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.     

Different spontaneous plant communities in Sanmen Pb/Zn mine tailing and their effects on mine tailing physico-chemical properties

Different plant communities have established spontaneously on Sanmen Pb/Zn mine tailing. The site was inspected and four different plant communities were identified according to their species composition. To understand the effects of different communities on mine tailing physico-chemical properties, a community survey was carried out in Sanmen Pb/Zn mine tailing, and the physico-chemical properties and heavy metal (Cu, Pb, Cd and Zn) distribution of mine tailings were determined. Results showed that there were four types of communities (I, II, III and IV) in Sanmen Pb/Zn mine tailing. From community I to IV, the number of plant species and community characteristics (aboveground biomass, underground biomass, coverage and height) consistently increased. Moreover, the nutrient pool and physico-chemical properties of mine tailing consistently reestablished from community I to IV, while the total heavy metal content consistently decreased. The contents of residual fractions, Fe–Mn oxide fractions for Pb, Zn, Cu and Cd and exchangeable fractions for Pb and Zn also consistently decreased. However, the contents of organically bound fraction had no obvious change from community I to IV. Moreover, the contents of Cu organically bound fraction reversely increased. Results demonstrate that communities I, II, III and IV should be a progressive community succession. Moreover, along with the progressive community succession, phytostabilization and phytoextraction of mine tailings are more and more effective.     

Changes in lead and zinc lability during weathering-induced acidification of desert mine tailings: Coupling chemical and micro-scale analyses

Desert mine tailings may accumulate toxic metals in the near surface centimeters because of low water through-flux rates. Along with other constraints, metal toxicity precludes natural plant colonization even over decadal time scales. Since unconsolidated particles can be subjected to transport by wind and water erosion, potentially resulting in direct human and ecosystem exposure, there is a need to know how the lability and form of metals change in the tailings weathering environment. A combination of chemical extractions, X-ray diffraction, micro-X-ray fluorescence spectroscopy, and micro-Raman spectroscopy were employed to study Pb and Zn contamination in surficial arid mine tailings from the Arizona Klondyke State Superfund Site. Initial site characterization indicated a wide range in pH (2.5–8.0) in the surficial tailings pile. Ligand-promoted (DTPA) extractions, used to assess plant-available metal pools, showed decreasing available Zn and Mn with progressive tailings acidification. Aluminum shows the inverse trend, and Pb and Fe show more complex pH dependence. Since the tailings derive from a common source and parent mineralogy, it is presumed that variations in pH and “bio-available” metal concentrations result from associated variation in particle–scale geochemistry. Four sub-samples, ranging in pH from 2.6 to 5.4, were subjected to further characterization to elucidate micro-scale controls on metal mobility. With acidification, total Pb (ranging from 5 to 13 g kg⁻¹) was increasingly associated with Fe and S in plumbojarosite aggregates. For Zn, both total (0.4–6 g kg⁻¹) and labile fractions decreased with decreasing pH. Zinc was found to be primarily associated with the secondary Mn phases manjiroite and chalcophanite. The results suggest that progressive tailings acidification diminishes the overall lability of the total Pb and Zn pools.     

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.     

Behavior of heavy metals in sulfide mine tailings and bottom sediment (Salair,Kemerovo region,Russia)

The given work focused on solving the problem of environmental geochemistry related to investigation of element speciation, their mobility, and migration in polluted areas. The purpose was to describe quantitatively migration, distribution, and redistribution of heavy metals by the example of the old tailings (Talmovaya sands) of the Lead Zinc Concentration Plant (Salair, Kemerovo region, Russia) and technogenic bottom sediments of the Malaya Talmovaya river. Contents of elements in the sulfide tailings range in the following limits: Zn: 1,100–27,000 ppm, Cd: 1.3–240 ppm, Pb: 0.01–0.81 ppm, Cu: 220–960 ppm, As: 15–970 ppm, Fe: 19,000–76,000 ppm, and Ba: 80,000–1,00,000 ppm. Element concentrations in the river sediment are proportional to the element contents in the sulfide tailings. Element speciations in the sulfide tailings and technogenic bottom sediments were investigated by the modified sequential extraction procedure. Chemical forms of heavy metals in pore water and surface water were calculated by WATEQ4F software. Principles of heavy metal migration in the sulfide tailings and technogenic bottom deposits were established. The obtained results about element species in the sulfide tailings and sediment explain the main principles of element migration and redeposition. In the mine waste and technogenic bottom deposits, there is vertical substance transformation with formation of geochemical barriers.     

