Mobilization and attenuation of heavy metals within a nickel mine tailings impoundment near Sudbury, Ontario, Canada

 The oxidation and the subsequent dissolution of sulfide minerals within the Copper Cliff tailings area have led to the release of heavy metals such as Fe, Ni, and Co to the tailings pore water. Dissolved concentrations in excess of 10 g/l Fe and 2.2 g/l Ni have been detected within the shallow pore water of the tailings, with increasing depth these concentrations decrease to or near analytical detection limits. Geochemical modelling of the pore-water chemistry suggests that pH-buffering reactions are occurring within the shallow oxidized zones, and that secondary phases are precipitating at or near the underlying hardpan and transition zones. Mineralogical study of the tailings confirmed the presence of goethite, jarosite, gypsum, native sulfur, and a vermiculite-type clay mineral. Goethite, jarosite, and native sulfur form alteration rims and pseudo-morphs of the sulfide minerals. Interstitial cements, composed of goethite, jarosite, and gypsum, locally bind the tailings particles, forming hardpan layers. Microprobe analyses of the goethite indicate that it contains up to 0.6 weight % Ni, suggesting that the goethite is a repository for Ni. Other sinks detected for heavy metals include jarosite and a vemiculite-type clay mineral which locally contains up to 1.6 weight % Ni. To estimate the mass and distribution of heavy metals associated with the secondary phases within the shallow tailings, a series of chemical extractions was completed. The experimental design permitted four fractions of the tailings to be evaluated independently. These four fractions consisted of a water-soluble, an acid-leachable, and a reducible fraction, as well as the whole-rock total. Twenty-five percent of the total mass of heavy metals was removed in the acid-leaching experiments, and 100% of the same components were removed in the reduction experiments. The data suggest that precipitation/coprecipitation reactions are providing an effective sink for most of the heavy metals released by sulfide mineral oxidation. In light of these results, potential decommissioning strategies should be evaluated with the recognition that changing the geochemical conditions may alter the stability of the secondary phases within the shallow tailings. Received: 9 April 1997 · Accepted: 21 July 1997     

Speciation and colloid transport of arsenic from mine tailings

In addition to affecting biogeochemical transformations, the speciation of As also influences its transport from tailings at inoperative mines. The speciation of As in tailings from the Sulfur Bank Mercury Mine site in Clear Lake, California (USA) (a hot-spring Hg deposit) and particles mobilized from these tailings have been examined during laboratory-column experiments. Solutions containing two common, plant-derived organic acids (oxalic and citric acid) were pumped at 13 pore volumes d⁻¹ through 25 by 500 mm columns of calcined Hg ore, analogous to the pedogenesis of tailings. Chemical analysis of column effluent indicated that all of the As mobilized was particulate (1.5 mg, or 6% of the total As in the column through 255 pore volumes of leaching). Arsenic speciation was evaluated using X-ray absorption spectroscopy (XAS), indicating the dominance of arsenate [As(V)] sorbed to poorly crystalline Fe(III)-(hydr)oxides and coprecipitated with jarosite [KFe₃(SO₄, AsO₄)₂(OH)₆] with no detectable primary or secondary minerals in the tailings and mobilized particles. Sequential chemical extractions (SCE) of <45 μm mine tailings fractions also suggest that As occurs adsorbed to Fe (hydr)oxides (35%) and coprecipitated within poorly crystalline phases (45%). In addition, SCEs suggest that As is associated with 1 N acid-soluble phases such as carbonate minerals (20%) and within crystalline Fe-(hydr)oxides (10%). The finding that As is transported from these mine tailings dominantly as As(V) adsorbed to Fe (hydr)oxides or coprecipitated within hydroxysulfates such as jarosite suggests that As release from soils and sediments contaminated with tailings will be controlled by either organic acid-promoted dissolution or reductive dissolution of host phases.     

Mechanisms controlling acid neutralization and metal mobility within a Ni-rich tailings impoundment

