Mineralogical and geochemical alteration of Hitura sulphide mine tailings with emphasis on nickel mobility and retention

Weathering of Hitura (W Finland) nickel sulphide mine tailings and release of heavy metals into pore water was studied with mineralogical (optical and electron microscopy, X-ray diffraction) and geochemical methods (selective extractions). Tailings were composed largely of serpentine, micas and amphiboles with only minor carbonates and sulphides. Sulphides, especially pyrrhotite, have oxidized intensively in the shallow tailings in 10–15 years, but a majority of the tailings have remained unchanged. Oxidation has resulted in depletion of carbonates, slightly decreased pH, and heavy metal (Ni, Zn) release in pore water as well as in the precipitation of secondary Fe precipitates. Nevertheless, in the middle of the tailings area, where the oxidation front moves primarily downward, released heavy metals have been adsorbed and immobilized with these precipitates deeper in the oxidation zone. In contrast to what was seen in pore water pH, but in accordance with static tests of the previous studies, the neutralisation potential ratio (NPR) calculated based on the mineralogical composition and the total sulphur content suggested that tailings are ‘not potentially acid mine drainage (AMD) generating’. However, the calculated buffering capacity of the tailings resulted largely from the abundant serpentine because of the low carbonate content. Despite its slow weathering rate, serpentine may buffer the acidity to some extent through ion exchange processes in fine ground tailings. Nevertheless, in practice, acid production capacity of the tailings depends primarily on the balance between Ca–Mg carbonates and iron sulphides. NPR calculation based on carbonate and sulphur contents suggested, that the Hitura tailings are ‘likely AMD generating’. The study shows that sulphide oxidation can be significant in mobilisation of heavy metals even in apparently non-acid producing, low sulphide tailings. Therefore, prevention of oxygen diffusion into tailings is also essential in this type of sulphide tailings.     

Immobilization of toxic elements in mine residues derived from mining activities in the Iberian Pyrite Belt (SW Spain): Laboratory experiments

In the mining environments of the Iberian Pyrite Belt (IPB), the oxidation of sulphide wastes generates acid drainage with high concentrations of SO₄, metals and metalloids (Acid Mine Drainage, AMD). These acid and extremely contaminated discharges are drained by the fluvial courses of the Huelva province (SW Spain) which deliver high concentrations of potentially toxic elements into the Gulf of Cádiz. In this work, the oxidation process of mine tailings in the IPB, the generation of AMD and the potential use of coal combustion fly ash as a possible alkaline treatment for neutralization of and metal removal from AMD, was studied in non-saturated column experiments. The laboratory column tests were conducted on a mine residue (71.6 wt% pyrite) with artificial rainfall or irrigation. A non-saturated column filled solely with the pyrite residue leached solutions with an acid pH (approx. 2) and high concentrations of SO₄ and metals. These leachates have the same composition as typical AMD, and the oxidation process can be compared with the natural oxidation of mine tailings in the IPB. However, the application of fly ash to the same amount of mine residue in another two non-saturated columns significantly increased the pH and decreased the SO₄ and metal concentrations in the leaching solutions. The improvement in the quality of leachates by fly ash addition in the laboratory was so effective that the leachate reached the pre-potability requirements of water for human consumption under EU regulations. The extrapolation of these experiments to the field is a promising solution for the decontamination of the fluvial courses of the IPB, and therefore, the decrease of pollutant loads discharging to the Gulf of Cádiz.     