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.     

Tailings dam seepage at the rehabilitated Mary Kathleen uranium mine,Australia

This study reports on the seepage of metals, metalloids and radionuclides from the Mary Kathleen uranium mill tailings repository. Since rehabilitation in the 1980s, the capped tailings have developed a stratified hydrochemistry, with acid (pH 3.7), saline, metal-rich (Fe, Mn, Ni, U ± As, Pb, Zn), oxygenated (1.05 mg L⁻¹ DO), radioactive waters in the upper tailings pile and near-neutral pH (pH 7.57), metal-poor, reduced (0.08 mg L⁻¹ DO) waters at depth. Seepage (∼0.5 L s⁻¹) of acid (pH 5.5), metal-rich (Fe, Mn ± Ni, U, Zn), radioactive (U-235, U-238, Ra-226, Ra-228, Ac-227) waters occurs from the base of the tailings dam retaining wall into the former evaporation pond and local drainage system. Oxygenation of the seepage waters causes the precipitation of Fe and coprecipitation and adsorption of other metals (U, Y), metalloids (As), rare earth elements (Ce, La) and radionuclides (U-235, U-238). By contrast, alkalis and alkaline–earth elements (Ca, K, Mg, Na, Sr), Mn, sulfate and to some degree metals (U, Zn, Ni), rare earth elements (Ce, La) and radionuclides (U-235, U-238, Ra-226, Ra-228) remain in solution until pH neutralisation and evaporation lead to their precipitation in efflorescences and sulfate-rich evaporative sediments. While the release of contaminant loads from the waste repository through seepage is insignificant (e.g. ∼5 kg of U per year), surface waters downstream of the tailings impoundment possess TDS, U and SO₄ concentrations that exceed Australian water quality guideline values in livestock drinking water. Thus, in areas with a semi-arid climate, even insignificant load releases of contaminants from capped tailings repositories can still cause the deterioration of water quality in ephemeral creek systems.     

Characterization of Kolar gold field mine tailings for cyanide and acid drainage

The gold mining process at Kolar gold field (KGF) mines has generated about 32 million tons of tailings. Gold was extracted from the mined ores using cyanidation technique that involved dissolution of gold in the ore by water soluble alkali metal cyanides (example, sodium cyanide or potassium cyanide). Of the several dumps that received the mine tailings only the Kennedy’s Line dump was active prior to closure of the KGF mines in the year 2000. The Kennedy’s Line dump received sulfide bearing tailings in slurry form that comprised of spent ore and process water bearing soluble alkali metal cyanide. Depending on the pH of the tailing slurry, the free cyanides may exist as aqueous hydrogen cyanide that can escape to the atmosphere as hydrogen cyanide gas or occur as soluble cyanide (CN⁻) ions that can be leached by infiltrating water to the sub-surface environment. Additionally, the presence of pyrite minerals in the Kennedy’s Line dump makes them susceptible to acid drainage. This study examines the potential of gold tailings of Kennedy’s Line dump to release cyanide ions (CN⁻) and acid drainage to the sub-surface environment by performing physico-chemical and leaching tests with tailing samples collected from various depths of the dump, sub-surface soil samples beneath the dump and groundwater samples from vicinity of Kennedy’s Line dump. The chemical mechanisms responsible for the ambient cyanide and pH levels of the tailing dump, sub-surface soil samples and groundwater are also inferred from the laboratory results.     