Low-quality pore waters containing high concentrations of dissolved H⁺, SO₄, and metals have been generated in the East Tailings Management Area at Lynn Lake, Manitoba, as a result of sulfide-mineral oxidation. To assess the abundance, distribution, and solid-phase associations of S, Fe, and trace metals, the tailings pore water was analyzed, and investigations of the geochemical and mineralogical characteristics of the tailings solids were completed. The results were used to delineate the mechanisms that control acid neutralization, metal release, and metal attenuation. Migration of the low-pH conditions through the vadose zone is limited by acid-neutralization reactions, resulting in the development of distinct pore-water pH zones at depth; the neutralization reactions involve carbonate (pH ⩾ 5.7), Al-hydroxide (pH ⩾ 4.0), and aluminosilicate solids. As the zone of low-pH pore water expands, the pH will then be primarily controlled by less soluble solids, such as Fe(III) oxyhydroxides (pH < 3.5) and the relatively more recalcitrant aluminosilicates (pH ⩾ 1.3). Precipitation/dissolution reactions involving secondary Fe(III) oxyhydroxides and hydroxysulfates control the concentrations of dissolved Fe(III). Concentrations of dissolved SO₄ are principally controlled by the formation of gypsum and jarosite. Geochemical extractions indicate that the solid-phase concentrations of Ni, Co, and Zn are associated predominantly with reducible and acid-soluble fractions. The concentrations of dissolved trace metals are therefore primarily controlled by adsorption/complexation and (or) co-precipitation/dissolution reactions involving secondary Fe(III) oxyhydroxide and hydroxysulfate minerals. Concentrations of dissolved metals with relatively low mobility, such as Cu, are also controlled by the precipitation of discrete minerals. Because the major proportion of metals is sequestered through adsorption and (or) co-precipitation, the metals are susceptible to remobilization if low-pH or reducing conditions develop within the tailings.     

Detrital transport of metals by glaciers, an example from the Pinchi Mine, central British Columbia

 Abundant cinnabar (HgS) mineralization is associated with the Pinchi Fault in central British Columbia. Two formerly producing mercury mines have been developed on this fault: Pinchi and Bralorne Takla. The mercury content of till (a sediment type directly deposited by glaciers) in the area of this fault is primarily controlled by the occurrence of cinnabar mineralization in bedrock and the direction of ice flow. Cinnabar-bearing bedrock was eroded by glaciers, transported in the direction of ice flow, and deposited "down-ice" from its source. An example of such a dispersal train is documented for the Pinchi Mine area where mercury ore was transported over a distance of 12 km, as measured in the clay-sized fraction (< 0.002 mm) of till, and could have been transported over 24 km according to heavy mineral concentrates (specific gravity >3.3) of this same sediment. Antimony, chromium, and nickel dispersal trains were also detected in the region. These data indicate that natural glacial processes can result in the "mobilization" of metals in the surficial environment, a factor which has to be considered at mine sites in glaciated terrain, where mine reclamation and remediation measures are now required. Received: 31 October 1996 · Accepted: 27 May 1997     

Chemical availability of arsenic and heavy metals in sediments from abandoned cinnabar mine tailings

The understanding of the solid-phase speciation of arsenic in soils and sediments is important in the evaluations of its potential mobility and availability in the environment. The spoil heaps of abandoned mercury mines contain waste materials with high arsenic and heavy metals concentrations. The weathering of these tailings can cause their mobilization to the surroundings. In this work, the mobility and availability of arsenic and some heavy metals were evaluated in sediments from two heavily polluted mercury mining districts in Asturias (NW Spain). For this purpose, a slightly modified version of the Bureau Community of Reference sequential extraction scheme was applied to sediments. The total contents in the operationally defined fractions were analysed by inductively coupled plasma-atomic emission spectrometry. Extremely high total arsenic concentrations were found in all sediments ranging from 4,000 to 24,800 mg kg^?1. High easily mobilizable arsenic contents were found in the first mining area, related to the solubilization of Ca-bearing phases, supported by extracts analyses, X-ray diffraction results and the positive correlation found among the As and Ca fractionations. Ni and Zn were the most mobile among heavy metals, being Cr the least mobile, suggesting an anthropogenic origin due to the metallurgical processes, transport or dispersion generated from neighbour spoil heaps. In the second mining area, the bulk of As was concentrated in the residual phase, as well as Cr, Cu, Fe, Pb, Ti, indicating a mineralogical origin and the low availability of these elements. The strong correlations established between As and Fe and Ti distributions support the hypothesis that As is mainly associated to structural mineral phases in these sediments.     

Release ofRa from uranium mill tailings by microbial Fe(III) reduction

Uranium mill tailings were anaerobically incubated in the presence of H₂ with Alteromonas putrefaciens, a bacterium known to couple the oxidation of H₂ and organic compounds to the reduction of Fe(III) oxides. There was a direct correlation between the extent of Fe(III) reduction and the accumulation of dissolved²²⁶Ra. In sterile tailings in which Fe(III) was not reduced, there was negligible leaching of²²⁶Ra. The behavior of Ba was similar to that of Ra in inoculated and sterile systems. These results demonstrate that under anaerobic conditions, microbial reduction of Fe(III) may result in the release of dissolved²²⁶Ra from uranium mill tailings.     

