Particle-size dependence on metal(loid) distributions in mine wastes: Implications for water contamination and human exposure

The mining and processing of metal-bearing ores has resulted in contamination issues where waste materials from abandoned mines remain in piles of untreated and unconsolidated material, posing the potential for waterborne and airborne transport of toxic elements. This study presents a systematic method of particle size separation, mass distribution, and bulk chemical analysis for mine tailings and adjacent background soil samples from the Rand historic mining district, California, in order to assess particle size distribution and related trends in metal(loid) concentration as a function of particle size. Mine tailings produced through stamp milling and leaching processes were found to have both a narrower and finer particle size distribution than background samples, with significant fractions of particles available in a size range (?250 μm) that could be incidentally ingested. In both tailings and background samples, the majority of trace metal(loid)s display an inverse relationship between concentration and particle size, resulting in higher proportions of As, Cr, Cu, Pb and Zn in finer-sized fractions which are more susceptible to both water- and wind-borne transport as well as ingestion and/or inhalation. Established regulatory screening levels for such elements may, therefore, significantly underestimate potential exposure risk if relying solely on bulk sample concentrations to guide remediation decisions. Correlations in elemental concentration trends (such as between As and Fe) indicate relationships between elements that may be relevant to their chemical speciation.     

Toxic metal(loid) speciation during weathering of iron sulfide mine tailings under semi-arid climate

Toxic metalliferous mine-tailings pose a significant health risk to ecosystems and neighboring communities from wind and water dispersion of particulates containing high concentrations of toxic metal(loid)s (e.g., Pb, As, Zn). Tailings are particularly vulnerable to erosion before vegetative cover can be reestablished, i.e., decades or longer in semi-arid environments without intervention. Metal(loid) speciation, linked directly to bioaccessibility and lability, is controlled by mineral weathering and is a key consideration when assessing human and environmental health risks associated with mine sites. At the semi-arid Iron King Mine and Humboldt Smelter Superfund site in central Arizona, the mineral assemblage of the top 2 m of tailings has been previously characterized. A distinct redox gradient was observed in the top 0.5 m of the tailings and the mineral assemblage indicates progressive transformation of ferrous iron sulfides to ferrihydrite and gypsum, which, in turn weather to form schwertmannite and then jarosite accompanied by a progressive decrease in pH (7.3–2.3).Within the geochemical context of this reaction front, we examined enriched toxic metal(loid)s As, Pb, and Zn with surficial concentrations 41.1, 10.7, 39.3 mmol kg⁻¹ (3080, 2200, and 2570 mg kg⁻¹), respectively. The highest bulk concentrations of As and Zn occur at the redox boundary representing a 1.7 and 4.2-fold enrichment relative to surficial concentrations, respectively, indicating the translocation of toxic elements from the gossan zone to either the underlying redox boundary or the surface crust. Metal speciation was also examined as a function of depth using X-ray absorption spectroscopy (XAS). The deepest sample (180 cm) contains sulfides (e.g., pyrite, arsenopyrite, galena, and sphalerite). Samples from the redox transition zone (25–54 cm) contain a mixture of sulfides, carbonates (siderite, ankerite, cerrusite, and smithsonite) and metal(loid)s sorbed to neoformed secondary Fe phases, principally ferrihydrite. In surface samples (0–35 cm), metal(loid)s are found as sorbed species or incorporated into secondary Fe hydroxysulfate phases, such as schwertmannite and jarosites. Metal-bearing efflorescent salts (e.g., ZnSO₄·nH₂O) were detected in the surficial sample. Taken together, these data suggest the bioaccessibility and lability of metal(loid)s are altered by mineral weathering, which results in both the downward migration of metal(loid)s to the redox boundary, as well as the precipitation of metal salts at the surface.     

