Pyrite Weathering Research Articles

Distribution of arsenic, selenium, and other trace elements in high pyrite Appalachian coals: Evidence for multiple episodes of pyrite formation

Abstract Pennsylvanian coals in the Appalachian Basin host pyrite that is locally enriched in potentially toxic trace elements such as As, Se, Hg, Pb, and Ni. A comparison of pyrite-rich coals from northwestern Alabama, eastern Kentucky, and West Virginia reveals differences in concentrations and mode of occurrence of trace elements in pyrite. Pyrite occurs as framboids, dendrites, or in massive crystalline form in cell lumens or crosscutting veins. Metal concentrations in pyrite vary over all scales, from microscopic to mine to regional, because trace elements are inhomogeneously distributed in the different morphological forms of pyrite, and in the multiple generations of sulfide mineral precipitates. Early diagenetic framboidal pyrite is usually depleted in As, Se, and Hg, and enriched in Pb and Ni, compared to other pyrite forms. In dendritic pyrite, maps of As distribution show a chemical gradient from As-rich centers to As-poor distal branches, whereas Se concentrations are highest at the distal edges of the branches. Massive crystalline pyrite that fills veins is composed of several generations of sulfide minerals. Pyrite in late-stage veins commonly exhibits As-rich growth zones, indicating a probable epigenetic hydrothermal origin. Selenium is concentrated at the distal edges of veins. A positive correlation of As and Se in pyrite veins from Kentucky coals, and of As and Hg in pyrite-filled veins from Alabama coals, suggests coprecipitation of these elements from the same fluid. In the Kentucky coal samples (n = 18), As and Se contents in pyrite-filled veins average 4200 ppm and 200 ppm, respectively. In Alabama coal samples, As in pyrite-filled veins averages 2700 ppm (n = 34), whereas As in pyrite-filled cellular structures averages 6470 ppm (n = 35). In these same Alabama samples, Se averages 80 ppm in pyrite-filled veins, but was below the detection limit in cell structures. In samples of West Virginia massive pyrite, As averages 1700 ppm, and Se averages 270 ppm (n = 24). The highest concentration of Hg (≤ 102 ppm) is in Alabama pyrite veins. Improved detailed descriptions of sulfide morphology, sulfide mineral paragenesis, and trace-element concentration and distribution allow more informed predictions of: (1) the relative rate of release of trace elements during weathering of pyrite in coals, and (2) the relative effectiveness of various coal-cleaning procedures of removing pyrite. For example, trace element-rich pyrite has been shown to be more soluble than stoichiometric pyrite, and fragile fine-grained pyrite forms such as dendrites and framboids are more susceptible to dissolution and disaggregation but less amenable to removal during coal cleaning.

Clay-Mineral Formation in Soils Developed in the Weathering Zone of Pyrite-Bearing Schists: A Case Study from The Abandoned Pyrite Mine in Wieściszowice, Lower Silesia, SW Poland

AbstractIntense mineral transformations that produce acid soils from weathering zones of pyritebearing rocks, including alterations of layer silicates, are of critical importance to agricultural and environmental interests in various regions of the world. To date, the transformations of layer silicates in these soils have not been studied in detail. The aim of the present investigation was to examine the weathering pathways controlling processes of clay-mineral formation in acidic soils developed near the abandoned pyrite mine in Wieściszowice (Lower Silesia, SW Poland). A sequence of soils, from weakly developed technogenic soils (located on the mine dumps) to well developed natural soils, was selected. Bulk soil material and separated clay fractions were analyzed using X-ray diffractometry, Fouriertransform infrared spectroscopy, and scanning electron microscopy-energy dispersive spectrometry. The profiles analyzed were developed on pyrite-bearing schists containing trioctahedral Mg,Fe-chlorite and dioctahedral micas (muscovite and paragonite). Because of pyrite weathering, all the soils studied were strongly acidic (pH 2.8–4.4). Inherited chlorite and micas (K- and Na-mica) predominated in the clay fractions of soils developed on the mine dumps, whereas clays from natural soils were rich in pedogenic minerals (i.e. smectite, vermiculite, and mixed-layer minerals containing hydrated interlayers). The formation of both vermiculite and smectite at the expense of chlorite was observed in the soils studied. The transformation probably led to smectite formation via intermediate stages of mixed-layer minerals (i.e. chlorite-vermiculite, chlorite-smectite, and/or vermiculite-smectite). The process of chlorite dissolution took place simultaneously with the transformation. Micas were mainly transformed to smectite and mixedlayer mica-smectite. Neoformation of kaolinite occurring in A horizons of the soils investigated was also documented. Metal-hydroxy interlayers in Bw horizons of well developed soils were found. The process of interlayer development appeared to be pH dependent and took place at pH ⩾4.2. The processes of claymineral formation in soils developed in the weathering zone of a pyrite-bearing schist are similar to those occurring in podzols (Spodosols).