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.     

Geochemistry of waters associated with the old mine workings at Fonte Santa (NE of Portugal)

The quartz veins containing scheelite from Fonte Santa mine cut the Lower Ordovician quartzites. A muscovite–biotite granite (G1) and a muscovite granite (G2), both S-type, crop out close to the Fonte Santa mine and are related to the Moncorvo–Bemposta shear zone. The most altered samples of G2 show intense muscovitization and microclinization and contain chlorite, columbite–tantalite, wolframite, W-ixiolite and Fe-oxides. The tin-bearing granites contain 18 ppm (G1) and 73 ppm (G2) Sn. The most altered samples of G2 correspond to a tungsten granite. The quartz veins contain muscovite, chlorite, tourmaline, scheelite, pyrrhotite, pyrite, sphalerite, chalcopyrite, galena, arsenopyrite, iron oxides, Fe sulfates, phosphates of Pb, Fe and Al. The Fonte Santa mine area was exploited for W between 1942 and 1982. At the end of November 2006, a flood event damaged the tailings dam of Fonte Santa mine, releasing contaminated material and increasing contaminant levels in water within the area of influence of the mine. The waters related to the Fonte Santa mine are poorly mineralized, with electrical conductivity of < 965 µS/cm, and of a mixed type or HCO₃⁻ and SO₄²⁻ types. Most pH values (5.0−8.5) indicate that there is no significant acidic drainage in the region, as found in other areas. More acidic values (pH = 3.4) were found in the mine's lagoon. Waters associated with mineralized veins and old mine activities have Fe and Mn concentrations that forbid their use for human consumption and agriculture. Natural Na, Mg and K water contents are associated with the alteration of albite, chlorite and muscovite of country rock, while Ca with the W-bearing quartz veins. Weathering agents are carbonic and sulphuric acids and the latter has a strong influence in areas draining fine-grained mine tailings.     

Arsenic and lead mobility: From tailing materials to the aqueous compartment

This study concerns the mineralogy of the tailings of a former Ag–Pb mine (Auzelles district, France) and the contribution of the waste materials to the heavy metal dissemination in the environment. Accumulation of metals in fish flesh was reported and this pollution is attributed to past mining activities. Tailings were studied to establish the major transfer schemes of As and Pb in order to understand their mobility that leads to contamination of a whole ecosystem. Mineralogical investigation, solubility and compliance tests were performed to assess the stability of the metal-bearing phases. Among the various metallic elements measured, As and Pb show the highest bulk concentrations (up to 0.7% and 6.3% respectively) especially for samples presenting near neutral pH values. According to X-ray diffraction (XRD), Scanning Electron Microscopy (SEM-EDX), Electron Probe Micro-Analysis (EPMA) and micro-Raman spectrometry (μRS), tailings mineralogy still contain primary minerals such as sulfides (e.g., galena, pyrite), phosphates (monazite, apatite) and/or carbonates (e.g., (hydro-)cerussite, dolomite, siderite). Sulfates (e.g., anglesite, lanarkite, plumbojarosite and beudantite) are the main secondary metal-bearing phases with other interesting phases accounting for metals mobility such as Fe and/or Pb and/or Mn oxides (e.g., lepidocrocite, goethite -up to 15 wt% of Pb was measured-, plumboferrite-type phase, mimetite). The lowest Pb solubilities were obtained at pH 8–9 and at a larger range than for As for which the lowest solubilities are reached around pH 6–7. At this minimum solubility pH value, Pb concentrations released still over exceed the National Environmental Quality Standards (NEQS), whatever the samples. The highest solubility is reached at pH 2 for both elements whatever the considered sample. This represents up to 51% of total Pb and up to 46% of total As remobilized and concentrations exceeding the NEQS. As and Pb released mainly depends on the Fe/Mn oxides (e.g., goethite, lepidocrocite) and carbonates (cerussite) which are the less stable phases. Compliance tests also show that Pb concentrations released are higher than the upper limit for hazardous waste landfills. Determination of the mineralogy allows understanding both the solubility and leaching test experiments results, as well as to forecast the impact of the residues on the water quality at a mid-term scale.     