Aquifer geochemistry at potential aquifer storage and recovery sites in coastal plain aquifers in the New York city area,USA

The effects of injecting oxic water from the New York city (NYC) drinking-water supply and distribution system into a nearby anoxic coastal plain aquifer for later recovery during periods of water shortage (aquifer storage and recovery, or ASR) were simulated by a 3-dimensional, reactive-solute transport model. The Cretaceous aquifer system in the NYC area of New York and New Jersey, USA contains pyrite, goethite, locally occurring siderite, lignite, and locally varying amounts of dissolved Fe and salinity. Sediment from cores drilled on Staten Island and western Long Island had high extractable concentrations of Fe, Mn, and acid volatile sulfides (AVS) plus chromium-reducible sulfides (CRS) and low concentrations of As, Pb, Cd, Cr, Cu and U. Similarly, water samples from the Lloyd aquifer (Cretaceous) in western Long Island generally contained high concentrations of Fe and Mn and low concentrations of other trace elements such as As, Pb, Cd, Cr, Cu and U, all of which were below US Environmental Protection Agency (USEPA) and NY maximum contaminant levels (MCLs). In such aquifer settings, ASR operations can be complicated by the oxidative dissolution of pyrite, low pH, and high concentrations of dissolved Fe in extracted water.     

Distribution of trace elements in filtered and non filtered aqueous fractions: Insights from rivers and streams of Sardinia (Italy)

The distribution of several trace elements in different aqueous fractions has been studied in running waters from Sardinia (Italy). Trace elements and major components were determined in water samples collected at high- and low-discharge from rivers (90 samples) and streams (70 samples). At selected sites, total (non filtered samples) and dissolved (0.4 μm and 0.015 μm pore-size filtered samples) amounts of trace elements were determined, and the composition of the solid matter retained on the filters was investigated for estimating the eventual interrelationship. The elements B, Li, Rb, Sr, Ba, As, Sb, Mo, Tl and U in the studied waters showed small differences between total and dissolved amounts; dissolved concentrations were higher under low flow conditions, when the contribution of rainwater to the rivers was minimum; their concentrations were often correlated with total dissolved solids (TDS), and appeared to be related to the intensity of water-rock interaction processes. The elements Al, Fe, Mn, Pb, Zn, Cd, Cu, Co, Ni, Cs, Y, REE and Th were not related to TDS and/or major ions; they showed higher concentrations under high flow conditions; marked differences occurred between total and dissolved amounts; much lower concentrations were generally observed in the water filtered through 0.015 μm than in the water filtered through 0.4 μm, especially when sampling was carried out after heavy rain events that enhanced the load of solid matter in the water. These observations indicate an aqueous transport via sorption processes on very fine particles, such as Fe-oxide/hydroxide and clay mineral particles, which have been inferred by SEM-EDX analyses of the matter retained on the filters.     

Sediment pore-water interactions associated with arsenic and uranium transport from the North Cave Hills mining region,South Dakota,USA

The extent of historical U mining impacts is well documented for the North Cave Hills region of Harding County, South Dakota, USA. While previous studies reported watershed sediment and surface water As and U concentrations up to 90× established background concentrations, it was unclear whether or how localized changes in sediment redox behavior may influence contaminant remobilization. Five pore-water equilibration samplers (peepers) were spatially and temporally deployed within the study area to evaluate seasonal solid–liquid As and U distributions as a function of sediment depth. Pore-water and solid phase As and U concentrations, Fe speciation, Eh and pH were measured to ascertain specific geochemical conditions responsible for As and U remobilization and transport behavior. At a mine overburden sedimentation pond adjacent to the mine sites, high total aqueous As and U concentrations (4920 and 674 μg/L, respectively) were found within surface water during summer sampling; however pond dredging prior to autumn sampling resulted in significantly lower aqueous As and U concentrations (579 and 108 μg/L, respectively); however, both As and U still exceeded regional background concentrations (20 and 18 μg/L, respectively). At a wetlands-dominated deposition zone approximately 2 km downstream of the sedimentation pond, pore-water geochemical conditions varied seasonally. Summer conditions promoted reducing conditions in pore water, resulting in active release of As(III) to the water column. Autumn conditions promoted oxidizing conditions, decreasing pore-water As (As_pw) 5× and increasing U_pw 10×. Peak U pore-water concentrations (781 μg/L) were 3.5× greater than determined for the surface water (226 μg/L), and approximately 40× background concentrations. At the Bowman–Haley reservoir backwaters 45 km downstream from the mine sites, As and U pore-water concentrations increased significantly between the summer and autumn deployments, attributed to increased Fe reduction processes. Geochemical modeling suggests solid-phase Fe reduction promotes the liberation of pore-water As and U via suppressing the formation of thioarsenite. Intermittent hydrological processes facilitate As and U transport and deposition throughout the watershed, while biogeochemical-influenced redox changes cycle As and U between pore and surface water within localized environments.     