Sedimentation processes in an impoundment,Union lake,New Jersey

A small (3 75 km²) impoundment. Union Lake, on the Maurice River in southern New Jersey contains fine-grained sediment and organic material being transported through the surface water system Sedimentation is slow and rates calculated from¹³⁷Cs-dated cores indicate a decrease through time from 2 6 mm/yr to 0 57 mm/yr Sediment from shallow areas (<3 m) consists of winnowed preimpoundment fluvial sand, whereas sediment from deeper areas (>3 m) is dy composed of diatoms, organic matter, and silt- and clay-sized mineral grains Sediment distribution is controlled by water moving from the river entrance southward toward the outlet and by wind-generated water motion from shallow areas fringing the shore toward deeper portions of the impoundment     

沐官岛水库蓄水初期盐分运移数值模拟

沐官岛水库是一个拟建的河口海湾水库,库底为富含咸水的潮滩沉积物。这一特殊的地质及水环境条件直接关系到水库未来的水质安全和正常的调度运行,所以必须准确地确定水库水体中盐分空间分布这一关键问题。本文依据现场调查、钻探及室内实验资料,通过垂直方向线性插值技术,建立了沐官岛水库蓄水初期盐分运移准三维模型,模拟了水库蓄水初期在内源盐分释放影响下,库水盐分的演化过程。结果表明:若遇平水年开始蓄水,当蓄水至1.5m时,该层含盐量在平面上的变化范围主要在0.30~1.30g/L之间;当蓄水至4.5m时,该层含盐量在平面上的变化范围主要在0.30~1.55g/L。     

Multiphase flow and reactive transport model in vadose tailings

Weathering processes affecting pyritic wastes may generate huge amounts of acid waters with high concentrations of potentially toxic contaminants (acid mine drainage). Acid mine drainage is mainly produced in the vadose zone. In the present study, a coupled non-isothermal multiphase flow and reactive transport model of the vadose zone of sulfide mine tailings was developed. The geochemical model included kinetically controlled reactions for Fe(II)-oxidation and for the dissolution of sulfide and aluminosilicate phases and the Pitzer ion-interaction model to describe the behavior of the pore-water solutions. Model results were compared with experimental observations in unsaturated column experiments under strongly evaporative conditions similar to arid or semiarid climates. Evolution trends for temperature, water saturation, evaporation rates, pore-water hydrochemistry and mineral phases observed during the drying experiment were adequately reproduced. The coupled model reproduced the increase of solute concentrations in the column top and the precipitation of a crust of secondary mineral phases. This crust became a barrier for water vapour diffusion to the atmosphere and modified the thermohydraulic behavior of the tailings. Enhanced downward migration of water vapour and its condensation in this colder end of the column were correctly taken into account by the model, which reproduced the dilution observed in the lower part of the column during the experiments.     

Effects of acid-sulfate weathering and cyanide-containing gold tailings on the transport and fate of mercury and other metals in Gossan Creek: Murray Brook mine,New Brunswick,Canada

Gossan Creek, a headwater stream in the SE Upsalquitch River watershed in New Brunswick, Canada, contains elevated concentrations of total Hg (Hg_T up to 60 μg/L). Aqueous geochemical investigations of the shallow groundwater at the headwaters of the creek confirm that the source of Hg is a contaminated groundwater plume (neutral pH with Hg and Cl concentrations up to 150 μg/L and 20 mg/L, respectively), originating from the Murray Brook mine tailings, that discharges at the headwaters of the creek. The discharge area of the contaminant plume was partially delineated based on elevated pH and Cl concentrations in the groundwater. The local groundwater outside of the plume contains much lower concentrations of Hg and Cl (<0.1 μg/L and 3.8 mg/L, respectively) and displays the chemical characteristics of an acid-sulfate weathering system, with low pH (4.1–5.5) and elevated concentrations of Cu, Zn, Pb and SO₄ (up to 5400 μg Cu/L, 8700 μg Zn/L, 70 μg Pb/L and 330 mg SO₄/L), derived from oxidation of sulfide minerals in the Murray Brook volcanogenic massive sulfide deposit and surrounding bedrock. The Hg_T mass loads measured at various hydrologic control points along the stream system indicate that 95–99% of the dissolved Hg_T is attenuated in the first 3–4 km from the source. Analyses of creek bed sediments for Au, Ag, Cu, Zn, Pb and Hg indicate that these metals have partitioned strongly to the sediments. Mineralogical investigations of the contaminated sediments using analytical scanning electron microscopy (SEM), transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM), reveal discrete particles (<1–2 μm) of metacinnabar (HgS), mixed Au–Ag–Hg amalgam, Cu sulfide and Ag sulfide.     

