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.     

尾矿中硫化物风化氧化模拟实验研究

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

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.     

Thermodynamics and organic matter: constraints on neutralization processes in sediments of highly acidic waters

The controls on the internal neutralization of low productivity, highly acidified waters by sulfide accumulation in sediments are yet poorly understood. It is demonstrated that the neutralization process is constrained by organic matter quality and thermodynamic effects which control the relative rates of SO₄ and Fe reduction, and the fate of the reduced Fe and S in the sediments. The investigated sediments were rich in dissolved Fe(II) (0.005–12 mmol l⁻¹) and SO₄ (1.3–22 mmol l⁻¹). The pH ranged from 3.0 to 6.8. Contents of reduced inorganic S (0.1–9.5%), molar C/N ratios of the organic matter (12–80) and metabolic turnover rates (1–110 μeq cm⁻³ a⁻¹) varied strongly. Substantial amounts of Fe sulfides were only found at a simultaneous partial thermodynamic and solubility equilibrium of the involved biogeochemical processes. Sulfide oxidation was apparently inhibited, and SO₄ and Fe reduction coexisted. In this type of sediment increases in C availability cause enhanced neutralization rates. In the absence of a partial equilibrium, the sediments were in a sulfide oxidizing and Fe reducing state, and did not accumulate Fe sulfides. The latter type of sediment will increase neutralization rates in response to decreasing deposition of reactive Fe oxides but not necessarily in response to increases in lake productivity by e.g. fertilization measures.     

Sulfate reducing bioreactor dependence on organic substrates for remediation of coal-generated acid mine drainage: Field experiments

Field experiments were conducted over a 460-day period to assess the efficiency of different mixtures of organic substrates to remediate coalmine-generated acid mine drainage (AMD). Five pilot-scale, flow-through bioreactors containing mixtures of herbaceous and woody organic substrates along with one control reactor containing only limestone were constructed at the Tab-Simco site and exposed to AMD in situ. Tab-Simco is an abandoned coal mine near Carbondale, Illinois that produces AMD with pH ∼2.5 and notably high average concentrations of SO₄ (5050 mg/L), Fe (950 mg/L), Al (200 mg/L), and Mn (44 mg/L). Results showed that the sequestration of SO₄ and metals was achieved in all reactors; however, the presence and type of organic carbon matrix impacted the overall system dynamics and the AMD remediation efficiency. All organic substrate-based reactors established communities of sulfate reducing microorganisms that contributed to enhanced removal of SO₄, Fe, and trace metals (i.e., Cu, Cd, Zn, Ni) via microbially-mediated reduction followed by precipitation of insoluble sulfides. Additional mechanisms of contaminant removal were active in all reactors and included Al- and Fe-rich phase precipitation and contaminant surface sorption on available organic and inorganic substrates. The organic substrate-based reactors removed more SO₄, Fe, and Al than the limestone-only control reactor, which achieved an average removal of ∼19 mol% SO₄, ∼49 mol% Fe, 36 mol% Al, and 2 mol% Mn. In the organic substrate-based reactors, increasing herbaceous content correlated with increased removal efficiency of SO₄ (26–35 mol%), Fe (36–62 mol%), Al (78–83 mol%), Mn (2–6 mol%), Ni (64–81 mol%), Zn (88–95 mol%), Cu (72–85 mol%), and Cd (90–92 mol%), while the diversity of the intrinsic microbial community remained relatively unchanged. The extrapolation of these results to the full-scale Tab-Simco treatment system indicated that, over the course of a 460-day period, the predominantly herbaceous bioreactors could remove up to 92,500 kg SO₄, 30,000 kg Fe, 8,950 kg Al, and 167 kg Mn, which represents a 18.3 wt%, 36.8 wt%, 4.1 wt% and 82.3 wt% increase in SO₄, Fe, Al, and Mn, respectively, removal efficiency compared to the predominantly ligneous bioreactors.The results imply that anaerobic organic substrate bioreactors are promising technologies for remediation of coal-generated AMD and that increasing herbaceous content in the organic substrate matrix can enhance contaminant sequestration. However, in order to improve the remediation capacity, future designs must optimize not only the organic carbon substrate but also include a pretreatment phase in which the bulk of dissolved Fe/Al-species are removed from the influent AMD prior to entering the bioreactor because of 1) seasonal variations in temperature and redox gradients could induce dissolution of the previously formed redox sensitive compounds, and 2) microbially-mediated sulfate reduction activity may be inhibited by the excessive precipitation of Al- and Fe-rich phases.     

