Applied Geochemistry (v.24, #12)

Mineralogical, geochemical, and microbial investigation of a sulfide-rich tailings deposit characterized by neutral drainage by Matthew B.J. Lindsay; Peter D. Condon; John L. Jambor; Kerry G. Lear; David W. Blowes; Carol J. Ptacek (2212-2221).
Mineralogical, geochemical and microbial characterization of tailings solids from the Greens Creek Mine, Juneau, Alaska, was performed to evaluate mechanisms controlling aqueous geochemistry of near-neutral pH pore water and drainage. Core samples of the tailings were collected from five boreholes ranging from 7 to 26 m in depth. The majority of the 51 samples (77%) were collected from the vadose zone, which can extend >18 m below the tailings surface. Mineralogical investigation indicates that the occurrence of sulfide minerals follows the general order: pyrite [FeS2] >> sphalerite [(Zn,Fe)S] > galena [PbS], tetrahedrite [(Fe,Zn,Cu,Ag)12Sb4S13] > arsenopyrite [FeAsS] and chalcopyrite [CuFeS2]. Pyrite constitutes <20 to >35 wt.% of the tailings mineral assemblage, whereas dolomite [CaMg(CO3)2] and calcite [CaCO3] are present at ⩽30 and 3 wt.%, respectively. The solid-phase geochemistry generally reflects the mineral assemblage. The presence of additional trace elements, including Cd, Cr, Co, Mo, Ni, Se and Tl, is attributed to substitution into sulfide phases. Results of acid–base accounting (ABA) underestimated both acid-generating potential (AP) and neutralization potential (NP). Recalculation of AP and NP based on solid-phase geochemistry and quantitative mineralogy yielded more representative results. Neutrophilic S-oxidizing bacteria (nSOB) and SO4-reducing bacteria (SRB) are present with populations up to 107  and 105 cells g−1, respectively. Acidophilic S-oxidizing bacteria (aSOB) and iron-reducing bacteria (IRB) were generally less abundant. Primary influences on aqueous geochemistry are sulfide oxidation and carbonate dissolution at the tailings surface, gypsum precipitation–dissolution reactions, as well as Fe reduction below the zone of sulfide oxidation. Pore-water pH values generally ranged from 6.5 to 7.5 near the tailings surface, and from approximately 7–8 below the oxidation zone. Elevated concentrations of dissolved SO4, S2O3, Fe, Zn, As, Sb and Tl persisted under these conditions.

Secondary minerals formed in tailings derived from a W-rich deposit were investigated in detail using transmission electron microscopy (TEM). The study focused on secondary minerals that formed in the vicinity of oxidized sphalerite [ZnS] and tennantite [Cu10(Fe,Zn)2As4S13] grains. Samples for TEM analysis were prepared directly from petrographic thin sections using a focused ion beam instrument. This method insured that spatial relationships among primary grains, secondary minerals and the pore spaces were maintained. The results from this study indicate that the secondary coatings associated with sphalerite and tennantite are composed of several discrete phases. The phases identified in this study include an Fe–Zn–As–O phase, secondary sulfides, native Cu, an Fe–Si–O phase, an In–O phase, and wulfenite [PbMoO4]. The Fe–Zn–As–O phase precipitates directly from the pore water and the nearby primary mineral grains act as a source for some of the elements (e.g., Zn from sphalerite, As from tennantite). Secondary Cu sulfides were found at the outer margins of sphalerite and roquesite [CuInS2] grains. It is likely that these Cu sulfides form as a result of interactions between the primary grain and aqueous Cu(II) present in the pore water, similar to what occurs in supergene environments. A secondary sulfide that was composed of variable amounts of Cu, Zn, As, Fe and S was also identified along the outer margins of tennantite. Native Cu was found in association with chalcopyrite [CuFeS2] inclusions that were present in one of the sphalerite grains and probably represents a low-temperature secondary phase. The oxidation of chalcopyrite in the presence of aqueous Si leads to the formation of a nanocrystalline or amorphous Fe–Si–O phase. Roquesite oxidation leads to the formation of a crystalline In–O phase, which is likely dzhalindite [In(OH)3]. Wulfenite was found in the interstitial voids present in the Fe–Zn–As–O phase suggesting that it forms by direct precipitation from the local pore water. The results from this study indicate that secondary coatings consist of complex secondary phases that may only be distinguished at the nanoscale. The TEM investigations reveal details regarding mineralogical sinks and sources for aqueous components that may otherwise be overlooked.