Arsenic and iron speciation in uranium mine tailings using X-ray absorption spectroscopy

In northern Saskatchewan, Canada, high-grade U ores and the resulting tailings can contain high levels of As. An environmental concern in the U mining industry is the long-term stability of As within tailings management facilities (TMFs) and its potential transfer to the surrounding groundwater. To mitigate this problem, U mill effluents are neutralized with lime to reduce the aqueous concentration of As. This results in the formation of predominantly Fe³⁺–As⁵⁺ secondary mineral phases, which act as solubility controls on the As in the tailings discharged to the TMF. Because the speciation of As in natural systems is critical for determining its long-term environmental fate, characterization of As-bearing mineral phases and complexes within the deposited tailings is required to evaluate its potential transformation, solubility, and long-term stability within the tailings mass. In this study, synchrotron-based bulk X-ray absorption spectroscopy (XAS) was used to study the speciation of As and Fe in mine tailings samples obtained from the Deilmann TMF at Key Lake, Saskatchewan. Comparisons of K-edge X-ray absorption spectra of tailings samples and reference compounds indicate the dominant oxidation states of As and Fe in the mine tailings samples are +5 and +3, respectively, largely reflecting their generation in a highly oxic mill process, deposition in an oxidized environment, and complexation within stable oxic phases. Linear combination fit analyses of the K-edges for the Fe X-ray absorption near edge spectra (XANES) to reference compounds suggest Fe is predominantly present as ferrihydrite with some amount of the primary minerals pyrite (8–15% in some samples) and chalcopyrite (5–15% in some samples). Extended X-ray absorption fine structure (EXAFS) analysis of As K-edge spectra indicates that As⁵⁺ (arsenate) present in tailings samples is adsorbed to the ferrihydrite though an inner-sphere bidentate linkage.     

Particulate trace metal speciation in stream sediments and relationships with grain size: Implications for geochemical exploration

Sediment samples were collected from streambeds in an undisturbed watershed in eastern Quebec (Gaspé Peninsula). Two sampling sites were located on a stream draining an area of known mineralization (Cu, Pb, Zn) and two on a control stream. The sediment samples were separated into 8 distinct size classes in the 850 μm to <1 μm size range by wet sieving, gravity sedimentation or centrifugation. Each sediment subsample was then subjected to a sequential extraction procedure designed to partition the particulate heavy metals into five fractions: (1) exchangeable; (2) specifically adsorbed or bound to carbonates; (3) bound to Fe-Mn oxides; (4) bound to organic matter; (5) residual. The following metals were analyzed in each extract: Cu, Pb, Zn; Fe, Mn.Comparison of samples from the mineralized area with control samples revealed the expected increase in total concentrations for Cu, Pb and Zn. Non-detrital metals were mainly associated with Fe oxides (specifically adsorbed; occluded) and with organic matter or resistant sulfides. For a given sample, variation of trace metal levels in fractions 2 and 3 with grain size reflected changes in the available quantities of the inorganic scavenging phase (FeOx/MnOx); normalization with respect to Fe and Mn content in fraction 3 greatly reduced the apparent dependency on grain size.The results of this study suggest that a single reducing extraction (NH₂OH.HCl) could be used advantageously to detect anomalies in routine geochemical surveys. A second leaching step with acidified H₂O₂ could also be included, as the trace metal concentrations in fraction 4, normalized with respect to organic carbon content, also showed high {anomaly/background} ratios.     