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。     

Mobilization and attenuation of metals downstream from a base-metal mining site in the Mátra Mountains, northeastern Hungary

Regional geochemical baseline values have been established for Hungary by the use of low-density stream-sediment surveys of flood-plain deposits of large drainage basins and of the fine fraction of stream sediments. The baseline values and anomaly thresholds thus produced helped to evaluate the importance of high toxic element concentrations found in soils in a valley downstream of a polymetallic vein-type base-metal mine. Erosion of the mine dumps and flotation dump, losses of metals during filtering, storage and transportation, human neglects, and operational breakdowns, have all contributed to the contamination of a small catchment basin in a procession of releases of solid waste. The sulfide-rich waste material weathers to a yellow color; this layer of `yellow sand' blankets a narrow strip of the floodplain of Toka Creek in the valley near the town of Gyöngyösoroszi. Contamination was spread out in the valley by floods. Metals present in the yellow sand include Pb, As, Cd, Cu, Zn, and Sb. Exposure of the local population to these metals may occur through inhalation of airborne particulates or by ingestion of these metals that are taken up by crops grown in the valley. To evaluate the areal extent and depth of the contamination, active stream sediment, flood-plain deposits, lake or reservoir sediments, soils, and surface water were sampled along the erosion pathways downstream of the mine and dumps. The flood-plain profile was sampled in detail to see the vertical distribution of elements and to relate the metal concentrations to the sedimentation and contamination histories of the flood plain. Downward migration of mobile Zn and Cd from the contaminated upper layers under supergene conditions is observed, while vertical migration of Pb, As, Hg and Sb appears to be insignificant. Soil profiles of ¹³⁷Cs which originated from above-ground atomic bomb tests and the Chernobyl accident, provide good evidence that the upper 30–40 cm of the flood-plain sections, which includes the yellow sand contamination, were deposited in the last 30–40 years.     

Geochemical transport modelling of drainage from experimental mine tailings cells covered by capillary barriers

The use of covers with capillary barrier effects (CCBEs) for reducing acid mine drainage (AMD) from sulphidic mine tailings is simulated using the MIN3P finite volume model for coupled groundwater flow, O₂ diffusion and multi-component reactive transport. The model is applied to simulate five pilot-scale in situ test cells containing reactive tailings from the Manitou mine site, Val d’Or, Que., Canada. Four of the cells were constructed with CCBEs over the tailings, while the fifth tailings cell was left uncovered. Observed and simulated discharge from the base of each cell showed that the capillary barrier covers significantly reduced sulphide oxidation and AMD. Compared to acidic discharge from the uncovered cell, discharge from the four CCBE-covered cells had neutral pH levels and 1–7 orders of magnitude lower concentrations of SO₄, Fe, Zn, Cu and Al. The simulations showed that the moisture retaining layer of the CCBEs reduced AMD by inhibiting O₂ diffusion into the underlying reactive wastes. Provided the moisture-retention layer of the CCBE remains close to saturation, its thickness had a relatively minor effect. Under such near-saturated conditions, O₂ availability is limited by its diffusion rate through the bulk porous medium and not by the diffusion rate through the oxidized grain shells. The model is providing important new insights for comparing design alternatives for reducing or controlling AMD.     

Water quality assessment and hydrochemical characteristics of groundwater on the aspect of metals in an old town,Foshan, south China

The present study is aimed at assessing the water quality and discussing the hydrochemical characteristics and seasonal variation of shallow groundwater on the aspect of metals in the eastern Chancheng district of Foshan city, south China. Multivariate analytical methods such as principal components analysis (PCA) and hierarchical cluster analysis (HCA) were used in this study. The results show that 45% of groundwater in the east-central of study area is not suitable for drinking purpose due to high concentrations of Fe, Pb and Mn. The mean concentrations of Fe, Hg, Cu, Pb, and Mn in dry season are higher than that in wet season. On the contrary, the mean concentrations of Cd, Co, Zn, Ba, Cr, Mo, Ni and Al in wet season are higher than that in dry season. PCA results show that four PCs are responsible for the 78.6% of the total hydrochemical variables in groundwater. Three groups were generated from HCA method. Group 1 reflects the characteristic of wet season and the low ion exchange capacity; group 2 is mainly influenced by the dry season. Reducing environment and high ion exchange capacity are responsible for group 3. The results are useful in addressing future measures in groundwater resource management for local government.     

Mobility of heavy metals from tailings to stream waters in local zinc smelting activities contaminated site

It has been found that stream waters were severely contaminated with wastes from a long-time smelting factory in Hezhang, Guizhou, China. The main sources of contamination are the smelting wastes stored in the open air and abandoned in the vicinity of stream. A method of lead isotope was adopted in order to identify relations between tailings and water contamination. Representative samples of tailings and stream sediments were collected. Mineralogical characterizations were conducted using XRD and TEM/SEM, while acid digestion was carried out for determining metal contents. BCR sequential leaching tests were performed in order to assess metal mobility. The tremendous ‘actual＇ and ‘potential＇ mobility of heavy metals indicates that the smelting waste and stream sediments present a considerable threat to the environment. Besides the chemical remobilization of heavy metals from the sediments and the reworking of riverbed sediments act as a secondary source of pollution. Also groundwater and stream water were sampled in specific locations and were measured.     

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.