Changes in lead and zinc lability during weathering-induced acidification of desert mine tailings: Coupling chemical and micro-scale analyses by Sarah M. Hayes; Scott A. White; Thomas L. Thompson; Raina M. Maier; Jon Chorover (2234-2245).
Desert mine tailings may accumulate toxic metals in the near surface centimeters because of low water through-flux rates. Along with other constraints, metal toxicity precludes natural plant colonization even over decadal time scales. Since unconsolidated particles can be subjected to transport by wind and water erosion, potentially resulting in direct human and ecosystem exposure, there is a need to know how the lability and form of metals change in the tailings weathering environment. A combination of chemical extractions, X-ray diffraction, micro-X-ray fluorescence spectroscopy, and micro-Raman spectroscopy were employed to study Pb and Zn contamination in surficial arid mine tailings from the Arizona Klondyke State Superfund Site. Initial site characterization indicated a wide range in pH (2.5–8.0) in the surficial tailings pile. Ligand-promoted (DTPA) extractions, used to assess plant-available metal pools, showed decreasing available Zn and Mn with progressive tailings acidification. Aluminum shows the inverse trend, and Pb and Fe show more complex pH dependence. Since the tailings derive from a common source and parent mineralogy, it is presumed that variations in pH and “bio-available” metal concentrations result from associated variation in particle–scale geochemistry. Four sub-samples, ranging in pH from 2.6 to 5.4, were subjected to further characterization to elucidate micro-scale controls on metal mobility. With acidification, total Pb (ranging from 5 to 13 g kg−1) was increasingly associated with Fe and S in plumbojarosite aggregates. For Zn, both total (0.4–6 g kg−1) and labile fractions decreased with decreasing pH. Zinc was found to be primarily associated with the secondary Mn phases manjiroite and chalcophanite. The results suggest that progressive tailings acidification diminishes the overall lability of the total Pb and Zn pools.

Sediment samples were analyzed as part of ongoing environmental investigations of historical U mining impacts within Custer National Forest in Harding County, South Dakota. Correlations between As and U content, grain size and soil mineralogy were determined to identify contaminant fate and transport mechanisms. Soil samples collected near the mining source zone and up to 61 km downgradient of the minesites were analyzed. Samples were homogenized and wet sieved through polymer screens, and metal(loid) concentrations were determined using inductively coupled plasma mass spectrometry (ICP-MS). Powder X-ray diffraction (XRD) analysis identified quartz as the primary mineral for all size fractions, with varying amounts of analcime, indicative of volcanic origin. Selected samples were examined for trace mineral composition using scanning electron microscopy (SEM). The presence of Fe sulfides and Fe (hydr)oxides indicate heterogeneity in redox potentials on a microscopic scale. Elevated metal(loid) concentrations were associated with trace concentrations of Fe sulfide, indicating an influence on metal transport during weathering. Sequential chemical extractions (SCE) performed on source sediment fractions demonstrated that most As and U was adsorbed to Fe- and Mn-oxides and carbonates with lesser amounts bound by ion exchange, organics and Fe sulfides. Large changes in U/Th and As/Th ratios were observed to coincide with geochemical changes in the watershed, suggesting that metal(loid)–Th ratios may be used in environmental investigations to identify geochemically-significant watershed conditions.

The characterization and accumulation pathway of metal-rich cyanide phases in mine-contaminated Balmer Lake (Ontario, Canada) were assessed through detailed examination of sediment mineralogy and porewater composition. The near-surface deposits in the lake consist of fine-grained calcareous tailings intermixed with natural organic-rich lake sediments. The tailings contain blue to greenish Fe-dominant cyanide that has formed in situ within the tailings. X-ray diffraction confirmed the presence of a mixed ferri/ferrocyanide [ Fe 4 III ( Fe II ( CN ) 6 ) 3 ] , commonly referred to as “Prussian Blue” but it is likely other metal–cyanide complexes are present as evidenced by the distinct colour variations. The cyanide phases occur in up to 1 wt.% as discrete particles and as bedded layers, where the cyanide phases act to cement other siliceous tailings components into a heterogeneous blend. Energy Dispersion X-ray Spectroscopy (EDS) analyses indicate that the authigenic cyanide precipitates contain variable amounts of Ni, Cu and Zn. Quantitatively, the cyanide compounds represent the dominant repository for Cu in Balmer Lake sediments. For Ni and Zn, cyanide associations are secondary in importance to Fe oxyhydroxides. High-resolution porewater profiles and solubility considerations suggest that the formation of the cyanide complexes is a feature of historical (pre-1990) conditions when aqueous cyanide concentrations were higher in the lake.

