Environmental impacts of the abandoned mercury mine in Podljubelj, Slovenia

The Podljubelj mercury mine lies in the NW part of Slovenia. The ore is of hydrothermal-vein type. The ore deposit was exploited between the years 1557 and 1902. Total production of the mine was 110000 tons of ore （360 tons of Hg）. A smelter located close to the mine had been in operation since 1855. The waste material from the mine and the smelter was dumped in close vicinity of the mine. Total quantity of the waste has been estimated at 170000 tons. In order to establish environmental impacts, soil and stream sediment samples were investigated. Soil samples were collected at two different depths （horizons A and B） in a 100 m grid within an 88 ha area. In the vast area also 11 samples of stream sediments were considered. Heavy metals were determined by means of cold vapor atomic absorption spectrometry CV-AAS after aqua regia digestion. Based on the chemical analyses of samples, the estimated mercury mean for soils is 3.67 mg/kg （0.35-244 mg/kg） for horizon A and 1.39 mg/kg （0.17-71.7 mg/kg） for horizon B. The estimated mercury mean for stream sediments is 0.64 mg/kg （0.065-1.36 mg/kg）. The concentrations of mercury in soils generally decrease with depth and distance from the mine. The highest content of Hg was determined in a sample taken in the immediate vicinity of the smelter （719 mg/kg）. The results have shown that on the 9 ha of the study area, the contents of Hg in soils exceeded the officially set limit value for soils （10 mg/kg）. High contents of Hg in soil around the abandoned smelter are a consequence of former atmospheric emissions and technological losses. High contents of Hg were also found in the mine and smelter waste dump. At the edges of the study area and in the samples of stream sediments, Hg concentrations are low.     

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.     

Mercury contents in the vertical profiles through alluvial sediments as a reflection of mining in Idrija (Slovenia)

The influence of geomorphological factors to Hg contamination of the Idrijca River alluvial sediments because of the historical mining and ore roasting activities has been studied. Main source of Hg in alluvial sediments was dumping of ore roasting residues and mining waste into the river channel and its erosion downstream. The position of the material in relation to the geomorphological properties is highly related with its Hg content. Floodplains were found to be the most contaminated geomorphological units (mean Hg content 335 mg/kg), with Hg concentration rapidly dropping in the first terrace (155 mg/kg). The least contaminated material was found in the higher terraces (3.8 mg/kg). Sampling upstream Idrija (average Hg content is 22.1 mg/kg) shows that not only mine and ore roasting plant increased Hg levels in alluvial deposits but also contaminated sites upstream Idrija contribute to Hg contamination. Geochemical background for alluvial sediments for this area is estimated to be 0.75 mg/kg. Downstream Idrija, 9 hotspots were determined where highly contaminated material is actively eroded and carries a high risk of further contamination of the So?a River and northern Adriatic Sea ecosystems.     

Geochemical characteristics of acid mine drainage and sediments from coal mines, Shanxi Province, China

In this study, geochemical characteristics of acid mine drainage （AMD） and its sediments from the Malan and Sitai coalmines, Shanxi Province, China, were investigated. Many analytical approaches such as IC, ICP-MS, XRD, XRF, and modeling calculation of hydrogeochemistry using PHREEQCI software were employed. The AMD is characterized by higher concentrations of iron and sulfate, a low pH, and elevated concentrations of a wide variety of heavy metals. The results of modeling calculation by PHREEQCI software demonstrate the metals in AMD are present mainly as Me^n＋ and MeSO4^n-2 species. The sediments of AMD are composed mainly of iron-beating minerals such as goethite and schwertmannite, which are controlled by pH, Fe and SO4^2- concentrations. The schwertmannite mineral has been found for the first time in China.     

江西九江城门山铜矿汞气测量找矿方法

在城门山铜矿系统开展了土壤壤中汞、热释汞、全汞的测量.结果表明,花岗闪长斑岩和破碎带上覆的土壤中具有明显的壤中汞气、热释汞的富集,土壤中汞气的主要源是深部的硫化物矿体.汞异常能够准确地反映出下伏矿体的赋存部位.土壤全汞因为本底汞的影响不能很好地反映矿化信息,利用土壤全量汞与热释汞含量的比值来抑制本底汞,突显热释汞,能更清晰地显示深部的矿化信息,是示踪深部矿化信息的有用的地球化学指标.     