Discriminating between background and mine-impacted groundwater at the Phoenix mine,Nevada USA

Differentiating between mineralized and non-mineralized background groundwater chemistry at a mine site can be challenging if there is an overprint of past and/or current mining on naturally mineralized conditions. At the Phoenix mine in the Copper Canyon mining district of Nevada, quantile–quantile H⁺/SO₄ plots were used to segregate four wells clearly impacted by historical mining activity. The mineralogy of rock at the elevation of the well screen interval was used to partition the 53 remaining wells into mineralized and non-mineralized populations. For each class, groundwater chemistry was examined to identify if SO₄ and H⁺ trends were stable (unimpacted) or increasing (impacted). Then each well was mapped as one of four resulting groundwater types across the mine site, defining the spatial extent of the different groups. Several groundwater regions were identified. A group of mineralized, mine-impacted wells (Type II) are located in Philadelphia Canyon adjacent to the Cu leach facility, with the anthropogenically impacted area bounded by several hydrologically downgradient, mineralized, unimpacted wells (Type I) to the south and east. There is a set of non-mineralized, impacted wells (Type III) downgradient from the tailings pond facility, where a historical release of SO₄ is apparent in the well record. However, in some downgradient wells the tailings pond pump-back mitigation system has resulted in recovery of the groundwater quality to a non-mineralized background condition. Finally, in the vicinity of the Reona heap leach pad, there is a group of non-mineralized, unimpacted wells (Type IV). Not surprisingly, most mineralized wells (Types I and II) are located in or near mined areas, while non-mineralized wells (Types III and IV) tend to be in the southern portion of the facility in the alluvia of Buffalo and Reese River valleys.     

Structure and reactivity of zinc sulfide precipitates formed in the presence of sulfate-reducing bacteria

The biologically mediated formation of metal sulfide precipitates in anoxic sediments represents a potentially important mechanism for the sequestration of toxic metals. Current knowledge of the structure and reactivity of these biogenic metal sulfides is scarce, limiting the ability to effectively assess contaminant sequestration in, and remobilization from, these solids. In this study, SO₄-reducing bacteria (Desulfovibrio sp.) were grown for 5 days in a high-SO₄, minimal metal media amended with Zn at either 30 or 300 micromolar. Zinc speciation in the reactor solids was determined using X-ray absorption spectroscopy, and the results compared to spectra of known metal sulfide mineral phases and freshly formed metal sulfides synthesized through purely chemical processes. Biogenically mediated Zn sulfides showed significantly more short range crystallographic order than the abiotically prepared amorphous precipitates. The presence of dissolved Fe²⁺ at similar concentrations did not affect the nature of the Zn precipitates formed. The biogenic ZnS solids were also more resistant to re-oxidation than the chemical precipitates but more soluble than sphalerite mineral samples. These results suggest that Zn sulfides formed in anaerobic sediments are likely to be more resistant to re-oxidation than would be expected based on dissolution of Fe sulfides and/or sediment acid volatile sulfides.     

Isotope geochemistry of drainage from an acid mine impaired watershed,Oakland, California