Turquoise Lake is a water-supply reservoir located north of the historic Sugarloaf Mining district near Leadville, Colorado, USA. Elevated water levels in the reservoir may increase flow of low-quality water from abandoned mine tunnels in the Sugarloaf District and degrade water quality downstream. The objective of this study was to understand the sources of water to Dinero mine drainage tunnel and evaluate whether or not there was a direct hydrologic connection between Dinero mine tunnel and Turquoise Lake from late 2002 to early 2008. This study utilized hydrograph data from nearby draining mine tunnels and the lake, and stable isotope (δ18O and δ2H) data from the lake, nearby draining mine tunnels, imported water, and springs to characterize water sources in the study area. Hydrograph results indicate that flow from the Dinero mine tunnel decreased 26% (2006) and 10% (2007) when lake elevation (above mean sea level) decreased below approximately 3004 m (approximately 9855 feet). Results of isotope analysis delineated two meteoric water lines in the study area. One line characterizes surface water and water imported to the study area from the western side of the Continental Divide. The other line characterizes groundwater including draining mine tunnels, springs, and seeps. Isotope mixing calculations indicate that water from Turquoise Lake or seasonal groundwater recharge from snowmelt represents approximately 10% or less of the water in Dinero mine tunnel. However, most of the water in Dinero mine tunnel is from deep groundwater having minimal isotopic variation. The asymmetric shape of the Dinero mine tunnel hydrograph may indicate that a limited mine pool exists behind a collapse in the tunnel and attenutates seasonal recharge. Alternatively, a conceptual model is presented (and supported with MODFLOW simulations) that is consistent with current and previous data collected in the study area, and illustrates how fluctuating lake levels change the local water-table elevation which can affect discharge from the Dinero mine tunnel without physical transfer of water between the two locations.

The fate of antimony in a major lowland river system, the Waikato River, New Zealand by Nathaniel Wilson; Jenny Webster-Brown (2283-2292).
Antimony is an element that is becoming of increasing concern as an environmental contaminant. Geothermal systems are a source of Sb into some fresh waters of New Zealand’s North Island. The purpose of this research was to determine the factors controlling the behaviour of geothermally-derived Sb in the large lowland Waikato River system. The Waikato River is New Zealand’s longest and most utilised river. Antimony in the system exhibited mainly conservative behaviour, and seasonally variable dilution was found to be the most important control on Sb concentrations. The most significant potential removal process was identified as adsorption of Sb onto suspended particulate material (SPM). The adsorption of Sb onto the SPM is enhanced at low (<5) pH conditions, and in the anoxic base of stratified lakes. There was evidence that the adsorption of Sb is mainly onto Fe oxides in SPM, and changes with changing Fe concentrations. Therefore, Sb adsorption was higher in winter (when Fe concentrations in SPM were higher) than in summer. In Lake Ohakuri, which was stratified during the late summer/early autumn of 2007, there was also potential for removal of Sb as Sb2S3 in the presence of sulfide formed in the anoxic layer. The behaviour of Sb was conservative through the estuary at the mouth of the river.Antimony was compared to As, a metalloid often assumed to exhibit behaviour similar to Sb in aquatic environments. It was found that while the removal processes affecting Sb will also affect As, the inverse did not necessarily apply. Arsenic will adsorb more readily to SPM than Sb and, while there was evidence for bioaccumulation of As by freshwater macrophytes, there was no such evidence for Sb.

Organic matter degradation in paper sludge amendments over gold mine tailings by Christine Cousins; Glenn H. Penner; Bruce Liu; Peter Beckett; Graeme Spiers (2293-2300).
The long-term stability of paper sludge amendments as covers for reclaimed mine waste storage facilities must be assessed by the mining industry. This study examines a 6 yr old sequence of paper sludge amendments applied over wastes from historic Au mines located in Northern Ontario, Canada. As paper sludge is mostly comprised of C-rich organic compounds, elemental quantification, 13C cross polarization/magic angle spinning nuclear magnetic resonance (13C CP/MAS NMR) spectroscopy, and Fourier transform infrared (FTIR) spectroscopy were used to examine the minimal changes in the C content and speciation observed of the amendments over time. These results suggest that paper sludge covers are suitable for use in medium to long-term mining reclamation strategies.

