent of chemical contaminants mostly originating from the mine waste materials. Factorial analysis and the geostatistical methodologies allowed several approaches for the contamination cartography of mining areas.