江西九江城门山铜矿汞气测量找矿方法

在城门山铜矿系统开展了土壤壤中汞、热释汞、全汞的测量。结果表明,花岗闪长斑岩和破碎带上覆的土壤中具有明显的壤中汞气、热释汞的富集,土壤中汞气的主要源是深部的硫化物矿体。汞异常能够准确地反映出下伏矿体的赋存部位。土壤全汞因为本底汞的影响不能很好地反映矿化信息,利用土壤全量汞与热释汞含量的比值来抑制本底汞,突显热释汞,能更清晰地显示深部的矿化信息,是示踪深部矿化信息的有用的地球化学指标。     

江西九江城门山铜矿汞气测量找矿方法

在城门山铜矿系统开展了土壤壤中汞、热释汞、全汞的测量。结果表明,花岗闪长斑岩和破碎带上覆的土壤中具有明显的壤中汞气、热释汞的富集,土壤中汞气的主要源是深部的硫化物矿体。汞异常能够准确地反映出下伏矿体的赋存部位。土壤全汞因为本底汞的影响不能很好地反映矿化信息,利用土壤全量汞与热释汞含量的比值来抑制本底汞,突显热释汞,能更清晰地显示深部的矿化信息,是示踪深部矿化信息的有用的地球化学指标。     

Distribution and behavior of heavy metals in a river polluted by acid mine drainage in the Dabaoshan mine area, China

Acid mine drainage （AMD） has been recognized as a major environmental pollution problem over past decades. This pollutant effluent is complex and is characterized by elevated concentrations of iron and sulfate, low pH, and high concentrations of a wide variety of metals depending on the host rock geology. Massive inadvertent discharges from acid mines have given rise to dramatic cases of ecological damage. These events indicate an improved understanding of the mechanism controlling metal transport to the river is important, since the aquatic ecology will be affected, to some degree, dependent on the phase （dissolved or particulate） in which the metal is transported. In this study, polluted water samples were collected along the Hengshi River near the Dabaoshan mine, Guangdong, China, in April 2005. The concentrations of dissolved Cu, Zn, Cd and Pb have been determined using ICP-MS and the chemical speciation of those metals in suspended particles was examined using BCR methods and SEM/EDX mineralogical analysis. Combining these two sets of data, the intention was to develop geochemical concepts, which explain the behavior of Cu, Zn, Cd and Pb in particle-water interactions of heavy metals in AMD. The results show that the dissolved heavy metals exhibited non-conservative behavior in the Hengshi River. The dissolved and particulate Cu, Zn, Cd and Pb have the similar spatial distribution, which decreased gradually along the river except in the lower reaches because of the absorption-desorption between dissolved and particulate phases. Although the metal concentrations in both phases were elevated, dissolved metals were dominant and had the maximum concentrations in the low pH region.     

Heavy metal geochemistry of the acid mine drainage discharged from the Hejiacun uranium mine in central Hunan,China

The acid mine drainage (AMD) discharged from the Hejiacun uranium mine in central Hunan (China) was sampled and analyzed using ICP-MS techniques. The analyzing results show that the AMD is characterized by the major ions Fe_Total, Mn, Al and Si, and is concentrated with heavy metals and metalloids including Cd, Co, Ni, Zn, U, Cu, Pb, Tl, V, Cr, Se, As and Sb. During the AMD flowing downstream, the dissolved heavy metals were removed from the AMD waters through adsorption onto and co-precipitation with metal-oxhydroxides coated on the streambed. Among these metals, Cd, Co, Ni, Zn, U, Cu, Pb and Tl are negatively correlated to pH values, and positively correlated to major ions Fe, Al, Si, Mn, Mg, Ca and K. The metals/metalloids V, Cr, Se, As and Sb are conservative in the AMD solution, and negatively-correlated to major ions Na, Ca and Mg. Due to the above different behaviors of these chemical elements, the pH-negatively related metals (PM) and the conservative metals (CM) are identified; the PM metals include Cd, Co, Ni, Zn, U, Cu, Pb and Tl, and the CM metals V, Cr, Se, As and Sb. Based on understanding the geochemistry of PM and CM metals in the AMD waters, a new equation: EXT = (Acidity + PM)/pH + CM × pH, is proposed to estimate and evaluate extent of heavy-metal pollution (EXT) of AMD. The evaluation results show that the AMD and surface waters of the mine area have high EXT values, and they could be the potential source of heavy-metal contamination of the surrounding environment. Therefore, it is suggested that both the AMD and surface waters should be treated before they are drained out of the mine district, for which the traditional dilution and neutralization methods can be applied to remove the PM metals from the AMD waters, and new techniques through reducing the pH value of the downstream AMD waters should be developed for removal of the CM metals.     