Spatial variability of soils and stream sediments and the remediation effects in a Portuguese uranium mine area

The old Senhora das Fontes uranium mine, located in central Portugal, was closed down in 1971. The treatment of ores from this mine and other mines by heap-leach ended in 1982. Seven dumps partially covered by vegetation were left in the area. Soil and stream sediment samples were collected in December 2009. The remediation was carried out from May 2010 to January 2011. Stream sediment samples were collected again in October 2013. Before the remediation, soils from inside the mine influence area have higher Al, As, Co, Cr, Cu, Fe, Ni, Sr, Th, U and Zn concentrations than soils from outside this area, due to radionuclides, metals and metalloid released from the mine dumps. The principal component analysis (PCA) shows a distinction between soils from inside and outside the mine influence area. The U(VI), As(V) and metals from soils can be adsorbed to Fe-oxyhydroxides and the humic acid can increase the U uptake. Soils must not be used for public or private green and residential areas, because they are contaminated in U, As, Co, Cd and Ni. Before the remediation, downstream sediments have higher Al, As, Cu, Mn, Ni, Pb, U and Zn than upstream sediments, due to erosion and percolation of water through the mine dumps. The PCA shows a distinction between downstream and upstream sediments. The U(VI), Th and As(V) can be adsorbed to Fe-oxyhydroxides. The stream sediments are contaminated in As, Mn, Th and U. Downstream sediments are the most contaminated in U and As. After the remediation, upstream and downstream sediments have generally higher Al, Fe, As, Cr, Ni, Th, U and Zn concentrations than before the remediation, attributed to the relocation of dumps. Radionuclides, metals and metalloids were transported by surface water. Consequently downstream sediments have higher Al, As, Cu, Mn, Ni, Th, U and Zn concentrations than upstream sediments. The U(VI), Th and As(V) can be adsorbed to Fe-oxyhydroxides. Stream sediments became more contaminated in U, Th and As than before the remediation, but more intensively downstream.     

Trace metals in recharge and discharge ground waters at two sites at the Baltic coast of Sweden

The distribution and controls of trace elements (Cd, Cr, Cu, Ni, Pb, Zn and U) in shallow groundwater in discharge and recharge zones were analysed at two sites on the Baltic coast of Sweden; one granite-dominated and one with a significant addition of calcite. Although the study sites differ in overburden geochemistry and groundwater trace metal concentrations, which were well reflected in the general groundwater composition, the relative hydrochemical differences between recharge and discharge ground waters were similar at both sites, and temporally stable. The concentrations of Cd, Cu, Ni and U were higher in soil tubes in recharge areas, but Cr was higher in discharge zones. Also concentrations of HS, Fe, Mn and NH₄ were higher in discharge samples, which in combination with increased ³⁴S values provide strong evidence of a transition from oxidizing to more reducing conditions along the groundwater flow gradient. In terms of trace metals, this might mean either mobilisation due to dissolution of trace-metal carrying Fe(III) and Mn(IV) phases, or immobilisation caused by precipitation of discrete trace-metal sulfides or co-precipitation with Fe sulfides. The results from this study show that the latter is dominant in both the carbonate and granite environments for the metals Cd, Cu and Ni. Chromium concentrations were likely coupled to organic complexation and were higher in discharge groundwater, where DOC was also more abundant. As the concentration of several potentially toxic trace metals were found to differ between recharge and discharge areas, a climate driven change in hydrology might have a substantial impact on the distribution of these metals.     