缓冲期碳酸盐型尾矿重金属释放机制——柱淋滤实验研究

碳酸盐型尾矿在缓冲期/中性矿山废水(NMD)释放期的重金属污染问题易被忽视。本文以广西大厂锡石-硫化物尾矿作为研究对象,采用柱淋滤实验方法,探讨碳酸盐型尾矿在缓冲期重金属的释放机制,为此类型尾矿重金属污染的防治提供依据。实验结果表明,大厂尾矿在缓冲期(约7年,pH值为6. 6～8. 0)存在Sb、Zn、Cd、As(Pb)释放污染问题。在尾矿堆放初期(0. 5年,pH值由7. 6降至7. 2),Zn、Sb、Cd快速、大量释出;中期(0. 5～2. 5年,pH值由7. 2波动升高至8. 0),Sb较平稳释出;后期(2. 5～7年,pH值变化范围为8. 0～6. 6,呈降低趋势),受气温及pH值影响,As、Sb(Pb)呈波动或间歇振荡释出,即在夏季高温、pH值较高时,释出元素浓度较高,反之,在冬季低温、pH值较低时,释出元素浓度较低。重金属的释放与尾矿中硫化物的氧化程度高低及氧化先后顺序有关。这些矿物的氧化顺序大致为:闪锌矿(Zn、Cd)、辉锑锡铅矿(Sb)→脆硫锑铅矿(Sb)→毒砂(As)、方铅矿(Pb)。因此,对于(广西大厂)碳酸盐型尾矿在缓冲期的重金属污染应分阶段、季节(夏季),采取有针对性的防治措施;在缓冲期(7年)后应注意尾矿酸性矿山废水(AMD)+重金属(如As、Sb)复合污染的防治。     

Oxygen penetration and subsequent reactions in flooded sulphidic mine tailings: a study at Stekenjokk,northern Sweden

A study of O₂ penetration and pore water geochemistry of the flooded tailings at Stekenjokk has been performed. The results show that there is a diffusion of elements from the tailings pore water to the overlying water. The presence of elements such as Ca, Mg, S, Si, Ba and Sr are likely the result of diffusion of older process water trapped in the tailings. Oxygen concentrations in the tailings measured with microelectrodes show that there is O₂ available down to 16 to 17 mm depth in the tailings. Pore water analyses show that there are subsurface maxima for the elements Cu, Zn, Ni, Co and Cd at depths of 0.25 to 2.75 cm. The highest concentrations of almost all elements were found where previously oxidised material was deposited before the flooding. Lower pH is measured in the uppermost part of the tailings compared with the pond water and the tailings pore water at depth. Oxidation of sulphides in the uppermost part of the tailings is probably occurring. A decrease in oxidation rate can be expected in the future due to deposition of organic material at the tailings surface. Flooding seems to be an efficient remediation method at Stekenjokk.     

Formation and composition of cemented layers in low-sulphide mine tailings, Laver, northern Sweden

Cemented layers (hardpans) are common in carbonate or sulphide-rich mine tailings and where pyrrhotite is the predominating Fe-sulphide. Laver, northern Sweden, is an abandoned Cu-mine where the tailings have low pyrrhotite content, almost no pyrite and no carbonates. Two cemented layers at different locations in the Laver tailings impoundment were investigated, with the aim to determine their effects on metal mobility. The cementing agents were mainly jarosite and Fe-oxyhydroxides in the layer formed where the tailings have a barren surface, whereas only Fe-oxyhydroxides were identified below grass-covered tailings surface. Arsenic was enriched in both layers which also exhibit high concentrations of Mo, V, Hg and Pb compared to unoxidised tailings. Sequential extraction indicates that these metals and As were mainly retained with crystalline Fe-oxides, and therefore potentially will be remobilised if the oxic conditions become more reducing, for instance as a result of remediation of the tailings impoundment.An erratum to this article can be found at     

Prediction of the long-term performance of abandoned lead zinc mine tailings in a Welsh catchment

