Hydrochemistry, mineralogy and chemical fractionation of mine and processing wastes associated with porphyry copper mines: A case study from the Sarcheshmeh mine, SE Iran

The Sarcheshmeh is one of the largest Oligo-Miocene porphyry Cu deposits in the world. Comparative hydrochemical, mineralogical and chemical fractionation associated with mining efflorescence salts and processing wastes of this mine are discussed. Hydrochemical results showed that rock waste dumps, reject wastes and old impoundments of tailings are the main sources of acid mine drainage waters (AMD) that contain potentially toxic metals such as Cd, Co, Cu, Mn, Ni and Zn as well as Al. Episodic fluxes of highly contaminated acidic waters were produced in a tailings dam over a short period of time. Secondary soluble minerals provide important controls on the quality of AMD produced, especially in old, dry tailings impoundments. Secondary sulfate minerals such as gypsum, magnesiocopiapite, hydronium jarosite, kornelite and coquimbite were found in rock waste drainages and in old weathered reject wastes. Highly soluble secondary minerals such as gypsum, eriochalcite, and bonattite are also observed in an evaporative layer on old tailings impoundments. Chemical fractionation patterns of potentially toxic elements showed that the geochemical behavior of metals is primarily controlled by the mineralogical composition of waste samples. Elements such as Co, Cr, Cu, Mn, Ni and Zn are readily released into the water soluble fraction from efflorescence salts associated with rock waste drainages, as well as from the evaporative layer of old tailings. Potentially toxic elements, such as As, Mo and Pb, are principally adsorbed or co-precipitated with amorphous and crystalline Fe oxides, but they may also be associated with oxidizing, primary sulfides and residual fractions. Following the development of the dammed tailings pond, the secondary minerals were dissolved, producing acidic waters contaminated by Al (154 mg L⁻¹), Cu (150 mg L⁻¹), Cd (0.31 m gL⁻¹), Co (2.13 mg L⁻¹), Mn (73.7 mg L⁻¹), Ni (1.74 mg L⁻¹), Zn (20.3 mg L⁻¹) and Cl (1690 mg L⁻¹). Therefore, the potential use of recycled water from the Sarcheshmenh dammed tailings pond is diminished by the presence of corrosive ions like Cl⁻ in highly acidic fluids that promote corrosion of pipes and pumps in the water recycling system.     

Geochemistry of arsenic in uranium mine mill tailings,Saskatchewan, Canada

The Rabbit Lake U mine in-pit tailings management facility (TMF) (425 m long×300 m wide×91 m deep) is located in northern Saskatchewan, Canada. The objectives of this study were to quantify the distribution of As phases in the tailings and evaluate the present-day geochemical controls on dissolved As. These objectives were met by analyzing pore fluid samples collected from the tailings body for dissolved constituents, measuring Eh, pH, and temperature of tailings core and pore fluid samples, conducting sequential extractions on solid samples, conducting geochemical modeling of pore fluid chemistry using available thermodynamic data, and by reviewing historical chemical mill process records. Dissolved As concentrations in 5 monitoring wells installed within the tailings body ranged from 9.6 to 71 mg/l. Pore fluid in the wells had a pH between 9.3 and 10.3 and Eh between +58 and +213 mV. Sequential extraction analyses of tailings samples showed that the composition of the solid phase As changed at a depth of 34 m. The As above 34 m was primarily associated with amorphous Fe and metal hydroxides while the As below 34 m was associated with Ca, likely as amorphous poorly ordered calcium arsenate precipitates. The change in the dominant As solid phases at this depth was attributed to the differences in the molar ratio of Fe to As in the mill tailings. Below 34 m it was <2 whereas above 34 m it was >4. The high Ca/As ratio during tailings neutralization would likely precipitate Ca₄(OH)₂(AsO₄)₂:4H₂O type Ca arsenate minerals. Geochemical modeling suggested that if the pore fluids were brought to equilibrium with this Ca-arsenate, the long-term dissolved As concentrations would range between 13 and 126 mg/l.     