Direct observation of heavy metal-mineral association from the Clark Fork River Superfund Complex: Implications for metal transport and bioavailability

Two sets of samples from riverbeds and adjacent floodplains, separated by 80 river kilometers, were collected from the Clark Fork River Superfund Complex, Montana, (the largest Superfund site in the United States), and studied primarily with transmission electron microscopy (TEM) with several supporting techniques to determine heavy metal-mineral association. Seven of the eight samples studied were strongly influenced by material that once resided in mining and smelting dumps and impoundments; this material was transported downstream sometime during the last century and a half from the Butte/Anaconda areas. The eighth sample was from a deeper floodplain level and dates to premining days. The TEM observations afford a direct look, down to the nanometer level, at secondary mineral formation as a result of the breakdown of sulfides and silicates in the acid environment of this massive mine-drainage system. In the shallow, oxic floodplain sediments, heavy metals of concern in this system (As, Cu, Pb, and Zn) are taken up by the formation of sulfates (particularly Pb in jarosite), as well as hydrous metal oxides (As, Cu, Pb, and Zn in and on ferrihydrite, and a possibly new vernadite-like mineral). The oxides are long-lived in these systems, as they were also found in the anoxic riverbeds. Metals are also taken up by the formation of sulfides in sulfate-reducing environments as observed in the formation of nanoclusters of chalcopyrite and sphalerite. In all samples, clays make up between 5 and 20% of the sediment and carry significant amounts of Cu and Zn. The hydrous oxides, secondary sulfides, and clays provide several routes for metal transport downstream over long distances. Besides the potential bioavailability of heavy metals exchanged on and off the hydrous metal oxides and clays, nanometer-sized sulfides may also be highly reactive in the presence of biologic systems.     

Selective chemical extraction of heavy metals in tailings and soils contaminated by mining activity: Environmental implications

Total concentrations of chemical elements in soils may not be enough to understand the mobility and bioavailability of the elements. It is important to characterise the degree of association of chemical elements in different physical and chemical phases of soil. Another geochemical characterisation methodology is to apply sequential selective chemical extraction techniques. A seven-step sequential extraction procedure was used to investigate the mobility and retention behaviour of Al, Fe, Mn, Cu, Zn, Pb, Cr, Co, Ni, Mo, Cd, Bi, Sn, W, Ag, As and U in specific physical–chemical and mineral phases in mine tailings and soils in the surroundings of the abandoned Ervedosa mine. The soil geochemical data show anomalies associated with mineralised veins or influenced by mining. Beyond the tailings, the highest recorded concentrations for most elements are in soils situated in mineralised areas or under the influence of tailings. The application of principal components analysis allowed recognition of (a) element associations according to their geochemical behaviour and (b) distinction between samples representing local geochemical background and samples representing contamination. Some metal cations (Mn, Cd, Cu, Zn, Co, Cr, Ni) showed important enrichment in the most mobilisable and bioavailable (i.e., water-soluble and exchangeable) fractions due likely to the acidic conditions in the area. In contrast, oxy-anions such as Mo and As showed lower mobility because of adsorption to Fe oxy-hydroxides. The residual fraction comprised largest proportions of Sn and Al and to a lesser extent Zn, Pb, Ni, Cr, Bi, W, and Ag, which are also present at low concentrations in the bioavailable fractions. The elements in secondary mineral phases (mainly Fe, Mn, Cu, Zn, Cd, Pb, W, Bi, Mo, Cr, Ni, Co, As and U) as well as in organic matter and sulphides are temporarily withheld, suggesting that they may be released to the environment by changes in physico-chemical conditions.     