In this study we investigated the sulphidic mine tailings from Frongoch and Grogwynion, two abandoned lead zinc mines in mid-Wales, UK. Despite falling within the same ore field the mine waste characterisation has identified differences in the tailings from the two sites. Bulk concentrations range from 10 to 52 g kg^− 1 for Pb, 1.1 to 2.9 g kg^− 1 for Zn in Grogwynion and from 1.0 to 130 g kg^− 1 for Pb, 11 to 110 g kg^− 1 for Zn in Frongoch. An experimental (European standard leaching tests TS 14429 and TS 14405) and geochemical modelling approach was used to study the leaching composition as a function of pH and liquid/solid ratio. There was little correlation between the tailings bulk metal concentrations and the leachate composition, but variations in Pb and Zn concentrations were found to be consistent with control of dissolved Pb and Zn by secondary minerals and the mechanisms of dissolution/precipitation/sorption involving them. Specifically, the Grogwynion mine tailings with near-neutral pH have predominantly lead and zinc carbonates controlling Pb and Zn solubility in the leachates, whereas the Pb and Zn concentrations in Frongoch leachates are best modelled with a surface complexation model for metal sorption to oxyhydroxides. The different speciation results in a greater sensitivity of Grogwynion tailings to acidification with a potential release of Pb in solution up to 10 times higher than in Frongoch, despite similar bulk Pb concentrations. At acid pH, Zn is similarly dissolved to a greater extent in Grogwynion than in Frongoch tailings. There was no evidence of sulphide oxidation during the batch and column leaching tests and the suitability of using these European leaching standards for the characterisation of sulphidic mine waste materials for waste management purposes has been considered.     

尾矿中硫化物风化氧化模拟实验研究

为防治矿山尾矿造成环境污染，对方铅矿，闪锌矿，磁黄铁矿、黄铜矿，黄铁矿进行了风化氧化实验研究，结果显示，硫化物的氧化速率顺序为：方铅矿＞闪锌矿＞磁黄铁矿＞黄铜矿＞黄铁矿，侵蚀液pH值越低，硫化物氧化速率越大，有机物存在对硫化物氧化起缓冲和抑制作用。     

Geochemistry of iron ochres and mine waters from Levant Mine,Cornwall

The geochemistry of metal-rich mine waters and mineral precipitates from the Levant mine, Cornwall, has been examined. Sulphide oxidation at Levant mine has produced a wide range of secondary sulphides, oxides, chlorides, sulphates and carbonates in a gossan environment. The mine waters display a wide variation in alkalinity, pH, chloride, sulphate, sodium, potassium and heavy metal content which can be explained by variable degrees of mixing between acidic, metal-rich, rock drainage waters and neutral to alkaline sea waters. Transition metals are soluble in the acidic mine waters with concentrations up to 665 mg/l Cu, 41 mg/l Zn, 76 mg/l Mn, 6 mg/l Co and >2500 mg/l total Fe. The production of acid rock drainage and leaching of metals can be related to sulphide oxidation. Where these metal-rich acidic waters mix with infiltrated sea water, neutralization occurs and some metals are precipitated (principally Cu). Where pools of mine drainage are stagnant native copper and cuprite are precipitated, frequently observed replacing iron pipes and rail tracks and wooden shaft supports, due to electrode potential differences. In these solutions, dissolved copper species are also reduced by interaction with wood-derived organic species. Precipitation of iron oxyhydroxides, caused by a pH increase, also occurs and leads. to coprecipitation of other metals, including Cd, Co, Ph, Mn, Ag and Zn, thus limiting the release of dissolved metals in solution from the mine. However, the release of suspended metal-rich ochres in mine discharge waters (with high Ph, Zn, Cd, Mn, Ni, Sn, Sb, As, Bi, Cu, Co and Ag) will still present a potential environmental hazard.     