Limestone drains to increase pH and remove dissolved metals from acidic mine drainage

Despite encrustation by Fe and Al hydroxides, limestone can be effective for remediation of acidic mine drainage (AMD). Samples of water and limestone (CaCO₃) were collected periodically for 1 a at 3 identical limestone-filled drains in Pennsylvania to evaluate the attenuation of dissolved metals and the effects of pH and Fe- and Al-hydrolysis products on the rate of CaCO₃ dissolution. The influent was acidic and relatively dilute (pH<4; acidity <90 mg) but contained 1–4 mg·L⁻¹ of O₂, Fe³⁺, Al³⁺ and Mn²⁺. The total retention time in the oxic limestone drains (OLDs) ranged from 1.0 to 3.1 hr. Effluent remained oxic (O₂>1 mg·L⁻¹) but was near neutral (pH=6.2–7.0); Fe and Al decreased to less than 5% of influent concentrations. As pH increased near the inflow, hydrous Fe and Al oxides precipitated in the OLDs. The hydrous oxides, nominally Fe(OH)₃ and Al(OH)₃, were visible as loosely bound, orange-yellow coatings on limestone near the inflow. As time elapsed, Fe(OH)₃ and Al(OH)₃ particles were transported downflow. The accumulation of hydrous oxides and elevated pH (>5) in the downflow part of the OLDs promoted sorption and coprecipitation of dissolved Mn, Cu, Co, Ni and Zn as indicated by decreased UK concentrations of the metals in effluent and their enrichment relative to Fe in hydrous-oxide particles and coatings on limestone. Despite thick (∼1 mm) hydrous-oxide coatings on limestone near the inflow, CaCO₃ dissolution was more rapid near the inflow than at downflow points within and the OLD where the limestone was not coated. The high rates of CaCO₃ dissolution and Fe(OH₃) precipitation were associated with the relatively low pH and high Fe³⁺ concentration near the inflow. The rate of CaCO₃ dissolution decreased with increased pH and concentrations of Ca²⁺ and HCO₃⁻ and decreased Pco₂. Because overall efficiency is increased by combining neutralization and hydrolysis reactions, an OLD followed by a settling pond requires less land area than needed for a two-stage treatment system consisting of an anoxic limestone drain an oxidation-settling pond or wetland. To facilitate removal of hydrous-oxide sludge, a perforated-pipe subdrain can be installed within an OLD.     

Depositional characteristics of uranium tailings from Saskatchewan,Canada

The management of uranium tailings, generated as a by-product of ore processing, is particularly important to minimize the environmental footprint of the industry. A clear understanding of tailings slurry behavior is required at the time of deposition to help evaluate the storage capacity and life span of the containment facilities. The main purpose of this study was to investigate the segregation and self-weight settling properties of uranium tailings. Detailed laboratory investigations were conducted on tailings from 4, 5, and 6 % nominal mill feeds (high-grade McArthur River ores blended with special wastes on site) from the Cameco Key Lake operation. The results indicate that the three uranium tailings can be characterized as a sandy silt material with a negligible amount of clay. Their depositional behavior is governed by the initial solids content of the slurry. The investigated tailings showed insignificant segregation between 25 and 40 % initial solids content. The initial hydraulic conductivity during settling was about 10^?4 m/s at a void ratio of 4 and was increased by half an order of magnitude for the 4 % mill feed, and by almost two orders of magnitude for the 5 and 6 % mill feeds at a void ratio of 8. Over the same range of initial void ratio, the settling potential increased threefold: from 8 to 24 % for the 4 % mill feed and from 12 to 36 % for the 5 and 6 % mill feeds. The better rate and amount of dewatering of future high mill feed tailings as compared to the current low mill feed tailings means that the onsite containment facility can store more tailings thereby supporting a longer life span of the mill.     

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.     