Oxidation of sulfides at the Leona Heights Sulfur Mine has resulted in the liberation of acid, SO₄ and metals to Leona Creek. Previous research at the site has indicated Fe(II) oxidation at rates faster than would be predicted by abiotic oxidation alone, particularly in the segment of stream between the Adit and Leona Street sample stations. In order to assess the mechanisms responsible for sulfide oxidation, samples were collected for isotopic analysis of water and SO₄, the results of which were used to develop a stoichiometric isotope-balance model. This exercise indicated that the percentage of water-derived oxygen in SO₄ increased spatially from between 56% and 64% at the Adit to between 71% and 72% at Leona Street, illustrating that increased sulfide oxidation via Fe(III) was occurring within, or as water flows over, the waste rock, relative to water emanating directly from the former mine. The incorporation of water-derived oxygen in SO₄ during pyrite oxidation is a process controlled by Fe oxidizing bacteria such as A. ferrooxidans at low pH. The role of bacteria was further supported by estimates of the rate constant for Fe oxidation between sampling stations, yielding values that were approximately 10⁶ faster than abiotic Fe oxidation alone. Stable isotopic analysis of water further indicates a close correlation of adit spring water to the local meteoric water line, while ³H data indicate a groundwater apparent age, or time of travel from its primary zone of recharge, of <5–18 a. Additionally, the δ³⁴S data, in conjunction with reported albitized feldspars within the Leona Rhyolite host rock, indicate a magmatic origin of ore sulfur, contrary to previous interpretations at the site.     

Estimation of potential pollution from mine tailings in the San Pedro River (1993–2005), Mexico–US border

The San Pedro River (SPR) is located in northern Sonora (Mexico) and southeastern Arizona (USA). SPR is a transboundary river that develops along the Sonora (Mexico) and Arizona (USA) border, and is considered the main source of water for a variety of users (human settlements, agriculture, livestock, and industry). The SPR originates in the historic Cananea mining area, which hosts some of the most important copper mineralizations in Mexico. Acid mine drainage derived from mine tailings is currently reaching a tributary of the SPR near Cananea City, resulting in the contamination of the SPR with heavy metals and sulfates in water and sediments. This study documents the accumulation and distribution of heavy metals in surface water along a segment of the SPR from 1993 to 2005. Total concentrations of Cd, Cu, Fe, Mn, Pb, and Zn in surface waters are above maximum permissible levels in sampling sites near mine tailing deposits. Nevertheless, a significant decrease in the Fe and SO₄ ²⁻ in surface water (SO₄ ²⁻: 7,180–460.39 mg/L; Fe: 1,600–9.51 mg/L) as well as a gradual decrease in the heavy and transition metal content were observed during the period from 1994 to 2005. Approximately 2.3 km downstream of the mine tailings, the heavy metal content of the water drops quickly following an increase in pH values due to the discharging of wastewater into the river. The attenuation of the heavy metal content in surface waters is related to stream sediment precipitation (accompanied by metal coprecipitation and sorption) and water dilution. Determining the heavy metal concentration led to the conclusion that the Cananea mining area and the San Pedro River are ecosystems that are impacted by the mining industry and by untreated wastewater discharges arising from the city of Cananea (Sonora, Mexico).     

Pollution of a water course impacted by acid mine drainage in the Imgok creek of the Gangreung coal field,Korea

The purposes of this study are to (i) determine the geochemical characteristics of Imgok creek impacted by acid mine drainage (AMD) generated from abandoned coal mines, (ii) to assess the pollution of heavy metals in the stream sediments and soils, and (iii) to identify the chemical form of Fe precipitates collected in the study area where there are 4 abandoned coal mines, which belong to the Grangreung coal field at the eastern part of Korea. AMD generated from mine adits and coal refuse piles shows low pH, and high concentrations of Fe, Al and SO₄, especially in the Youngdong coal mine. In Imgok creek, pH values increased, and total dissolved solids (TDS) values decreased with distance. The concentrations of toxic heavy metals and major cations except Fe decreased by dilution, but the concentration of Fe decreased rapidly due to the formation of precipitates. The quality of groundwater samples did not exceed the Korean drinking-water standard. In the stream sediments, the concentrations of Fe are relatively high in the Youngdong tributary and Imgok creek, but the concentrations of heavy metals are similar to those of unpolluted sediments. Pollution indices of agricultural soils range from 0.28 to 0.47. Yellowish red Fe precipitates collected in the study area turned out to be amorphous or poorly crystallized minerals (determined by X-ray diffraction patterns and Fe_ox/Fe_tot ratios) and to contain chemically bonded SO₄ and OH [determined by infra-red (IR) spectral analysis]. With these, the mol ratios of Fe/S ranging from 4.6 to 6.1 determined by electron probe micro-analysis (EPMA) in precipitates strongly support the existence of schwertmannite.     