Microbial mercury transformations in marine,estuarine and freshwater sediment downstream of the Idrija Mercury Mine,Slovenia

The Idrija Mine, the second largest Hg mine in the world, ceased operation in 1995, but still delivers large quantities of Hg downstream including into the northern Adriatic Sea, 100 km away. Transformation of Hg species in sediment in sites over 60 km from the mine, including marine sites in the Adriatic Sea, was measured to determine the ability of the system to transform and mobilize Hg and to produce methylmercury (MeHg). Cores from a freshwater impoundment, a brackish estuarine site, and three marine sites in the Gulf of Trieste were sectioned anaerobically, and Hg methylation and MeHg demethylation activities determined using radio-techniques (²⁰³Hg for methylation and ¹⁴C-MeHg for demethylation). Total and dissolved Hg and MeHg were determined as were other geochemical parameters. In addition, rates of SO₄ reduction were determined in marine sediment using a ³⁵S technique. Mercury was readily methylated and demethylated at all sites. Marine sediment was investigated in winter and summer with rates of Hg transformation and SO₄ reduction corresponding only in winter. Methylation of Hg in summer displayed subsurface peaks that may have been influenced by bioturbation. Total Hg and MeHg were most abundant in the freshwater, estuarine, and near-shore marine sites, but dissolved pore water Hg and MeHg were highest in the estuarine region where S cycling appeared ideal for the mobilization of Hg. The impoundment sediment also seemed to be a ‘hotspot’ of Hg transformations. MeHg demethylation occurred via the oxidative demethylation pathway (CO₂ produced from MeHg), except in surficial sediment offshore in the Gulf during winter, where sediment was more oxidizing and significant amounts of CH₄ were liberated during MeHg degradation via reductive demethylation. The CH₄ formation was likely due to an increased influence from the expression of MeHg degradative enzymes encoded by the mer detoxification bacterial genetic system. The freshwater site also liberated CH₄ from MeHg, but it appeared to be due to oxidative demethylation by methanogenic bacteria.     

Pollution of Osheepcheon Creek by abandoned coal mine drainage in Dogyae area,eastern part of Samcheok coal field,Kangwon-Do,Korea

Osheepcheon Creek running through the Dogyae area is being polluted by the influx of the abandoned coal mine drainage. Generally, the more polluted water has lower pH and Eh and higher conductivity values. The concentrations of Mg, Ca, Fe, SO₄, and some trace elements, such as Cd, Co, Cr, Mo, Ni, Pb, Rb, Sr, U and Zn, are tens to hundreds of times more concentrated in the abandoned coal mine drainage than in the unpolluted streamwater. However, most immobile toxic pollutants from the mine drainage are quickly removed from the streamwater by the precipitation of amorphous Fe hydroxide and sorption on the precipitated Fe hydroxide. The fast removal of the pollutants from the streamwater maintains the water quality of the creek as acceptable at most places along the stream path, except where the abandoned coal mine drainage flows in. However, the creek has the potential of deteriorating quickly if the mine drainage is allowed to be continuously combined with the streams. A function of pH, Eh, and conductivity has been developed with discriminant function analysis for the purpose of easy, fast, and inexpensive measurement of the degrees of pollution of the streams. The estimated pollution of the streams with the discriminant function are consistent with what the chemical compositions of the water samples indicate. The pollution map of the study area was constructed from the calculated scores with the discriminant function. The pollution map suggests that the pollutants mainly come from the west side of Osheepcheon Creek. Thus, the abandoned coal mine drainage from the west side has to be appropriately treated as soon as possible to prevent Osheepcheon Creek from being further polluted. Considering the topography, climate, and the amount of the mine drainage, an active treatment method is recommended.     