Combined hydrochemical,isotopic, and multivariate statistics techniques to assess the effects of discharges from a uranium mine on water quality in neighboring streams

The Caldas Uranium Mine (CUM), located on the Poços de Caldas Plateau in the southeastern region of Brazil, is presently undergoing a decommissioning process. The aim of the present investigation is to identify and characterize the effects of acid mine drainage (AMD) originating from the CUM on surface water quality. To achieve these aims, sampling stations were located at two AMD sources: the retention pond at the foot of waste rock pile#4 (WRP#4) and the settling pond that receives effluents from the tailings dam (TD). Ten additional sampling stations were located along watercourses in the vicinity, both downstream and upstream of the mine. Sampling was performed during the rainy and dry seasons in 2010 and 2011. The water analysis detected significant changes in pH, electrical conductivity, F^?, Cd, U, Zn, Al, Mn, As, Ca, SO₄ ^2?, Pb, ²³⁸U, ²²⁶Ra, ²¹⁰Pb, ²³²Th, ²²⁸Ra, and Mo in waters downstream of both pond discharge sites. It was demonstrated that the disequilibrium between ²²⁶Ra and ²³⁸U can be used to trace the extent of AMD impacts in nearby streams. Variations in ¹⁸O and ²H enabled the flow of mining-impacted water to be traced from the ponds to nearby streams. Multivariate analysis yielded a three-factor model: Factor 1 was interpreted as being associated with AMD (from WRP#4) and Factor 2 with a Ca–Mo relationship associated with the chemical constitution of the ore and with the treatment of tailings wastes in the area (from TD); Factor 3 was interpreted as being associated with the natural influence of geogenic processes on water quality in the area. The results of this study provide a scientific basis for recommending appropriate remedial actions during mine decommissioning.     

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.     

Methylmercury in tailings ponds of Amazonian gold mines (French Guiana): Field observations and an experimental flocculation method for in situ remediation

Sites of monomethylmercury (MMHg) production in Amazonian regions have been identified in hydraulic reservoirs, lake sediments and wetlands, but tailings ponds have not yet received sufficient attention for this purpose. This work evidenced high MMHg production within the water column and the interstitial water of two tailings ponds of French Guiana Au mines located; (i) in a small scale exploitation (Combat) where Hg was used for Au amalgamation, and (ii) in an industrial on-going Au mine (Yaoni) processing without Hg. The (MMHg)_D maximum (2.5 ng L⁻¹) occurred in the oxic water column above the sediment-water interface (SWI) of the most recent tailings pond (Combat), where the substrate was fresh, the redox transition was sharp and the pool of total Hg was large. In the Yaoni pond, the (MMHg)_D maximum concentration (1.4 ng L⁻¹) was located at the SWI where suboxic conditions prevailed. Using the (MMHg)_D concentration as a proxy for Hg methylation rates, the present results show that Hg methylation may occur in various redox conditions in tailings ponds, and are favored in areas where the organic matter regeneration is more active.A 3-month long laboratory experiment was performed in oxic and anoxic boxes filled with high turbidity waters from the Combat Au mine to simulate tailings ponds. Slaked lime was added in an experimental set (2 mg L⁻¹) and appeared to be very efficient for the reduction of suspended particulate matter (SPM) to environmentally acceptable concentrations. However, at the end of the experiment, large (MMHg)_D concentrations were monitored under treated anoxic conditions with the (MMHg)_D maximum located at the SWI above the Fe-reducing zones. No (MMHg)_D was detected in oxic experiments. The use of slaked lime for SPM decantation appears to be an efficient and non-onerous process for Au miners to avoid Hg methylation in tailings ponds when it is combined with rapid drainage of the mine waters. A subsequent human intervention is however necessary for the recovery of soil structure through the cover of dried ponds with organic rich materials and reforestation to avoid the stagnation of rain waters and the occurrence of anoxia.     