Geochemistry and mineralogy of arsenic in (natural) anaerobic groundwaters

Here new data from field bioremediation experiments and geochemical modeling are reported to illustrate the principal geochemical behavior of As in anaerobic groundwaters. In the field bioremediation experiments, groundwater in Holocene alluvial aquifers in Bangladesh was amended with labile water-soluble organic C (molasses) and MgSO₄ to stimulate metabolism of indigenous SO₄-reducing bacteria (SRB). In the USA, the groundwater was contaminated by Zn, Cd and SO₄, and contained <10 μg/L As under oxidized conditions, and a mixture of sucrose and methanol were injected to stimulate SRB metabolism. In Bangladesh, groundwater was under moderately reducing conditions and contained ∼10 mg/L Fe and ∼100 μg/L As. In the USA experiment, groundwater rapidly became anaerobic, and dissolved Fe and As increased dramatically (As > 1000 μg/L) under geochemical conditions consistent with bacterial Fe-reducing conditions. With time, groundwater became more reducing and biogenic SO₄ reduction began, and Cd and Zn were virtually completely removed due to precipitation of sphalerite (ZnS) and other metal sulfide mineral(s). Following precipitation of chalcophile elements Zn and Cd, the concentrations of Fe and As both began to decrease in groundwater, presumably due to formation of As-bearing FeS/FeS₂. By the end of the six-month experiment, dissolved As had returned to below background levels. In the initial Bangladesh experiment, As decreased to virtually zero once biogenic SO₄ reduction commenced but increased to pre-experiment level once SO₄ reduction ended. In the ongoing experiment, both SO₄ and Fe(II) were amended to groundwater to evaluate if FeS/FeS₂ formation causes longer-lived As removal. Because As-bearing pyrite is the common product of SRB metabolism in Holocene alluvial aquifers in both the USA and Southeast Asia, it was endeavored to derive thermodynamic data for arsenian pyrite to better predict geochemical processes in naturally reducing groundwaters. Including the new data for arsenian pyrite into Geochemist’s Workbench, its stability field completely dominates in reducing Eh–pH space and “displaces” other As-sulfides (orpiment, realgar) that have been implied to be important in previous modeling exercises and reported in rare field conditions.     

Organic carbon amendments for passive in situ treatment of mine drainage: Field experiments

A field-scale experiment was conducted to evaluate various organic C sources as amendments for passive treatment of tailings pore water. Varied mixtures of peat, spent-brewing grain (SBG) and municipal biosolids (MB) were assessed for the potential to promote dissimilatory sulfate reduction (DSR) and metal-sulfide precipitation. Five amended cells and one control were constructed in the vadose zone of a sulfide- and carbonate-rich tailings deposit, and the geochemistry, microbiology and mineralogy were monitored for 4 a. Increases in pore-water concentrations of dissolved organic C (DOC) and decreases in aqueous SO₄ concentrations of >2500 mg L⁻¹ were observed in cells amended with peat + SBG and peat + SBG + MB. Removal of SO₄ was accompanied by shifts in δ³⁴S-SO₄ values of >+30‰, undersaturation of pore water with respect to gypsum [CaSO₄·2H₂O], and increased populations of SO₄-reducing bacteria (SRB). Decreases in aqueous concentrations of Zn, Mn, Ni, Sb and Tl were observed for these cells relative to the control. Organic C introduction also supported growth of Fe-reducing bacteria (IRB) and increases in Fe and As concentrations. Enhanced Fe and As mobility occurred in all cells; however, maximum concentrations were observed in cells amended with MB. Subsequent decreases in Fe and As concentrations were attributed to DSR and metal-sulfide precipitation. The common presence of secondary Zn-S and Fe-S phases was observed by field emission-scanning electron microscopy (FE-SEM) and energy dispersive X-ray (EDS) spectroscopy. Selective extractions indicated that large decreases in water-soluble SO₄ occurred in cells that supported DSR. Furthermore, amendments that supported DSR generally were characterized by slight decreases in solid-phase concentrations of extractable metal(loid)s. Amendment of tailings with organic C amendments that supported ongoing DOC production and DSR was essential for sustained treatment.     