Sequential extraction and leaching characteristics of heavy metals in abandoned tungsten mine tailings sediments

The chemical speciation of potentially toxic elements (As, Cd, Cu, Pb, and Zn) in the contaminated soils and sulfides-rich tailings sediments of an abandoned tungsten mine in Korea was evaluated by conducting modified BCR sequential extraction tests. Kinetic and static batch leaching tests were also conducted to evaluate the potential release of As and other heavy metals by acidic rain water and the leaching behaviors of these heavy metals. The major sources of the elements were As-, Zn- and Pb-bearing sulfides, Pb carbonates (i.e., cerussite), and Pb sulfates (i.e., anglesite). The biggest pollutant fraction in these soil and tailing samples consists of metals bound to the oxidizable host phase, which can be released into the environment if conditions become oxidative, and/or to residual fractions. No significant difference in total element concentrations was observed between the tailings sediments and contaminated soils. For both sample types, almost no changes occurred in the mobility of As and the other heavy metals at 7 days, but the mobility increased afterwards until the end of the tests at 30 days, regardless of the initial pH. However, the mobility was approximately 5–10 times higher at initial pH 1.0 than at initial pHs of 3.0 and 5.0. The leached amounts of all the heavy metal contents were higher from tailings sediments than from contaminated soils at pH > 3.0, but were lower at pH < 3.0 except for As. Results of this study suggest that further dissolution of heavy metals from soil and tailing samples may occur during extended rainfall, resulting in a serious threat to surface and groundwater in the mine area.     

Trace metal and As solid-phase speciation in sulphide mine tailings – Indicators of spatial distribution of sulphide oxidation in active tailings impoundments

Redistribution of potentially harmful metals and As was studied based on selective extractions in two active sulphide mine tailings impoundments in Finland. The Hitura tailings area contains residue from Ni ore processing, while the Luikonlahti site includes tailings from the processing of Cu–Co–Zn–Ni and talc ores. To characterize the element solid-phase speciation with respect to sulphide oxidation intensity and the water saturation level of the tailings, drill cores were collected from border zones and mid-impoundment locations. The mobility and solid-phase fractionation of Ni, Cu, Co, Zn, Cr, Fe, Ca, Al, As, and S were analysed using a 5-step non-sequential (parallel) selective extraction procedure. The results indicated that metal redistribution and sulphide oxidation intensity were largely controlled by the disposal history and strategy of the tailings (sorting, exposure of sulphides due to delayed burial), impoundment structure and water table, and reactivity of the tailings. Metal redistribution suggested sulphide weathering in the tailings surface, but also in unsaturated proximal areas beside the earthen dams, and in water-saturated bottom layers, where O₂-rich infiltration is possible. Sulphide oxidation released trace metals from sulphide minerals at both locations. In the Hitura tailings, with sufficient buffering capacity, pH remained neutral and the mobilized metals were retained by secondary Fe precipitates deeper in the oxidized zone. In contrast, sulphide oxidation-induced acidity and rise in the water table after oxidation apparently remobilized the previously retained metals in Luikonlahti. In general, continuous disposal of tailings decreased the sulphide oxidation intensity in active tailings, unless there was a delay in burial and the reactive tailings were unsaturated after deposition.     

Grass cover density and metal speciation in profiles of a tailings-pile from a mining zones in Zacatecas,North-Central Mexico

The 7-year-old mine tailings pile P2 from Concepción del Oro has been revegetated spontaneously by xerophyte grasses, covering about the 30% of its surface. To elucidate the effect of the grass cover in the geochemical behavior of the sulfide minerals (SM) and metals, the strata of four selected profiles (P2-I, P2-II, P2-III and P2-IV, with high, middle, low, and null grass cover, respectively) were analyzed mineralogically and chemically, using scanner electron microscopy, X-ray diffractometer and performing a six-step sequential extraction method. An older (50-year-old) and uncovered (without grass cover) profile of the tailings pile P3 was also analyzed. In all the profiles from P2, the SM oxidation is not yet an extended process; however, the samples from the uncovered profile P2-IV showed evidences of SM (pyrite and chalcocite) oxidation, as well as the presence of gypsum and Fe oxides, as the major secondary phases resulted from the SM oxidation. Additionally, the carbonate content and pH values in P2-IV were lower than in the covered profiles from P2. The oldest and uncovered P3-I profile showed an extensive oxidation of sulfurs which resulted in the depletion of carbonates and a pH 2. Another distinctive characteristics of the covered profiles was that Pb, Cu, and Zn were mainly associated with the reducible fractions (carbonates and/or amorphous oxides); meanwhile, in the uncovered (P2-IV and P3-I) such metals were mainly associated with the oxidizable fraction (crystalline oxides). The results suggest that the mineralogical transformations control metal stability in plant-covered impoundments (phytostabilization): the occurrence of a thick grass cover, with an efficient water usage and retention, seems to shun both the acidic dissolution of carbonates and the reductive dissociation of the formerly present oxyhydroxides, which is desired for remediation tasks. This is the first report about the effects of grass cover for a carbonaceous and unsaturated mine tailings from a semiarid region, that can help in a better understanding of the scope of phytoremediation in such conditions.     