Heavy metal contamination of a Greenland fjord system by mine wastes

Since 1973, about 500,000 tons/yr of metal-rich particulate tailings from a lead/zinc flotation mill have been discharged through a submarine outfall into a two fjord system on the west coast of Greenland. Differential solubilization of particulate metals by seawater, seasonal water mixing, and sill exchange tailings dispersal processes have resulted in high, but seasonally variable Zn, Cd, and Pb contamination of the water, and suspended particulate matter (SPM).Chemical partition of the SPM shows that most (85-99 percent) of the Pb, but relatively low proportions of Zn (14-26 percent) and Cd (10–20 percent) are weakly bound to the SPM. Such particulate metal characteristics allow the real time effects of tailings discharges and dispersal on the system to be traced even in the sediments where tailings accumulation is very slow (0.1 cm/yr).Fjord seaweeds and blue mussels also contain varying amounts of Zn, Pb, and Cd depending on the metal and their location relative to the tailings outfall and apparently responded almost instantly to the metal contamination, as did the water and SPM. High Pb concentrations in the fjord mussels most likely derive from the preferential uptake of available particulate Pb, whereas the seaweeds appear to derive most of their heavy metal concentrations from the dissolved phase. The evidence from this and other sites as well as from experimental work, indicates that any discharge of Pb-bearing particles into the marine environment either directly as mine wastes or indirectly as from natural runoff from current and former lead mining sites results in immediate lead contamination of the in situ mussel population.     

Mercury in sediments from gold and copper exploitation areas in the Camaquã River Basin,Southern Brazil

Mercury concentrations were determined in stream sediments from the Camaquã River Basin, located in the shield region of the state of Rio Grande do Sul, southern Brazil. The resulting geochemical data show that overbank floodplain deposits exhibit higher concentrations than sediments collected from the active channel bed. In addition, higher Hg concentrations were measured in the fine(<63 μm) sediment fraction of the samples. Total Hg concentrations in the fine fraction of active stream sediments from Lavras do Sul County, which have been influenced by past gold mining activities, have decreased during the last five years to values ≤142 ng g⁻¹. However, in a settling pond containing abandoned mine wastes, the Hg concentration of a bulk sample remained exceptionally high (5220 ng g⁻¹). Preliminary speciation results show that Hg⁰ is the predominant species in most of the samples. This was the form of Hg released by the gold amalgamation activities in the area, and appears to be relatively stable under the existing E_h and pH conditions.     

Mobility and retention of trace elements in hardpan-cemented cassiterite tailings, north Queensland, Australia

This study reports on the mobility and retention of trace elements in cassiterite tailings at the inactive Jumna mill, tropical north Queensland. Since the 1980s, the uncapped tailings have developed laterally discontinuous Fe-rich hardpans, which are located in the higher parts of gently sloping tailings masses and at the top (<50 cm) of the tailings piles. Hardpan-cemented tailings comprise thin layers (typically ∼0.2–2 mm thick) of HFO (hydrous ferric oxides) and sulfate efflorescences cementing tailings grains. In comparison to the tailings, the hardpan-cemented tailings contain significantly higher median As, Ca, Cd, Co, Cu, Fe, In, Mn, Mo, S_total, Th, U, Y and Zn values. Partial leaching studies of tailings and pond water analyses indicate that wetting and acidification of Fe-cemented tailings removes significant proportions of trace elements into pore and surface waters. Tin shows no mobility due to the presence of weathering-resistant cassiterite (SnO₂) and, As and Pb display limited mobility possibly due to their coprecipitation with jarosite-type phases and HFO materials at the top of the tailings profile. By contrast, the trace elements Cd, Ce, Cu, La, Ni, Pb, U and Zn display the greatest mobility, possibly due to their incorporation in soluble sulfate efflorescences and sorption onto mineral and HFO surfaces. Hence, the Fe-rich hardpans do not protect the sulfidic tailings from further oxidation nor do they cause permanent sequestration of trace elements.     

Precipitation of aluminum and magnesium secondary minerals from uranium mill raffinate (pH 1.0–10.5) and their controls on aqueous contaminants