Hydrochemical Characteristics and Sodification of Groundwater in the Shirin Sou, Hamedan, Western Iran

Salinity and sodicity of groundwater are the principal water quality concerns in irrigated areas of arid and semi-arid regions. The hydrochemical characteristics and sodicity of groundwater in the Shirin Sou area, western Iran were investigated in this study by chemical analyses of groundwater samples from 49 wells. Chemical analysis of the groundwater showed that the mean concentration of the cations was in the order: Na+ > Ca2+ > Mg2+ > K+, while that for anions was SO32− > Cl− > HCO3− > NO3−. The most prevalent water type is Na–SO4 followed by water types Na–Cl and Ca–SO4. The chemical evolution of groundwater is primarily controlled by water–rock interactions: mainly weathering of aluminosilicates, dissolution of sulfate minerals, and cation exchange reactions. Sulfate dissolution and pyrite weathering may both contribute to the SO42− load of the groundwater. High Na+ concentrations in groundwater participate in ion-exchange processes, resulting in the displacement of base cations into solution and raised concentrations in groundwater. The principal component analysis (PCA) performed on groundwater identified three principal components controlling variability of groundwater chemistry. Electrical conductivity, Ca2+, Mg2+, Na+, SO42−, and Cl− content were associated in the same component (PC1) (salinity), most likely linked to anthropogenic activities.

Redox potential (Eh) and anion effects of pyrite (FeS 2) leaching at pH 1

Pyrite plays the central role in the environmental issue of acid rock drainage. Natural weathering of pyrite results in the release of sulphuric acid which can lead to further leaching of heavy and toxic metals from other associated minerals. Understanding how pyrite reacts in aqueous solution is critical to understanding the natural weathering processes undergone by this mineral. To this end an investigation of the effect of solution redox potential (Eh) and various anions on the rate of pyrite leaching under carefully controlled conditions has been undertaken. Leaching of pyrite has been shown to proceed significantly faster at solution Eh of 900 mV (SHE) than at 700 mV, at pH 1, for the leach media of HCl, H 2SO 4 and HClO 4. The predominant effect of Eh suggests electrochemical control of pyrite leaching with similar mechanism(s) at Eh of 700 and 900 mV albeit with different kinetics. Leach rates at 700 mV were found to decrease according to HClO 4 > HCl > H 2SO 4 while at 900 mV the leach rate order was HCl > HClO 4 > H 2SO 4. Solution Fe 3+ activity is found to continually increase during all leaches; however, this is not accompanied by an increase in leach rate. Synchrotron based photoemission electron microscopy (PEEM) measurements showed a localised distribution of adsorbed and oxidised surface species highlighting that pyrite oxidation and leaching is a highly site specific process mediated by adsorption of oxidants onto specific surface sites. It appears that rates may be controlled, in part, by the propensity of acidic anions to bind to the surface, which varies according to SO 4 2 - > Cl - > ClO 4 - , thus reducing the reactive or effective surface area. However, anions may also be involved in specific reactions with surface leach products. Stoichiometric dissolution data (Fe/S ratio), XPS and XRD data indicate that the highest leach rates (in HCl media at 900 mV Eh) correlate with relatively lower surface S abundance. Furthermore, there are indications that solution Cl − assists oxidation especially at higher Eh through the prevention of surface S 0 buildup at reactive surface sites.