安徽铜陵水木冲尾矿重金属赋存状态及污染特征研究

为探讨富硫化物尾矿酸化及重金属污染特征,选择安徽铜陵水木冲尾矿库浅层(0～90 cm)剖面为研究对象,对其结构特点、矿物组成、重金属(Pb、Cd、Zn、Ni、Cr、Mn、Cu和As)含量及赋存形态进行研究。结果表明,该尾矿库浅层出现分层现象,即表层为强硬化层,向下依次为弱硬化层和松散层,且呈酸性;矿物主要以辉石、长石、云母和石膏为主,由浅及深,金属硫化物及碳酸盐型矿物特征峰呈现增强的趋势;重金属呈现两种富集类型:表层(0～30cm,As、Pb)富集和中部(40～60 cm,Cd、Cu、Mn、Ni、Zn和Cr)富集型,其中Cu、Cd、As污染较为严重。由相关性分析可知,部分金属之间存在一定的伴生性,且p H值是影响重金属迁移的重要因素之一。该尾矿重金属主要以残渣态为主,其中Pb的潜在迁移能力最强,As最弱,顺序为Pb Cd Zn Ni Cr Mn Cu As。     

Subsurface variations in arsenic mineralogy and geochemistry following long-term weathering of gold mine tailings

Variations in arsenic (As) mineralogy and geochemical controls on its mobility were evaluated in subsurface tailings at the historical Montague and Goldenville mine sites in Nova Scotia, Canada. Tailings at these sites contain some of the highest As concentrations in Nova Scotia and are located in close proximity to local communities. Pore water in the subsurface tailings is characterized by circumneutral to alkaline pH (6.2 to 8.7) and mildly reducing to oxidizing redox conditions (+130 mV to +347 mV). Bulk chemistry, scanning electron microscopy, and synchrotron micro-X-ray diffraction analyses showed As mineral hosts differ with depth. The deepest tailings (max. 2 m) are in direct contact with partially decomposed vegetation, which supports reducing conditions and the precipitation of authigenic As and Fe sulfides. Under reducing conditions, dissolved As concentrations are also controlled by desorption of As from dissolution of Fe and Mn oxides and the sorption or co-precipitation of As with carbonates. These geochemical controls differ from those influencing dissolved As concentrations under oxidizing conditions. In the near surface, As mobility is controlled by oxidative dissolution of primary arsenopyrite, precipitation of secondary Fe arsenates, Fe oxyhydroxides and Mn oxides, secondary Ca-Fe arsenates, and sorption onto Fe oxyhydroxides and gangue minerals. Some of these mineral species are stable under different conditions yet occur in close association, indicating the importance of microenvironments. The results of this study show that the weathering characteristics of these tailings vary with depth, leading to the formation of new As hosts that are distinct from those observed in the near surface. Identification of these As hosts provides an understanding of current controls on As mobility and has implications for future reprocessing and/or remediation efforts.     

A comparative mineralogical and geochemical study of sulfide mine tailings at two sites in New Mexico, USA