Models of geochemical controls on elements of concern (EOCs; e.g., As, Se, Mo, Ni) in U tailings are dominated by ferrihydrite. However, the evolution of aqueous concentrations of Al and Mg through the Key Lake (KL) U mill bulk neutralization process indicates that secondary Al and Mg minerals comprise a large portion of the tailings solids. X-ray diffraction, Al K-edge XAS, and TEM elemental mapping of solid samples collected from a pilot-scale continuous-flow synthetic raffinate neutralization system of the KL mill indicate the secondary Al–Mg minerals present include Mg–Al hydrotalcite, amorphous Al(OH)₃, and an amorphous hydrobasaluminite-type phase. The ferrihydrite present contains Al and may be more accurately described as Al–Fe(OH)₃. In the final combined tailings sample (pH 10.5) collected from the model experiments using raffinate with Al, Mg, and Fe, solid phase EOCs were associated with Al–Fe(OH)₃ and Mg–Al hydrotalcite. In model experiments using raffinate devoid of Fe, aqueous EOC concentrations decreased greatly at pH 4.0 (i.e., where ferrihydrite would precipitate) and largely remained in the solid phase when increased to the terminal pH of 10.5; this suggests Al–Mg minerals can control aqueous concentrations of EOCs in the raffinate in the absence of Fe. Maximum adsorption capacities for individual and mixtures of adsorbates by Mg–Al hydrotalcite were determined. A revised model of the geochemical controls in U mill tailings is presented in which Al and Mg minerals co-exist with Fe minerals to control EOC concentrations.     

The mobility of radium-226 and trace metals in pre-oxidized subaqueous uranium mill tailings

The exchange of ²²⁶Ra and trace metals across the tailings-water interface and the mechanisms governing their mobility were assessed via sub-centimetre resolution profiling of dissolved constituents across the tailings–water interface in Cell 14 of the Quirke Waste Management Area at Rio Algom's Quirke Mine, near Elliot Lake, Ontario, Canada. Shallow zones (<1.5 m water depth) are characterized by sparse filamentous vegetation, well-mixed water columns and fully oxygenated bottom waters. Profiles of dissolved O₂, Fe and Mn indicate that the tailings deposits in these areas are sub-oxic below tailings depths of ∼3 cm. These zones exhibit minor remobilization of Ra in the upper 5 cm of the tailings deposit; ²²⁶Ra fluxes at these sites are relatively small, and contribute negligibly to the water column activity of ²²⁶Ra. The shallow areas also exhibit minor remobilization of Ni, As, Mo and U. The release of these elements to the water cover is, however, limited by scavenging mechanisms in the interfacial oxic horizons. The presence of thick vegetation (Chara sp.) in the deeper areas (>2 m water depth) fosters stagnant bottom waters and permits the development of anoxia above the benthic boundary. These anoxic tailings are characterized by substantial remobilization of ²²⁶Ra, resulting in a relatively large flux of ²²⁶Ra from the tailings to the water column. The strong correlation between the porewater profiles of ²²⁶Ra and Ba (r²=0.99), as well as solubility calculations, indicate that the mobility of Ra is controlled by saturation with respect to a poorly ordered and/or impure barite phase [(Ra,Ba)SO₄]. In the anoxic zones, severe undersaturation with respect to barite is sustained by microbial SO₄ reduction. Flux calculations suggest that the increase in ²²⁶Ra activity in the water cover since 1995 (from <0.5 to 2.5 Bq l⁻¹) can be attributed to an increase in the spatial distribution of anoxic bottom waters caused by increased density of benthic flora. The anoxic, vegetated areas also exhibit minor remobilization with respect to dissolved As, Ni and Zn. The removal of trace metals in the anoxic bottom waters appears to be limited by the availability of free sulphide. Collectively, the data demonstrate that while the water cover over the U mill tailings minimizes sulphide oxidation and metal mobility, anoxic conditions which have developed in deeper areas have led to increased mobility of ²²⁶Ra.     

高密度电法勘探数据在Voxler平台的三维可视化展示——及其在尾矿库隐患勘查中的应用

尾矿库内堆放的有污染的固体和液体废物若得不到合理妥善的处理, 会对周边的环境造成严重的污染. 为了确定尾矿库的稳定性, 分析尾矿库内的固、液废弃物对周边土壤和地下水的影响, 急需查明尾矿库的形态特征和库容规模. 高密度电法作为一种常规的物探方法, 以其简便、快捷、高效等特点, 在确定尾矿库形态特征方面成为现场探测的首选技术手段. 本研究运用高密度电法反演得到尾矿库的底界面范围, 并结合钻孔验证, 在Voxler平台构建了尾矿库的可视化三维模型, 从而更加精确计算尾矿砂的方量, 证明了高密度电法在确定尾矿库形态特征中的可行性.     