Lithological and geochemical record of mining-induced changes in sediments from Macquarie Harbour,southwest Tasmania,Australia

Macquarie Harbour in southwest Tasmania, Australia, has been affected severely by the establishment of mines in nearby Queenstown in the 1890s. As well as heavy metal-laden acid rock drainage from the Mount Lyell mine area, over 100 Mt of mine tailings and slag were discharged into the Queen and Ring Rivers, with an estimated 10 Mt of mine tailings building a delta of ca. 2.5 km² and ca. 10 Mt of fine tailings in the harbour beyond the delta. Coring of sediments throughout Macquarie Harbour indicated that mine tailings accreted most rapidly close to the King River delta source with a significant reduction in thickness of tailings and heavy metal contamination with increasing distance from the King River source. Close to the King River delta the mine tailings are readily discriminated from the background estuarine sediments on the basis of visual logging of the core (laminations, colour), sediment grain size, sediment magnetic susceptibility and elemental geochemistry, especially concentrations of the heavy metals Cu, Zn and Pb. The high heavy metal concentrations are demonstrated by the very high contamination factors (CF > 6) for Cu and Zn, with CF values mostly >50 for Cu for the mine-impacted sediments. Although the addition of mine waste into the King River catchment has ceased, the catchment continues to be a source of these heavy metals due to acid rock drainage and remobilisation of mine waste in storage in the river banks, river bed and delta. The addition of heavy metals to the harbour sourced from the Mount Lyell mines preceded the advent of direct tailings disposal into the Queen River in 1915 with the metals probably provided by acid rock drainage from the Mount Lyell mining area.     

Heavy metal concentrations in soils and plants in the vicinity of Arufu lead-zinc mine,Middle Benue Trough,Nigeria

This study focused on the influence of base metal mining on heavy metal levels in soils and plants in the vicinity of Arufu lead-zinc mine, Nigeria. Soil samples (0-15 cm depth) and plant samples were collected from cul-tivated farmlands in and around the mine, the unmineralized site and a nearby forest (the control site). The samples were analyzed for heavy metals (Fe, Zn, Mn, Cu, Pb, Cr and Cd) by Atomic Absorption Spectrophotometry (AAS). The physical properties of soils (pH and LOI) were also measured. Results showed that soils from cultivated farm-lands have neutral pH values (6.5-7.5), and low organic matter contents (10%). Levels of Zn, Pb and Cd in culti-vated soils were higher than the concentrations obtained from the control site. These heavy metals are most probably sourced from mining and agricultural activities in the study area. Heavy metal concentrations measured in plant parts decreased in the order of rice leavescassava tuberspeelings. In the same plant species, metal levels decreased in the order of ZnFeMnCuPbCrCd. Most heavy metals were found in plant parts at average concentrations normally observed in plants grown in uncontaminated soil, however, elevated concentrations of Pb and Cd were found in a few cassava samples close to the mine dump. A stepwise linear regression analysis identified soil metal contents, pH and LOI as some of the factors influencing soil-plant metal uptake.     