Geochemical characteristics of ores and surface waters for environmental risk assessment in the Pinpet iron deposit,southern Shan State,Myanmar

Mining operations in the Pinpet Fe deposit, which is the second‐largest Fe deposit in Myanmar, are currently suspended, in part because of possible contamination of heavy metals and hazardous elements (e.g., Fe, As, Cu, Zn, and U) into the surrounding aquatic environment and associated public concern. However, a scientific investigation of the source and degree of contamination in streams near the deposit has not yet been conducted. Therefore, we quantified heavy‐metal and hazardous‐element concentrations of stream waters and sediments in stream beds, and measured the speciation and concentration of these metals in deposit Fe ores using the sequential extraction method, to better understand the influence of mining activities on the surrounding environment. Geochemical results for Nan‐tank‐pauk stream and its tributaries indicate that the chemical compositions of their waters are controlled by carbonate bedrock and that no detectable contamination has occurred as a result of mining activity or hematite and limonite ore beneficiation processes in either the wet or dry seasons. All measured heavy‐metal and hazardous‐element concentrations were below the World Health Organization standards for drinking water and the proposed national drinking water quality standards in Myanmar. Bulk chemical compositions of stream‐bed and tailings dam sediments show that As, Zn, and Cu concentrations are similar to those in uncontaminated sediments. Results of bulk mineralogical and chemical analyses of ore samples reveal that some limonite ore samples contain substantial amounts of As (up to 2 wt%). However, sequential extraction results indicate that most (>90%) of the As in these As‐rich ores is hosted in insoluble fractions (e.g., crystalline Fe hydroxides and clays). Therefore, arsenic is unlikely to be released into the aquatic environment by interacting with water during ore beneficiation processes should the mine resume operations.     

Geochemical characteristics of particulate matter in the atmosphere surrounding a ceramic industrialized area

Total suspended particulate samples (TSP) were collected and concentrations measured during seventeen months in the vicinity of a ceramic industrial area. A method of fractionating was applied to the samples in order to obtain two fractions corresponding to mineral particulate coming from dust emissions (Upper-F fraction) and to amorphous matter (carbon plus small amounts of S, Ca, Fe, etc) coming mainly from traffic and other combustion processes. Also for TSP samples several element concentrations were measured following two previous treatments: extraction of elements mainly associated with the soluble fraction of the samples (B, Fe, P, As, NO^2–, NH⁴⁺, Cl^–, F) and acid digestion for trace metals and elements mainly associated with the non-soluble fractions of the samples (Fe, As, Cd, Ni, Pb, Zn Ca). Seasonal differences and the influence of meteorological parameters (temperature, relative humidity, pressure and wind conditions) on the air pollution levels, particles as well as ions, were studied.Results show different seasonal and weekly evolution for mineral and amorphous carbonaceous particles because of the different origins in dust emissions or combustion processes respectively, and the different physical properties such as size grain. Of the ions analyzed Fe, Ca and Zn were clearly associated to mineral phases and consequently related to dust emissions, and NO^2–, NH4+, P, Cl^– were related to amorphous matter coming from combustion. Ni and Cd show lower levels than those reported as guideline values and the source is mainly related to the enrichment of these elements in clay materials. B and As content result in elevated concentrations, with the tendency to increase during cold months. The emission of these elements was associated with vaporization or volatilization during high temperature ceramic processes. The original gaseous state is influenced by temperature. In the winter the content for B and As is higher due to enhanced condensation of gas-phase boron onto particles, while in the summer the increase of air temperature results in elevated evaporation.     

Distribution of environmental sensitive trace elements in the Eocene Sorgun coals, Turkey

The distribution of trace elements in the lower Eocene coal seam mined in the Yeniceltek, Kucukkohne and Ayridam coal mines from the Sorgun Basin was investigated in relation to ash content and maceral composition. The coal seam is mainly composed of huminite. In the present study, 35 samples from five seam sections were collected on the basis of megascopic characteristics. Results were determined using an energy dispersive polarised X-ray fluorescence (EDP-XRF) spectrometer on a whole-coal dry basis. Most of the major and trace elements studied are enriched in high-ash samples, while Ba, Br, Mn and W show relative enrichments in low-ash samples. Most of elements studied, such as Ga, Ce, La, Th, Nb, Rb, Zr, V, Cu, U, Pb, Sb, Cs, Sn, Cr, Se, Y and Zn, are primarily associated with mineral matter (clay minerals). Arsenic and a part of Zn, Se and Sb are probably concentrated in pyrites in the samples. Element concentrations show statistically significant negative correlations with many macerals and positive relationships with only attrinite that is mainly mixed with mineral matter (clay minerals and small quartz grains) in the samples. Nine trace elements (As, Cr, Mn, Ni, Pb, Sb, Se, Th and U), considered as potentially Hazardous Air Pollutants, are present in low to moderate concentrations. The mean values of trace element concentrations display relative enrichments in Se (2.8 ppm), Th (21 ppm) and W (26 ppm) in the investigated samples in comparison with other coals in the world.     