Release,transport and attenuation of metals from an old tailings impoundment

The oxidation of sulfide minerals from mine wastes results in the release of oxidation products to groundwater and surface water. The abandoned high-sulfide Camp tailings impoundment at Sherridon, Manitoba, wherein the tailings have undergone oxidation for more than 70 a, was investigated by hydrogeological, geochemical, and mineralogical techniques. Mineralogical analysis indicates that the unoxidized tailings contain nearly equal proportions of pyrite and pyrrhotite, which make up to 60 wt% of the total tailings, and which are accompanied by minor amounts of chalcopyrite and sphalerite, and minute amounts of galena and arsenopyrite. Extensive oxidation in the upper 50 cm of the tailings has resulted in extremely high concentrations of dissolved SO₄ and metals and As in the tailings pore water (pH < 1, 129,000 mg L⁻¹ Fe, 280,000 mg L⁻¹ SO₄, 55,000 mg L⁻¹ Zn, 7200 mg L⁻¹ Al, 1600 mg L⁻¹ Cu, 260 mg L⁻¹ Mn, 110 mg L⁻¹ Co, 97 mg L⁻¹ Cd, 40 mg L⁻¹ As, 15 mg L⁻¹ Ni, 8 mg L⁻¹ Pb, and 3 mg L⁻¹ Cr). The acid released from sulfide oxidation has been extensive enough to deplete carbonate minerals to 6 m depth and to partly deplete Al-silicate minerals to a 1 m depth. Below 1 m, sulfide oxidation has resulted in the formation of a continuous hardpan layer that is >1 m thick. Geochemical modeling and mineralogical analysis indicate that the hardpan layer consists of secondary melanterite, rozenite, gypsum, jarosite, and goethite. The minerals indicated mainly control the dissolved concentrations of SO₄, Fe, Ca and K. The highest concentrations of dissolved metals are observed directly above and within the massive hardpan layer. Near the water table at a depth of 4 m, most metals and SO₄ sharply decline in concentration. Although dissolved concentrations of metals and SO₄ decrease below the water table, these concentrations remain elevated throughout the tailings, with up to 60,600 mg L⁻¹ Fe and 91,600 mg L⁻¹ SO₄ observed in the deeper groundwater. During precipitation events, surface seeps develop along the flanks of the impoundment and discharge pore water with a geochemical composition that is similar to the composition of water directly above the hardpan. These results suggest that shallow lateral flow of water from a transient perched water table is resulting in higher contaminant loadings than would be predicted if it were assumed that discharge is derived solely from the deeper primary water table. The abundance of residual sulfide minerals, the depletion of aluminosilicate minerals in the upper meter of the tailings and the presence of a significant mass of residual sulfide minerals in this zone after 70 a of oxidation suggest that sulfide oxidation will continue to release acid, metals, and SO₄ to the environment for decades to centuries.     

Dispersion of tailings in the Knabena—Kvina drainage basin, Norway, 1: Evaluation of overbank sediments as sampling medium for regional geochemical mapping