Secondary copper enrichment in tailings at the Laver mine, northern Sweden

 Field and laboratory studies of the sulphide-bearing tailings at Laver, northern Sweden, show that the present release of metals from the tailings is low, especially with regard to Cu. A large part of the Cu released by sulphide oxidation is enriched in a distinct zone just below the oxidation front. The enrichment zone occurs almost all over the tailings area except in areas with a shallow groundwater table. The Cu enrichment is caused by formation of covellite and adsorption onto mineral surfaces. The transport of Zn, Co, Cd, Ni and S seems to be controlled mainly by adsorption. No secondary zone or secondary minerals containing these metals have been found. Just below the groundwater table, metals are released into solution when the enrichment zone reaches the groundwater due to the low pH. An increased release of metals, especially Cu, can be expected in the future, since the enrichment zone is moving towards the groundwater table. Received: 4 December 1997 · Accepted: 17 December 1998     

Acid neutralization mechanisms and metal release in mine tailings: a laboratory column experiment

Mining and milling of base metal ore deposits can result in the release of metals to the environment. When sulfide minerals contained in mine tailings are exposed to oxygen and water, they oxidize and dissolve. Two principal antagonistic geochemical processes affect the migration of dissolved metals in tailings impoundments: sulfide oxidation and acid neutralization. This study focuses on acid neutralization reactions occurring in the saturated zone of tailings impoundments. To simulate conditions prevailing in many tailings impoundments, 0.1 mol/L sulfuric acid was passed continuously through columns containing fresh, unoxidized tailings, collected at Kidd Creek metallurgical site. The results of this column experiment represent a detailed temporal observation of pH, Eh, and metal concentrations. The results are consistent with previous field observations, which suggest that a series of mineral dissolution-precipitation reactions control pH and metal mobility. Typically, the series consists of carbonate minerals, Al and Fe(III) hydroxides, and aluminosilicates. In the case of Kidd Creek tailings, the dissolution series consists of ankerite-dolomite, siderite, gibbsite, and aluminosilicates. In the column experiment, three distinct pH plateaus were observed: 5.7, 4.0, and 1.3. The releases of trace elements such as Cd, Co, Cr, Cu, Li, Ni, Pb, V, and Zn were observed to be related to the pH buffering zones. High concentrations of Zn, Ni, and Co were observed at the first pH plateau (pH 5.7), whereas Cd, Cr, Pb, As, V, and Al were released as the pH of the pore water decreased to 4.0 or less.     

The effect of mineralogy on the mobility of heavy metals in mine tailings: a case study in the Samsanjeil mine,Korea

This study examined the chemical speciation and mobility of As and heavy metals in a tailings impoundment in Samsanjeil mine located in Gosung, Korea, as well as the factors affecting them. XRD, SEM, and 5-step sequential extraction were used to examine the samples at two sampling sites (NN and SN sites). The pH of the tailings decreased with increasing depth at the NN site (from 7.2 to 2.8), whereas no significant differences were observed at the SN site (8.1–8.8). The samples at the SN site showed a larger amount of calcite than those at the NN site, indicating that calcite plays an important role buffering the pH in the study sites. Jarosite was found only at the lower part of the NN site, where calcite was not found. The mineralogical observation of jarosite and calcite was also confirmed by SEM. The concentrations of As and heavy metals in the tailings were as follows: Cu > As > Zn > > Pb > Co > Cr > Ni > Cd. The total concentrations of Ni, Zn, Co, and Cd were higher at the SN site than those at the NN site. On the other hand, the concentrations of As and Cr existing as oxyanions were higher at the NN site, which can be explained by the mobility changes of those elements affected by pH variations. At the NN site, the fractions of heavy metals bound to the Fe/Mn oxides, except for As and Cr, decreased, and Cu, Zn, and Co showed an increasing fraction of exchangeable metals with increasing depth. This suggests that the pH and resulting surface charge of minerals, such as goethite and jarosite, are the dominant factors controlling the chemical speciation of metals. These results highlight the importance of mineralogy in controlling the mobility and possible bioavailability of heavy metals in tailings.     