X-ray imaging of uranium in individual fluid inclusions

The spatial distribution of major (K, Ca, Mn, Fe) and trace elements (Ti, Cr, Cu, As, Br, Rb, Sr, Zr, Pb, Th, U) were determined in individual fluid inclusions from quartz veins of the Streltsov uranium deposit, Russia, using synchrotron radiation X-ray fluorescence (SXRF). The analyses were performed on the beamline ID-22 Micro-FID (Fluorescence, Imaging, Diffraction) of the European Synchrotron Research Facility (ESRF, Grenoble, France). Fluorescence X-ray maps of single fluid inclusions show a relatively homogeneous distribution of most elements throughout the inclusion, whereas Fe and, to a lesser extent, Sr display highly localized count rates. This observation argues for the presence of minute, optically invisible, compounds that are precipitated inside the inclusion. Simple model calculations indicate that relatively diluted solutions (10–100 ppm U) trapped at geologically relevant temperatures (e.g. 250 °C) would precipitate submicron sized particles. These particles would be highly reactive to the photon flux but not necessarily visible under the microscope. These results indicate that third-generation synchrotron light source can be a powerful technique to study the physical processes undergone by the fluid. When combined with chemical data, this technique can help to clarify fluid transport properties in natural systems.     

Post-depositional redistribution of trace metals in reservoir sediments of a mining/smelting-impacted watershed (the Lot River,SW France)

Mining/smelting wastes and reservoir sediment cores from the Lot River watershed were studied using mineralogical (XRD, SEM–EDS, EMPA) and geochemical (redox dynamics, selective extractions) approaches to characterize the main carrier phases of trace metals. These two approaches permitted determining the role of post-depositional redistribution processes in sediments and their effects on the fate and mobility of trace metals. The mining/smelting wastes showed heterogeneous mineral compositions with highly variable contents of trace metals. The main trace metal-bearing phases include spinels affected by secondary processes, silicates and sulfates. The results indicate a clear change in the chemical partitioning of trace metals between the reservoir sediments upstream and downstream of the mining/smelting activities, with the downstream sediments showing a 2-fold to 5-fold greater contribution of the oxidizable fraction. This increase was ascribed to stronger post-depositional redistribution of trace metals related to intense early diagenetic processes, including dissolution of trace metal-bearing phases and precipitation of authigenic sulfide phases through organic matter (OM) mineralization. This redistribution is due to high inputs (derived from mining/smelting waste weathering) at the water–sediment interface of (i) dissolved SO₄ promoting more efficient OM mineralization, and (ii) highly reactive trace metal-bearing particles. As a result, the main trace metal-bearing phases in the downstream sediments are represented by Zn- and Fe-sulfides, with minor occurrence of detrital zincian spinels, sulfates and Fe-oxyhydroxides. Sequestration of trace metals in sulfides at depth in reservoir sediments does not represent long term sequestration owing to possible resuspension of anoxic sediments by natural (floods) and/or anthropogenic (dredging, dam flush) events that might promote trace metal mobilization through sulfide oxidation. It is estimated that, during a major flood event, about 870 t of Zn, 18 t of Cd, 25 t of Pb and 17 t of Cu could be mobilized from the downstream reservoir sediments along the Lot River by resuspension-induced oxidation of sulfide phases. These amounts are equivalent to 13-fold (Cd), ∼6-fold (Zn), 4-fold (Pb) the mean annual inputs of the respective dissolved trace metals into the Gironde estuary.     