A comparative study of sulfide mine tailings from two sites near Silver City in southwest New Mexico has shown the need for environmental monitoring in a geological context. The Cyprus-Piños Altos and Cleveland deposits consist of Cu and Zn skarn mineralization in the Piños Altos Mountains of New Mexico. Primary ore minerals in both deposits include chalcopyrite, sphalerite, and galena. The Cyprus-Piños Altos Mine ceased operation in 1995 and the Cleveland Mill closed in 1950. The deposits have similar mineralogical characteristics; however, the tailings are different in terms of age, degree of oxidation and method of disposal. The Cyprus-Piños Altos tailings (CPAT) are stored in a lined, bermed impoundment. They are dominantly water-saturated and exhibit no secondary-phase formation. The grains are not cemented and show no evidence of primary-mineral dissolution. The geochemical data show a predominantly primary signature. The tailings pond water is neutral to slightly alkaline (pH?from 7 to 8.3), partly as a result of processing methods. The Cleveland mill tailings (CMT) were deposited in a valley at the headwaters of an ephemeral stream. They are highly oxidized and differentially cemented. They have undergone numerous wet/dry cycles resulting in extensive oxidation. Secondary minerals predominate, and consist mainly of jarosite, goethite, hematite, and Fe-oxyhydroxides and -oxyhydroxysulfates. The pH of the stream draining the CMT is as high as 2.15. Maximum metal contents in the stream immediately downstream from the tailings are 5305?ppm Zn, 454?ppm Cu, 1.16?ppm Pb, 17.5?ppm Cd, 1.4?ppm As, and 0.01?ppm Hg.     

Sorption of lead by phlogopite-rich mine tailings

The Pb sorption capacity of apatite ore mine tailings and its potential to act as a remediation agent in a Pb polluted areas were investigated. The tailings, originating from the Siilinjärvi carbonatite complex in Finland, consist mainly of phlogopite and calcite accompanied by apatite residues. The ability of the tailings to retain Pb from an aqueous solution was investigated using an isotherm technique. Furthermore, in a 3-month incubation experiment, uncontaminated mineral soil was amended with untreated tailings and with tailings artificially weathered with acid to increase the quantity of Al and Fe (hydr)oxides. Tailings of two particle-sizes (∅ > 0.2 mm and ∅ < 0.2 mm) somewhat differing in their mineralogical composition were investigated as separate amendments. All tailings materials were added to the soil in two dosages (5 g and 10 g of tailings per 125 g of soil). Following incubation, tailings-induced changes in the Pb sorption capacity of the soil were investigated with the isotherm technique. Finally, to investigate the distribution of sorbed Pb among various chemical pools, the soil samples amended with tailings were contaminated with Pb and then subjected to sequential fractionation analysis. The results revealed efficient removal of Pb from an aqueous solution by the tailings, presumably through precipitation and surface complexation mechanisms. Amending the soil with the tailings increased the mass-based maximum Pb sorption capacity from 10.8 mg kg⁻¹ of the control soil to 14–20.5 mg kg⁻¹ for the untreated tailings and to 32.1–72.1 mg kg⁻¹ for the acid-treated material. The tailings transferred Pb from the exchangeable pool to the non-extracted one and thereby substantially decreased its bioavailability. The material with a particle diameter of less than 0.2 mm had a higher mass-based Pb sorption capacity than the large-sized material. The results suggest that the tailings may potentially serve as an immobilizing agent in polluted areas.     

Stabilization of arsenic-contaminated mine tailings using natural and calcined oyster shells

Natural oyster shells (NOS) and calcined oyster shells (COS) were used to immobilize arsenic (As) from contaminated mine tailings. In addition, a blend of Portland cement (PC)/cement kiln dust (CKD) was used as a stabilizing agent. The Korean Standard Test (KST) method (1 N HCl extraction) was used to evaluate the effectiveness of the treatment. The experimental results showed that COS effectively immobilized As in treated mine tailings. Specifically, an As concentration less than 1 mg L⁻¹ was obtained following COS treatment at 25 and 30 wt%. However, all the samples subjected to NOS treatments failed the Korean warning standard of 1.2 mg L⁻¹ after 28 days of curing. All of the COS-PC treatments were successful meeting the Korean warning standard after 7 days of curing. However, the PC-only treatment failed to meet the Korean warning standard. Similarly, the CKD-only treatment was failed to meet the Korean warning standard after 7 days of curing. However, the COS-CKD treatment showed that when the COS content was greater than 20 wt%, less than 1 mg L⁻¹ of As leachability was obtained. Scanning electron microscopy–energy dispersive X-ray spectroscopy (SEM–EDX) showed needle-like and torpedo-like Ca–As phases in the COS-treated samples suggesting that As was strongly associated with Ca and O. X-ray absorption near edge structure (XANES) analyses confirmed that As(V) was prevalent in the tailings and that there were no changes in As speciation following NOS or COS treatment.     