Chemical characteristics and acid drainage assessment of mine tailings from Akara Gold mine in Thailand

Acid Mine Drainage (AMD) is a great concern in many abandoned mines because of its adverse effect on the environment. In mining processes, many kinds of wastes are produced. These wastes may become eventually sources of environmental degradation. The focus of this study is the geochemical characterization of the end-processed tailings generated by Akara Gold Mine, the biggest gold mine in Thailand. Tailing samples were systematically collected for analyses of chemical and mineralogical compositions. As a result, their quantitative chemical analyses are slightly different from place to place, but mineral components cannot be clearly differentiated. For instance, it may be assumed that the end-processed tailings, which were a mixture between high and low grade concentrates, would have similar mineral components. However, the little variation of chemical composition may be caused by the ore refining processes that are somehow varied in proportion to chemical additives, alkali cyanide and quick lime in particular. In addition, clay composition in ore-bearing layers may also influence alumina content of tailings, accordingly. Distribution of the tailings is not related to depth and distance of the tailing storage pond because the disposal has sped them over the pond during operation. Total heavy metals of the tailing samples were analyzed on the basis of the EPA 3052 method. Consequently, the most toxic elements (e.g., Co, Cu, Cd, Cr, Pb, Ni and Zn) were found falling within the standard of Thailand Soil Quality Standards for Habitat and Agriculture. Only Mn appears to have higher content than the standard. In addition, leaching tests proved that these tailings contain low metal concentrations. As a result, at pH 2, Mn can leach out exceeding the Thailand Surface Water Quality Standard for Agricultural (Mn <1 ppm) and the Thailand Industrial Effluent Standard (<5 ppm). Although leachate at pH 4 and neutral conditions contains lower Mn than the Industrial Effluent Standard it still exceeds the surface water quality standard. Interestingly, Pb can be leached out exceeding both standards (0.2 ppm for the industrial effluent standard and 0.05 ppm for the surface water quality standard). For Ni leaching, its concentration is lower than the Industrial Effluent Standard at all pH conditions but still exceeds the Surface Water Standard at pH 2 and 4. This information should be taken into consideration for further environmental monitoring. Acid generating potential of the tailings was estimated using acid–base accounting (ABA) and net acid generation (NAG) tests. The results of ABA and NAG tests show that the tailing samples contain a high amount of sulfur. However, they also contain high acid neutralization capacity. Consequently, these tailings may not have potential to generate acid drainage; in the other words, they can be classified as a non-acid forming (NAF) material. However, since these tailings contain some heavy metals (e.g., Ni, Mn and Pb) that are observed in leachates exceeding the standards at low pH, the AMD conditions may lead to heavy metal release. Therefore, prevention of oxidizing process and dissolution should be considered with great care. In addition, Mn and Pb can also be leached at neutral conditions. Barrier of air and water, clay layer for example, should be placed over the tailings pound before covering by topsoil for re-vegetation. Growing native grass is recommended for stabilization of the surface and reducing erosion rate. Monitoring of water quality should also be carried out annually.     

Metal extractability in acidic and neutral mine tailings from the Cartagena-La Unión Mining District (SE Spain)

Mine tailings are ubiquitous in the landscapes of mined areas. Metal solubilities were compared in two chemically distinct mine tailings from the old Mining District of Cartagena-La Unión (SE Spain). One of the tailings was acidic (pH 3.0) with 5400 mg/kg Zn, 1900 mg/kg As and 7000 mg/kg Pb. The other was neutral (pH 7.4) with 9100 mg/kg Zn, 5200 mg/kg Pb and 350 mg/kg As. In samples from the acidic tailings, more than 15% of the Zn and 55% of the Cd were extractable with 0.1 M NaNO₃, and distilled water. In the neutral tailings, using the same reagents, less than 1% of the metals were extractable. A sequential extraction procedure revealed that the sum of the residual and the Fe oxide fractions of Cu, Zn and Pb comprised 80–95% in the acidic tailings and 70–90% in the neutral tailings. The acidic mine tailings had a higher metal solubility, resulting in more metal leaching in the short-term, but also a higher fraction of inert metal. In contrast, in the neutral tailings, the metals were evenly distributed between, oxides and the residual fraction. This implies lower metal mobility in the short-term, but that metal mobility may increase in the long-term. When applied to mine tailings, sequential extractions may provide misleading results because the strong cation exchange capacity of some extractants may induce pH changes and thereby significantly change metal solubility.     