Molybdenum mining in the Knabena—Kvina drainage basin (1918–1973) left more than eight million tons of tailings in two small lakes in the headwater area of the Knabena river. The piles, that reach above the water surface, were freely eroded until a dam was built to reduce the dispersion in 1976. Sampling of tailings and fluvial sediments took place almost 20 years later. Sampling media were natural sediment sources, 1-cm-thick slices of overbank sediments of various depths, material from the tailings pond, sandbars, stream sediments, fjord sediments, and integrated samples of floodplain surfaces (0–25 cm). In total 734 samples were collected. Chemical analysis (ICP-AES after aqua regia or HNO₃ extraction) showed that overbank sediments at a certain depth represent the pre-industrial trace metal concentrations within the drainage basin. The tailings and recent fluvial sediments were enriched in approximately the same element suite. The highest enrichment factors were obtained for Cu (8–53) and Mo (22–57). Fluvial processes in the tailings pond have probably selectively eroded fine-grained, low-density particles. Thus, coarse chalcopyrite may have been left behind, while molybdate associated with fine-grained particles may have been selectively entrained causing dilution of Cu and enrichment of Mo in the downstream fluvial sediments. In the sandbars, the highest Cu and Mo concentrations were found in fine-grained sediments downstream of a low-gradient reach that act as a bedload trap. On the floodplains, it is seen that the first areas to be inundated in a flood situation (proximal to the river and in depressions) have the highest metal concentrations. For regional geochemical mapping it is suggested that overbank sediment profiles along river reaches with a laterally stable or slowly migrating channel, should be sampled. In such floodplains, pre-industrial overbank sediments are usually preserved at depth. In case of laterally unstable reaches upstream of the sampling point, polluted and unpolluted sediments may be interlayered or mixed. Therefore, samples should be collected from various depths or sedimentary units in such profiles. A similar sampling strategy should probably be adopted to detect vertical migration of elements especially in areas with acid rain and low bedrock buffer capacity. To obtain high contrasts between polluted and unpolluted drainage basins, the overbank sediment profiles should be within the proximal part of the floodplain.     

Mine waste water self-purification (arsenic) in neutral hydrogeochemical ecosystem: A case study from V-Ti-Fe mine tailings

The fate of the arsenic (As) under neutral hydrogeochemical conditions in the mining ecosystem has attracted increasing concern, as the ecological restoration of As provides a possibility for safe use of mine water. However, successful cases are still inadequately reported worldwide. Therefore, to investigate the As-behavior in the mine tailings ecosystem, a study of the Wanniangou tailings pond (regional largest V-Ti-Fe mine tailings pond, Sichuan province, China) and the downstream (Rehe River) was conducted. It involves hydro-geochemistry, mineralogy, biogeochemistry, and the Geographically Weighted Regression model (GWR). The results reveal that: (1) the pH range of the mine water is 6.32 to 7.21. The chemical weathering of tailings resulted in an abnormal As concentration in water (e.g., transport pipe wastewater 76.5 μg L⁻¹, the outlet of tailings pond 28.4 μg L⁻¹), and it declines to the national water quality guideline (<10 μg L⁻¹) after 2.59 km from the pond outlet. (2) Although sulfide oxidation boosts As migration in the tailings, As ecological refixation is promoted by tailings particle percolation, river sediment absorption, and aquatic plant uptake. The As refixation behaviors vary spatially, corresponding with the diversity of precipitation and absorption. Besides, Manganese (oxides or/and hydroxides) is conducive to As coprecipitation in the neutral hydrogeochemical environment. (3) The site selection of the V-Ti-Fe mine tailings pond with a downstream longer than 3 km creates a toxic metals self-restoration buffer zone, which could relieve the contamination probability and make the mining wastewater re-utilization feasible.     

Behavior of Uranium in the Yellow River Plume (Yellow River Estuary)

The Yellow River (Huanghe) is the second largest river in China and is known for its high turbidity. It also has remarkably high levels of dissolved uranium (U) concentrations (up to 38 nmol 1^-1). To examine the mixing behavior of dissolved U between river water and seawater, surface water samples were collected along a salinity gradient from the Yellow River plume during September 2004 and were measured for dissolved U concentration,²³⁴U:²³⁸U activity ratio, phosphate (PO₄ ^3–), and suspended particulate matter. Laboratory experiments were also conducted to simulate the mixing process in the Yellow River plume using unfiltered Yellow River water and filtered seawater. The results showed a nonconservative behavior for dissolved U at salinities < 20 with an addition of U to the plume waters estimated at about 1.4 X 10⁵ mol yr^–1. A similarity between variations in dissolved U and PO₄ ^3– with salinity was also found. There are two major mechanisms, desorption from suspended sediments and diffusion from interstitial waters of bottom sediments, that may cause the elevated concentrations of dissolved U and PO₄ ^3– in mid-salinity waters. Mixing experiments indicate that desorption seems more responsible for the elevated dissolved U concentrations, whereas diffusion influences more the enrichment of PO₄ ^3–.     

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.