Spatial distribution of trace elements in floodplain alluvium of the upper Blackfoot River,Montana

The Mike Horse Mine tailings dam in western Montana was partially breached in 1975 due to heavy rainfall and a failed drainage bypass. Approximately 90,000 tons of metal and arsenic-enriched tailings flowed into Beartrap Creek and the Blackfoot River. The spatial distribution of trace elements As, Cd, Cu, Mn, Pb, and Zn in floodplain alluvium of the upper Blackfoot River were examined along 20 transects in the upper 105 river kilometers downstream from the tailings dam. Trace element concentrations decrease with distance from the failed dam, with As reaching background concentrations 15 km from the Mike Horse dam, Cd and Pb at 21 km, Cu at 31 km, and Mn and Zn at 37 km. Distance from the Mike Horse tailings dam and mine area is the dominating factor in explaining trace element levels, with R ² values ranging from 0.67 to 0.89. Maximum floodplain trace element concentrations in the upper basin exceed US. EPA ecological screening levels for plants, birds and other mammals, and reflect adverse hazard quotients for exposure to As and Mn for ATV/motorcycle use. Trace element concentrations in channel bank and bed alluvium are similar to concentrations in floodplain alluvium, indicating active transport of trace elements through the river and deposition on the floodplain. The fine fraction (<2 mm) of floodplain alluvium is dominated by sand-sized particles (2.0–0.05 mm), with Cu and Mn significantly correlated with silt-sized (0.05–0.002 mm) alluvium. Ongoing remediation in the headwaters area will not address metal contamination stored downstream in the channel banks and on the floodplain. Additionally, some trace elements (Cu, Mn and Zn) were conveyed farther downstream than were others (As, Cd, Pb).     

Geological analogue for circumneutral pH mine tailings: implications for long-term storage,Macraes Mine,Otago, New Zealand

Tailings from the Macraes Au mine cyanidation process are stored in an impoundment about 0.6 km² and 80 m deep whose pH is maintained near 8 by the neutralizing capacity of the gangue minerals. The tailings are sandy (>50 μm particles), have a hydraulic conductivity of about 10⁻² m/day, and contain 0.1–1.0 wt.% S and 0.1–1.5 wt.% graphitic C from the primary deposit. Concentrations of As in the pore water of the mixed tailings, which are a combination of various tailings types, range from 0.1 to 20 ppm, HCO₃^- is 100 to 200 ppm, and dissolved SO₄ is 100–1700 ppm. The mixed tailings will be stored in this impoundment in perpetuity after mining ceases. Confidence in the long-term pH stability of these tailings can be gained from examination of mineralogically and chemically similar geological analogues in the immediate vicinity. A sequence, typically about 5 m thick, of sands and gravels derived from the Macraes mineralized zone 12–28 ka ago contains rounded detrital sulfide mineral grains which are unoxidized despite their close proximity to the surface and the occasional incursion of oxygenated waters. These sediments have a hydraulic conductivity of about 10⁻⁴ m/day. Saturating water pH is currently 7–8. Sands with 0.2–0.8 wt.% organic C host SO₄-reducing bacteria (SRB), and local cementation by authigenic framboidal pyrite has occurred. SRB were found in water-saturated sediments with decreased hydraulic conductivity and alkaline and anoxic conditions. These bacteria are involved in the formation of authigenic framboidal pyrite, reducing the cycling of dissolved Fe in the sediments. Carbon is not a limiting factor in this process as organic matter is present in the sandstone and ground water contains up to 180 ppm HCO₃^-. Comparison of the 28 ka old sediments with the modern tailings suggests that the chemical behaviour of the two will be similar, possibly with the crystallization of authigenic pyrite in the tailings over the long term. As long as the present slightly anoxic and circumneutral pH environmental conditions are maintained in the mixed tailings impoundment, sulfide decomposition and acidification are unlikely.     