内蒙古废弃钨钼矿区周围土壤重金属污染生态环境评价及成因分析

为研究内蒙古赤峰市废弃钨钼矿区周围土壤重金属污染特征、潜在生态风险及成因分析，共采集83份表层土壤样品和6个土壤钻孔。采用ArcGIS空间插值分析方法研究As、Cd、Cr、Cu、Ni、Pb、Mo和Zn的空间分布，构建重金属扰动指数函数研究重金属受人类活动的污染程度，利用地累积指数法验证矿区周围土壤重金属污染程度，通过相关性分析判断重金属来源并讨论污染成因。结果表明：矿区周围土壤As、Cd、Cu、Pb、Zn和Mo平均含量明显高于矿区周边背景值，高含量主要分布尾矿库周围，主要来源为矿山采选活动；Cr和Ni基本无污染，主要来源为母岩风化。通过重金属扰动指数函数计算发现：采用区域背景值对矿区周围进行重金属污染评价夸大了矿山采选活动对矿区周围土壤重金属的污染，矿区周围土壤重金属污染是由于天然重金属富集和采矿活动共同作用下的“双驱动模式”导致，尾矿库周围土壤重金属污染程度随着与尾矿库水平距离的增加和深度的加大而逐渐降低。降水量丰富程度是影响重金属迁移能力的关键因素，该矿处于降水量匮乏地区，尾矿库对周围土壤重金属污染范围有限，对生态环境影响轻微。     

Sequential extractions on mine tailings samples after and before bioassays: implications on the speciation of metals during microbial re-colonization

Mine tailings may be remediated using metal tolerant microorganisms as they may solve the limiting conditions for healthy development of plants (i.e., low organic mater content and poor physical conditions). The aim of this study was to investigate the consequences of microbial colonization on the chemical speciation of trace metals. Surface samples from the Valenciana mine tailings (Guanajuato, Mexico) were used for long-term bioassays (BA), which consisted in the promotion of microorganisms, development on tailings material under stable laboratory conditions (humidity, temperature, and light exposure). A five-step sequential extraction method (exchangeable, carbonate/specifically adsorbed, Fe–Mn oxides, organic matter (OM)/sulfide, and residual fractions) was performed before and after BA. Extraction solutions and leachates were analyzed by inductively coupled plasma-mass spectrometry. OM content, cationic exchange capacity, and pH values were also assessed before and after BA. The results indicate that trace elements are generally present in nonresidual fractions, mainly in the Fe–Mn oxides fraction. The concentration of total Zn, As, Se, Pb, and exchangeable Cu and Pb is above the recommendable limits for soils. Despite the high bioavailability of the former elements, biofilms successfully colonized the tailing samples during the BA. Cyanobacteria and green algae, heterotrophic fungi, aerobic bacteria, and anaerobic bacteria composed the developed biofilms. Chemical controls of trace elements could be attributed to absorption onto inorganic complexes (carbonates, metal oxides), while biofilm occurrence seems to enhance complexation and immobilization of Cr, Ni, Cu, Zn, As, and Pb. The biofilm developed does not increase the bioavailable forms and the leaching of the trace elements, but significantly improves the OM contents (natural fertilization). The results suggest that biofilms are useful during the first steps of the mine tailings remediation.