土壤／沉积物中汞污染地球化学及污染防治措施研究

本文综述了汞的来源,介绍了汞的形态及形态分析方法的研究进展,讨论了影响汞吸附和解吸的主要因素,比较了对土壤/沉积物中汞污染进行风险评价的方法,提出了生物修复、减少汞污染的排放等治理我国汞污染的有效措施。最后对汞在土壤/沉积物中的地球化学行为等研究方面进行了展望。     

Mercury pollution in the atmosphere-soil-biology ecosystem along the trunk road in Guilin

Based on the mercury distribution in soil, atmosphere and plant in seven sections beside the trunk road, some advances are obtained： （1） Mercury content of fuel oil of petrol station in Guilin is 3.66-9.74 ng/g, higher than that reported by other countries （0.7-3.2 ng/g）. The higher the number of petrol, the lower the content. Number 90 petrol widely used is the highest （9.74 ng/g）. （2） Mercury content in soil is commonly 0.30-0.80 μg/g near the road, （0.30-2.60 μg/g） besides the street, both are higher than the average of Guilin background value （0.204 μg/g）. Mercury content in vegetable near the road is generally 0.025-0.055 μg/g, higher than that far away from the road （0.022-0.038 μg/g）. The content in cinnamon leaves on both sides of the street is 0.06-0.16 μg/g, also higher than that far away from the street （0.051-0.067 μg/g）. Guilin Highway atmospheric mercury content is usually 7-12 ng/m^3, higher than the mean background value （4.4-6.6 ng/m^3）. Atmospheric mercury content near rural roads is below the level on urban roads. The atmospheric mercury content increases apparently in traffic-intensive stations and intersections. （3） The average concentration of mercury in vegetables is mostly 0.025-0.055 μg/g. Mercury content in various tissues of vegetable follows the order of leaves （mostly 0.044）.09 μg/g）〉roots （mostly 0.02-0.05 lag/g）〉stems （mostly 0.01-0.04 μg/g）. （4） The distribution of mercury in soil, plants and atmosphere near the road is of certain similarity, with a single peak, nearly symmetrical. As far away from road, the content reduces gradually, which shows the release of exhaust gas mercury is the main source of atmospheric mercury pollution.     

贵州滥木厂汞矿区土壤与大气间气态汞交换通量及影响因素研究

利用动力学通量箱-大气自动测汞仪联用技术,分别于2002年12月和2003年5月对贵州省西南部滥木厂汞矿区5个采样点的土壤汞释放通量进行了系统的测定.结果表明该区土壤是大气的重要汞释放源.5个采样点土壤释汞通量最高值达10 543.7 ng/(m2·h),平均值最高达(2 283.3±2 434.2)ng/(m2·h)(n=152).结果显示土壤总汞含量与土壤释汞通量关系密切,是决定土壤汞释放的内在因素,光照、温度、湿度和大气汞含量等环境因素与土壤释汞通量有较好的相关性,对土壤汞的释放有显著的影响.     

贵州万山汞矿区稻田土壤汞的分布及污染特征

受历史汞矿开采活动影响,万山汞矿区稻田遭受了严重的汞污染.为了查明万山汞矿区稻田土壤的汞污染现状以及评估其环境质量改善情况,系统采集了受汞矿区影响的五条主干河流沿岸稻田土壤进行汞含量分析,评价总汞和甲基汞污染程度及其生态风险,并与2008 年以来该区域稻田土壤汞数据进行对比.结果表明,研究区稻田土壤的总汞含量为0.21...     