Environmental impact and geochemistry of old tailing pile from the Sanggok mine creek, Republic of Korea

This study evaluates the pollution load on a creek based on the physicochemical and mineralogical properties of old tailings. The Sanggok mine is one of the largest lead–zinc producers in the Hwanggangri mining district, Republic of Korea. The vertical profile of the old tailings in the mine area can be divided into three units based on color change, and mineralogical and textural variations, as well as physical and chemical properties. Unit I (surface accumulation and oxidized heterogeneous tailing soil) has lower pH and higher Eh than unit II (originally unoxidized dumped tailing soil) and unit III (pebble-bearing bottom soil). The conductivity data indicates that unit I and II have very high values compared to unit III and basement. The mine area consists mainly of carbonate rocks; however, mineral constituents of tailing soil and sediments near the mine were mainly composed of quartz, mica, feldspar, amphibole, calcite, dolomite, magnesite, and clay minerals. Units I and II are characterized by high abundances of siderite, locally pyrite, and dolomite. Precipitates in the mining drainage mainly included: smectite, illite, berthierine, quartz, siderite, hexahydrite, and Ca-ferrate. Among the separated metallic minerals, tailing soils and sediments of highly concentrated toxic metals are found: some pyrite, arsenopyrite, chalcopyrite, sphalerite, galena, malachite, goethite, various hydroxide, and uncertain secondary minerals. Units I and II are characterized by relatively high concentrations of Ca, Fe, Mn and low contents of Al, Mg, K, Na, Ti, rare earth elements (REEs) that correlated with the proportion of secondary minerals. Potentially toxic elements such as Ag, As, Cd, Cu, Pb, Sb, and Zn are highly enriched in the upper two units. This metal concentration can be influenced by changes in the depth because of oxic and suboxic zonal distribution. The removal zone (unit I) has probably migrated below the elevation of the maximum enrichment layer due to deepening of the oxic/suboxic boundary. In most of the materials, the enrichment index is higher than 3.62. The highest value of 42.55 is found in the oxidation surface soils of the tailing pile. An average enrichment index of the profiles and precipitates are 27.62 and 22.62, respectively. Rocky basement soils have an average enrichment index of 6.63, which is influenced by overlying the tailing pile. The water quality and habitat of the Sanggok creek are severely polluted. Polluted surface water may also negatively impact the agricultural soil and groundwater.     

Hydrochemistry of superficial waters in the Adoria mine area (Northern Portugal): environmental implications

The purpose of this work is to characterize the hydrochemical behavior of acid mine drainages (AMD) and superficial waters from the Adoria mine area (Northern Portugal). Samples of superficial and mine drainage water were collected for one year, bi-monthly, with pH, temperature, Eh, conductivity and HCO₃ determined in situ with chemical analyses of SO₄, Ca, K, Mg, Na, Cl, Ag, As, Bi, Co, Cu, Fe, Mn, Ni, Pb, Zn and Cd. In the mine, there are acidic waters, with low pH and significant concentrations of SO₄, and metals (Fe, Mn, Zn, Cu, Pb, Cd and Ni), while in the superficial natural stream waters outside the mine, the pH is close to neutral, with low conductivity and lower metal concentrations. The stream waters inside the mine influence are intermediate in composition between AMD and natural stream waters outside the mine influence. Principal Component Analysis (PCA) shows a clear separation between AMD galleries and AMD tailings, with tailings having a greater level of contamination.