Transport and fate of ammonium and its impact on uranium and other trace elements at a former uranium mill tailing site

The remediation of ammonium-containing groundwater discharged from uranium mill tailing sites is a difficult problem facing the mining industry. The Monument Valley site is a former uranium mining site in the southwest US with both ammonium and nitrate contamination of groundwater. In this study, samples collected from 14 selected wells were analyzed for major cations and anions, trace elements, and isotopic composition of ammonium and nitrate. In addition, geochemical data from the U.S. Department of Energy (DOE) database were analyzed. Results showing oxic redox conditions and correspondence of isotopic compositions of ammonium and nitrate confirmed the natural attenuation of ammonium via nitrification. Moreover, it was observed that ammonium concentration within the plume area is closely related to concentrations of uranium and a series of other trace elements including chromium, selenium, vanadium, iron, and manganese. It is hypothesized that ammonium–nitrate transformation processes influence the disposition of the trace elements through mediation of redox potential, pH, and possibly aqueous complexation and solid-phase sorption. Despite the generally relatively low concentrations of trace elements present in groundwater, their transport and fate may be influenced by remediation of ammonium or nitrate at the site.     

金属硫化物微生物氧化的机制和效应

岩石露头和矿山废弃物中的金属硫化物在地表、近地表条件下的氧化作用往往导致多种环境问题,因此,金属硫化物的地表风化一直是备受关注的表生过程之一。越来越多的证据表明微生物对矿物的氧化在金属硫化物风化过程中发挥着重要作用。实验研究发现:微生物在金属硫化物表面附着并形成微生物膜,在矿物-微生物膜界面微环境中存在着强烈的微生物氧化和化学氧化作用,两种氧化作用相互协同、共同促进。在此过程中,金属硫化物的S、As、Fe等元素经历了复杂的电子传递、逐级氧化的动力学过程,最终形成稳定的高铁硫酸盐或氧化物,并形成大量的酸性排水。该过程受多种因素的影响,包括细菌种类、光照和溶液Fe~(2+)浓度等。金属硫化物的微生物氧化直接导致重金属大量释放和严重的环境危害,释放的酸性排水还引发碳酸盐矿物分解和CO_2排放,会对全球碳循环产生不可忽视的影响。在地球演化的早期阶段,金属硫化物氧化消耗大气氧气可能导致大氧化进程滞后。尽管关于金属硫化物-微生物相互作用研究取得了长足的进展,但金属硫化物微生物氧化的分子机制和全球尺度的元素地球化学循环还有待深入研究,原位纳米观测技术的引入和全球物质循环模型研究具有必要性和紧迫性,同时也对生物冶金技术的发展有着重要的意义。     

Comparison of metal(loid) concentrations in water, sediments and fish from two large shallow lakes

Hulun Lake and Taihu Lake are both large shallow lakes in China. In summer and winter of 2009, water, sediments and fish samples were collected from the two lakes and the concentrations of metal(loids) were analyzed. The results demonstrated that aqueous concentrations of arsenic (As), chromium (Cr), cadmium (Cd), nickel (Ni) and copper (Cu) in Hulun Lake were significantly higher than those in Taihu Lake. Especially, the As concentrations (about 130 μg/L) in Hulun Lake dramatically exceeded the permissible level of drinking water. Compared with Taihu Lake, metal(loid) concentrations in the sediments of Hulun Lake were significantly lower, which might have less impacts on the metal exchanges between water and sediments. In contrast, concentrations of the measured metal(loids) (including As) in fish from Hulun Lake and Taihu Lake were comparable, suggesting that the dramatic difference in aqueous and sediment metal(loid) concentrations had less influence on the metal(loid) bioavailability. The higher concentrations of dissolved organic carbon (DOC) and cations (e.g., Na⁺, K⁺ and Mg²⁺) in lake water might contribute to the reduced metal(loid) bioavailability to fish in Hulun Lake.