Transport and sediment–water partitioning of trace metals in acid mine drainage: an example from the abandoned Kwangyang Au–Ag mine area, South Korea

Transport and sediment–water partitioning of trace metals (Cr, Co, Fe, Pb, Cu, Ni, Zn, Cd) in acid mine drainage were studied in two creeks in the Kwangyang Au–Ag mine area, southern part of Korea. Chemical analysis of stream waters and the weak acid (0.1 N HCl) extraction, strong acid (HF–HNO₃–HClO₄) extraction, and sequential extraction of stream sediments were performed. Heavy metal pollution of sediments was higher in Chonam-ri creek than in Sagok-ri creek, because there is a larger source of base metal sulfides in the ores and waste dump upstream of Chonam-ri creek. The sediment–water distribution coefficients (K _d) for metals in both creeks were dependent on the water pH and decreased in the order Pb ≈ Al > Cu > Mn > Zn > Co > Ni ≈ Cd. K _d values for Al, Cu and Zn were very sensitive to changes in pH. The results of sequential extraction indicated that among non-residual fractions, Fe–Mn oxides are most important for retaining trace metals in the sediments. Therefore, the precipitation of Fe(–Mn) oxides due to pH increase in downstream sites plays an important role in regulating the concentrations of dissolved trace metals in both creeks. For Al, Co, Cu, Mn, Pb and Zn, the metal concentrations determined by 0.1 N HCl extraction (Korean Standard Method for Soil Pollution) were almost identical to the cumulative concentrations determined for the first three weakly-bound fractions (exchangeable + bound to carbonates + bound to Fe–Mn oxides) in the sequential extraction procedure. This suggests that 0.1 N HCl extraction can be effectively used to assess the environmentally available and/or bioavailable forms of trace metals in natural stream sediments.     

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.     

湖泊沉积物中重金属的环境地球化学

概要地回顾了近年来国内外湖泊沉积物中重金属环境污染方面的研究成果,介绍了湖相沉积物重金属研究的主要内容、方法和可能的发展方向。认为就重金属成因方面应加强区分其主要来源是岩石和矿物风化的碎屑产物、大气降尘、人类活动等的研究;重金属污染方面更应重视污染物质的生物有效性、迁移转化机理和重金属“二次污染”的研究;研究手段上,注重运用同位素示踪与定年技术来研究重金属的来源和污染历史,应用高分辨率沉积物钻心研究环境的变迁。最后提出加强多学科的综合研究,建立中国湖泊基准数据库,为探讨湖泊湿地的可持续发展提供依据。     

武汉城市湖泊汞的环境地球化学评价

汞由于其在环境中的持久性、生物地球化学可循环性以及潜在的生态威胁性而受到格外关注。对武汉远郊、城乡结合部和市区三种环境中6个湖泊的水、沉积物和生物(鱼)中汞污染特征进行了调查采样,用原子荧光光谱仪进行了汞含量的测定。采用Hakanson提出的潜在生态危害指数法直接评价了武汉湖泊汞的生态效应。结果表明,与国家食品卫生标准鱼肉中汞含量(≤300ng/g)相比,除梁子湖乌鱼(汞含量为676ng/g)外,6个湖泊3种鱼肉中汞含量均未超标,表明武汉城市湖泊汞元素尚未造成明显的生态效应;与国家Ⅲ类水质汞含量标准(0.1μg/L)相比,除金银湖水汞含量(0.137μg/L)略有超标外,其他湖水汞含量分布在0.048～0.081μg/L之间,均在合格标准线以下,武汉地区湖水中重金属汞污染不严重,不会构成严重的环境问题;应用Hakanson评价模型,据单个金属的潜在生态危害系数,排出所研究湖泊沉积物汞污染程度的序列为:东湖>墨水湖>金银湖>梁子湖>汤逊湖>鲁湖。     

河流沿岸土壤对上游矿山及矿山开发的环境地球化学响应——以广西刁江流域为例

刁江流域上游的矿山和矿山开发引发了显著的土壤环境地球化学变化,突出表现是沿岸形成了严重的土壤重金属污染带。污染带的分布与近20多年来的洪水淹没区和引水灌溉区呈现高度的一致性。上游地带的土壤污染区有明显的尾砂沉积,污染呈显性状态,而下游地带的尾砂沉积现象不明显,污染表现为隐性。无论是上游还是下游,土壤中的As、Pb、Zn、Cd含量均异常高。水田的犁底层对污染物质具有明显的隔断作用,而旱地淀积层中的污染物含量比较高,对污染物质的隔断作用不明显。污染耕地上生产的玉米中的Cd、Pb、Zn含量和大米中的Cd、Pb含量超过国家食品卫生标准。