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

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

Secondary mineral-forming processes in natural—anthropogenic hydrogeological systems at sulfide deposits. Simulation of the origin of the phase (Fe,Mg)SO4 · 7H2O in the course of sulfide oxidation at the Degtyarka copper sulfide deposit

Data on the decommissioned Degtyarka Cu sulfide deposit, Urals, confirm the hypothesis that the flooding of abandoned mine workings is associated with the synthesis of secondary sulfates. Numerical simulation of hydrogeochemical processes in the rock—water system imitating the flooding of an underground void makes it possible to evaluate the conditions under which kirovite (Fe,Mg)SO₄ · 7H₂O and melanterite are formed at the oxidation of ore sulfides. Secondary sulfates are formed when the redox potential of the system is transformed from reducing to oxidizing within the stability field of Fe(II) species. The Fe/Mg ratio of the kirovite (Fe,Mg)SO₄ · 7H₂O is controlled first of all by the percentage of sulfides in the rock—water system, the rock/water ratio, the openness of the system with respect to atmospheric gases, and the temperature.     

Geochemical and mineralogical investigation of uranium in multi-element contaminated,organic-rich subsurface sediment

Subsurface regions of alluvial sediments characterized by an abundance of refractory or lignitic organic carbon compounds and reduced Fe and S bearing minerals, which are referred to as naturally reduced zones (NRZ), are present at the Integrated Field Research Challenge site in Rifle, CO (a former U mill site), and other contaminated subsurface sites. A study was conducted to demonstrate that the NRZ contains a variety of contaminants and unique minerals and potential contaminant hosts, investigate micron-scale spatial association of U with other co-contaminants, and determine solid phase-bounded U valence state and phase identity. The NRZ sediment had significant solid phase concentrations of U and other co-contaminants suggesting competing sorption reactions and complex temporal variations in dissolved contaminant concentrations in response to transient redox conditions, compared to single contaminant systems. The NRZ sediment had a remarkable assortment of potential contaminant hosts, such as Fe oxides, siderite, Fe(II) bearing clays, rare solids such as ZnS framboids and CuSe, and, potentially, chemically complex sulfides. Micron-scale inspections of the solid phase showed that U was spatially associated with other co-contaminants. High concentration, multi-contaminant, micron size (ca. 5–30 μm) areas of mainly U(IV) (53–100%) which occurred as biogenic UO₂ (82%), or biomass – bound monomeric U(IV) (18%), were discovered within the sediment matrix confirming that biotically induced reduction and subsequent sequestration of contaminant U(VI) via natural attenuation occurred in this NRZ. A combination of assorted solid phase species and an abundance of redox-sensitive constituents may slow U(IV) oxidation rates, effectively enhancing the stability of U(IV) sequestered via natural attenuation, impeding rapid U flushing, and turning NRZs into sinks and long-term, slow-release sources of U contamination to groundwater.     

Sulphur,organic carbon and iron relationships in estuarine and freshwater sediments: effects of sedimentation rate

Concentrations of S, organic C and Fe were investigated in profiles of sediments from two estuarine systems in the SW of Western Australia. In marine-affected sediments, inorganic S dominates total S and concentrations of total S correlate with Fe and not with organic C. In freshwater sediments, organic S dominates total S and concentrations of total S correlate with organic C and not with Fe. Molar Fe/S ratios in the estuarine sediments decrease with increasing salinity and approach unity for marine conditions. Net accumulation rates of S in sediments were estimated with a numerical computer model, calibrated with published data on profiles of marine sediments for diffusion of SO²⁻₄, sedimentation rates and distributions of S. Measured depth-integrated reduction rates of SO²⁻₄ in the marine-affected estuarine sediments approach those obtained for Fe-limited marine conditions at similar rates of sedimentation. Measured concentrations of inorganic S in anoxic freshwater sediments fit a numerically calculated relationship between inorganic S and sedimentation rate.     