Field multi-step limestone and MgO passive system to treat acid mine drainage with high metal concentrations by Manuel A. Caraballo; Tobias S. Rötting; Francisco Macías; José Miguel Nieto; Carlos Ayora (2301-2311).
Passive treatment systems have become one of the most sustainable and feasible ways of remediating acid mine drainage (AMD). However, conventional treatments show early clogging of the porosity or/and coating of the reactive grains when high acidity and metal concentrations are treated. The performance of fine-grained reagents dispersed in a high porosity matrix of wood shavings was tested as an alternative to overcome these durability problems. The system consisted of two tanks of 3 m3 filled with limestone sand and wood shavings, and one tank of 1 m3 with caustic magnesia powder and wood shavings, separated by several oxidation cascades and decantation ponds. The system treated about 1.5 m3/day of AMD containing an average of 360 mg/L Fe, 120 mg/L Al, 390 mg/L Zn, 10 mg/L Cu, 300 μg/L As and 140 μg/L Pb, a mean pH of 3.08 and a net acidity of 2500 mg/L as CaCO3 equivalent. The water reached pH 5 and 6 in the first and second limestone tanks, respectively (suitable to remove trivalent metals); and pH 8–9 in the MgO tank (suitable to remove divalent metals). After 9 months of operation, the system achieved an average removal of 100% Al, Cu, As, Pb, more than 70% Fe, about 25% Zn and 80% acidity. Goethite, schwertmannite, hydrobasaluminite, amorphous Al(OH)3 and gypsum were the main precipitates in the two limestone tanks. Precipitation of divalent metals (Fe (II), Zn, and traces of Cd, Ni and Co) were complete inside the third tank of MgO, but preferential flow along the walls was responsible for its low treatment performance. Goethite, gypsum, Zn-schulenbergite and sauconite are the crystalline solid phases identified in the MgO tank.

The capacity of mine waste to trap CO2 is, in some cases, much larger than the greenhouse gas production of a mining operation. In mine tailings, the presence of secondary carbonate minerals that trap CO2 can therefore represent substantial fixation of this greenhouse gas. The abilities of three methods of quantitative phase analysis to measure trace nesquehonite (MgCO3·3H2O) in samples of processed kimberlite have been assessed: the method of reference intensity ratios (RIR), the internal standard method, and the Rietveld method with X-ray powder diffraction data. Tests on synthetic mixtures made to resemble processed kimberlite indicate that both the RIR and Rietveld methods can be used accurately to quantify nesquehonite to a lower limit of approximately 0.5 wt.% for conditions used in the laboratory. Below this value, estimates can be made to a limit of approximately 0.1 wt.% using a calibration curve according to the internal standard method. The RIR method becomes increasingly unreliable with decreasing abundance of nesquehonite, primarily as a result of an unpredictable decline in preferred orientation of crystallites. For Rietveld refinements, structureless pattern fitting was used to account for planar disorder in lizardite by considering it as an amorphous phase. Rietveld refinement of data collected from specimens that were serrated to minimize preferred orientation of crystallites gives rise to systematic overestimates of refined abundances for lizardite and underestimates for other phases. The resulting pattern of misestimates may be mistaken for the effect of amorphous and/or nanocrystalline material in samples. This effect is mitigated by collecting data from non-serrated specimens, which typically give relative errors on refined abundances for major and minor phases in the range of 5–20%. However, relative error can increase rapidly for abundances less than 5 wt.%. Nonetheless, absolute errors are sufficiently small that estimates can be made for the amount of CO2 stored in secondary nesquehonite using the RIR method or the Rietveld method for abundances ⩾0.5 wt.% and a calibration curve for abundances <0.5 wt.%. The extent to which C is being mineralized in an active mine setting at the Diavik Diamond Mine, Northwest Territories, Canada, has been investigated. Rietveld refinement results and calibrated abundances for trace nesquehonite are used to estimate the amount of CO2 trapped in Diavik tailings. Results of quantitative phase analysis are also used to calculate neutralization potentials for the kimberlite mine tailings and to estimate the contribution made by secondary nesquehonite.