Volatile organic acids and microbial processes in the Yegua formation,east-central Texas

Geochemical and microbiological evidence indicates that viable microorganisms produce and consume volatile organic acids (VOA) in the Yegua formation. Acetic and propionic acid concentrations in mudstones range from 200 to 1270 and 20 to 38 nmol·gdw⁻¹ respectively, whereas concentrations in sands are 50–200 and less than 20 nmol·gdw⁻¹. VOA concentrations in sediments and in laboratory incubations suggest net production of VOAs by microorganisms in mudstones, and net consumption of VOAs by SO₄ reducing bacteria (SRB) in sands. Notably, SRB activity is mostly confined to aquifer sands.Vertical diffusion and advection were modeled to estimate acetic acid transport from aquitard to aquifer. Assuming that SRB completely respire the acetic acid transported into the aquifer (3.2 μmol·l⁻¹·m·a⁻¹), the CO₂ production rate in the aquifer sands is 5.3 μmol·l⁻¹·a⁻¹. This slow mineralization rate of in situ organic matter is within the range for deep aquifers, and probably accounts for the long-term survival of microorganisms in oligotrophic environments. Finally, the microbial communities in Yegua sediments appear to exhibit a loose commensalism, with microorganisms in aquitards providing VOAs for respiratory processes (i.e., SO₄ reduction) in aquifers.     

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.     

Heavy metal contamination of soils and waters in and around the Imcheon Au–Ag mine,Korea

The heavy metal contamination of soils and waters by metalliferous mining activities in an area of Korea was studied. In the study area of the Imcheon Au–Ag mine, soils and waters were sampled and analyzed using AAS for Cd, Cu, Pb and Zn. Analysis of HCO₃⁻, F⁻, NO₃⁻ and SO₄²⁻ in water samples was also undertaken by ion chromatography. Elevated concentrations of the metals were found in tailings. The maximum contents in the tailings were 9.4, 229, 6160 and 1640 mg/kg extracted by aqua regia and 1.35, 26.4, 70.3 and 410 mg/kg extracted by 0.1 N HCl solution for Cd, Cu, Pb and Zn, respectively. These metals are continuously dispersed downstream and downslope from the tailings by clastic movement through wind and water. Because of the existence of sulfides in the tailings, a water sample taken on the tailings site was very acidic with a pH of 2.2, with high total dissolved solids (TDS) of 1845 mg/l and electric conductivity (EC) of 3820 μS/cm. This sample also contained up to 0.27, 1.90, 2.80, 53.4, 4,700 mg/l of Cd, Cu, Pb, Zn and SO₄²⁻, respectively. TDS, EC and concentrations of metals in waters decreased with distance from the tailings. The total amount of pulverized limestone needed for neutralizing the acid tailings was estimated to be 46 metric tons, assuming its volume of 45,000 m³ and its bulk density of 1855 kg/m³.     

Metal and metalloid leaching from tailings into streamwater and sediments in the old Ag–Pb–Zn Terramonte mine,northern Portugal

Tailings deposited over the Castanheira, a stream which flows through the old Ag–Pb–Zn Terramonte mine area, showed a great potential environmental risk due to sulphide weathering, facilitated by the tailings–water interaction. The high concentrations of Al, Fe, Pb and Zn in the tailings are associated with the exchangeable, reducible and sulphide fractions and suggest sphalerite and pyrite occurrences. Oxidation of pyrite is responsible for the low pH values (3.38–4.89) of the tailings. The water from the Castanheira stream is not suitable for human consumption due to high concentrations of SO₄ ^2?, Mn, Al, Cd, Ni, and Pb. The lowest concentrations of metals and metalloids were detected in downstream stretches of the Castanheira. However, As, Fe and Zn in deeper sediments tend to increase downstream. Significant concentrations of trivalent forms of arsenic were detected in water samples. In downstream stretches of the Castanheira, some free ions (Fe²⁺, Mn²⁺ and Zn²⁺) also predominate and the water is saturated with ferrihydrite, goethite, hematite, lepidocrosite and magnetite.