Microbial reduction of ferrous arsenate: Biogeochemical implications for arsenic mobilization by Michael G. Babechuk; Christopher G. Weisener; Brian J. Fryer; Dogan Paktunc; Christian Maunders (2332-2341).
In reduced aqueous environments, the presence of As in solution is a function of both biotic and abiotic mechanisms. Recent studies have demonstrated a significant release of As(III) through the microbial reduction of dissolved and mineral-bound As(V), which raises health concerns when the greater comparative mobility and toxicity of As(III) is considered. These release mechanisms do not operate in isolation but occur in concert with a number of removal processes, including secondary mineralization and sorption to other natural substrates. Thermodynamic and applied experimental studies have shown that ferrous arsenates, such as symplesite [Fe(II)3(As(V)O4)2·8H2O], may provide a significant sink for Fe(II) and As(V). In this study, the stability of a representative ferrous arsenate phase in the presence of the arsenate-reducing bacterium Shewanella sp. strain ANA-3 is examined. The reduction of ferrous arsenate by ANA-3 results in the release of aqueous As(III) and, subsequently, the progressive nucleation of a biogenic ferrous arsenite phase proximal to the microbial cells. The valence states of secondary solid-phase products were verified using X-ray absorption spectroscopy (XAS). Electron microscopy reveals that nucleation occurs on cellular exudates which may imply a role of extracellular reduction through c-type cytochromes as investigated in recent literature. These observations provide new insights into the reduction mechanisms of ANA-3 and the biogeochemical cycling of As(III) in natural systems.

Arsenopyrite oxidation – A review by C.L. Corkhill; D.J. Vaughan (2342-2361).
Arsenopyrite (FeAsS) is the most common As-bearing sulfide mineral. Under oxidising conditions, such as those in mine waste systems, it breaks down to release acids of As and S into the environment, resulting in acid mine drainage with high concentrations of dissolved As. In this communication, current knowledge of arsenopyrite oxidation is reviewed based on a survey of the existing literature, which has focused on processes and reactions at the mineral surface. X-ray photoelectron spectroscopy (XPS) has shown that the oxidation of arsenopyrite in acid is more rapid than in air, water, or in alkaline solutions. Oxidation products reported by XPS include Fe(III) oxide, As(III), As(V), SO 3 2 - and SO 4 2 - . The elemental constituents of arsenopyrite oxidise at different rates, although there is no consensus as to which is the fastest or slowest to oxidise. Electrochemical studies have highlighted the formation of elemental S on the arsenopyrite surface, while XPS studies suggest that only oxy-anions of S form. Kinetic studies of arsenopyrite oxidation suggest that O2 and Fe3+ are the dominant inorganic agents causing arsenopyrite dissolution. The bacterially-mediated oxidation of arsenopyrite by acidophilic Fe- and S-oxidising bacteria such as Acidithiobacillus ferrooxidans and Acidithiobacillus caldus, is more extensive than abiotic oxidation. The literature pertaining to arsenopyrite oxidation is divided regarding the reaction stoichiometry, and the composition and layering of surface overlayers.

Mine drainage from the weathering of sulfide minerals and magnetite by M.C. Moncur; J.L. Jambor; C.J. Ptacek; D.W. Blowes (2362-2373).
Pyrite and pyrrhotite are the principal minerals that generate acid drainage in mine wastes. Low-pH conditions derived from Fe-sulfide oxidation result in the mobilization of contaminant metals (such as Zn, Cd, Ni and Cr) and metalloids (such as As) which are of environmental concern. This paper uses data from detailed mineralogical and geochemical studies conducted at two Canadian tailings impoundments to examine the mineralogical changes that pyrite, pyrrhotite, sphalerite and magnetite undergo during and after sulfide oxidation, and the subsequent release and attenuation of associated trace elements. The stability of sphalerite in tailings impoundments generally is greater than that of pyrrhotite, but less than pyrite. Dissolved Ni and Co derived from Fe sulfides, and to a lesser extent, dissolved Zn and Cd from sphalerite, are commonly attenuated by early-formed Fe oxyhydroxides. As oxidation progresses, a recycling occurs due to continued leaching from low-pH pore waters and because the crystallinity of Fe oxyhydroxides gradually increases which decreases their sorptive capacity. Unlike many other elements, such as Cu, Pb and Cr, which form secondary minerals or remain incorporated into mature Fe oxyhydroxides, Zn and Ni become mobile. Magnetite, which is a potential source of Cr, is relatively stable except under extremely low-pH conditions. A conceptual model for the sequence of events that typically occurs in an oxidizing tailings impoundment is developed outlining the progressive oxidation of a unit of mine waste containing a mixed assemblage of pyrrhotite and pyrite.