Re-assessing the surface cycling of molybdenum and rhenium

We re-evaluate the cycling of molybdenum (Mo) and rhenium (Re) in the near-surface environment. World river average Mo and Re concentrations, initially based on a handful of rivers, are calculated using 38 rivers representing five continents, and 11 of 19 large-scale drainage regions. Our new river concentration estimates are 8.0 nmol kg −1 (Mo), and 16.5 pmol kg −1 (Re, natural + anthropogenic). The linear relationship of dissolved Re and SO 4 2 - in global rivers ( R 2 = 0.76) indicates labile continental Re is predominantly hosted within sulfide minerals and reduced sediments; it also provides a means of correcting for the anthropogenic contribution of Re to world rivers using independent estimates of anthropogenic sulfate. Approximately 30% of Re in global rivers is anthropogenic, yielding a pre-anthropogenic world river average of 11.2 pmol Re kg −1. The potential for anthropogenic contribution is also seen in the non-negligible Re concentrations in precipitation (0.03–5.9 pmol kg −1), and the nmol kg −1 level Re concentrations of mine waters. The linear Mo– SO 4 2 - relationship ( R 2 = 0.69) indicates that the predominant source of Mo to rivers is the weathering of pyrite. An anthropogenic Mo correction was not done as anthropogenically-influenced samples do not display the unambiguous metal enrichment observed for Re. Metal concentrations in high temperature hydrothermal fluids from the Manus Basin indicate that calculated end-member fluids (i.e. Mg-free) yield negative Mo and Re concentrations, showing that Mo and Re can be removed more quickly than Mg during recharge. High temperature hydrothermal fluids are unimportant sinks relative to their river sources 0.4% (Mo), and 0.1% (pre-anthropogenic Re). We calculate new seawater response times of 4.4 × 10 5 yr ( τ Mo) and 1.3 × 10 5 yr ( τ Re, pre-anthropogenic).

Characteristics and potential environmental influences of mine waste in the area of the closed Mežica Pb–Zn mine (Slovenia)

About 19 million tons of Pb–Zn ore were excavated and processed during more than 300 years of mining and metallurgical activities in the Meža Valley, leaving behind large amounts of mine and ore processing wastes, which were deposited as spoil heaps in narrow valleys and on steep slopes of small streams and in abandoned mine shafts at about 30 locations. After the mine and processing facilities were closed in 1995, dumps of low-grade ore and ore processing wastes persisted as a source of potentially toxic elements in the environment. In the presented research, detailed chemical and scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) analyses of three of the most important mine waste deposits, the Štopar, Kavšak, and Fridrih waste deposits, were carried out with the purpose of determining the influence of mine waste deposits on high contents of potentially toxic elements in environmental media, determining modes of occurrence of metals in waste deposit material, and assessing the stability and mobility of toxic elements on the basis of solubility data of metal-bearing phases and minerals. Chemical analysis showed that the highest contents of Pb, Zn, and Cd occurred in the Štopar waste deposit and the highest contents of Mo, V, and As in the Fridrih waste deposit. SEM/EDS analysis revealed that Pb, Zn, V, and Mo in the waste deposit material occur mostly as primary ore minerals, such as cerussite, sphalerite, smithsonite, descloizite, and wulfenite. A considerable amount of Pb and Zn was found bound to secondary weathering products, such as Fe-oxy-hydroxides, Mn-oxides, Fe-oxy-hydroxy sulfates, and Al-silicates. Solubility of primary ore minerals is generally restricted to the pyrite weathering zones and consequently they are relatively stable in the carbonate environment of mine waste deposits. With the exception of Fe-oxy-hydroxy sulfates, which are considered unstable in high-pH environments, secondary weathering products are stable and thus represent sustainable trapping and stabilization media for Pb and Zn in the investigated mine waste deposits. However, mine waste material is being washed out into the nearby streams, where the changes in environmental conditions may cause leaching and mobilization of potentially toxic elements into water.

Sulfate and Phosphate Speleothems at Jenolan Caves, New South Wales, Australia

Sulfate and phosphate deposits at Jenolan Caves occur in a variety of forms and compositions including crusts, ‘flowers’ and fibrous masses of gypsum (selenite), and clusters of boss-like speleothems (potatoes) of ardealite (calcium sulphate, phosphate hydrate) with associated gypsum. This boss-like morphology of ardealite does not appear to have been previously described in the literature and this is the first report of ardealite in New South Wales. Gypsum var. selenite occurs in close association with pyrite-bearing palaeokarst, while the ardealite gypsum association appears to relate to deposits of mineralised bat guano. Isotope studies confirm that the two gypsum suites have separate sources of sulfur, one from the weathering of pyrite (-1.4 to +4.9 δ 34 S) for gypsum (selenite) and the other from alteration of bat guano (+11.4 to +12.9 δ 34 S) for the ardealite and gypsum crusts.

Geochemistry of mine waters draining a low-sulfide, gold-quartz vein deposit, Bralorne, British Columbia

Abstract The Bralorne and Pioneer mines, now inactive, produced over 4 million ounces of Au from an orogenic lode Au deposit located on the eastern edge of the Coastal Mountains of SW British Columbia. Between 2007 and 2009, drainage from a recently developed exploration adit was investigated in order to better understand and anticipate potential environmental management issues associated with the development of this type of deposit in the future. Portal discharge rate and specific conductance were monitored continuously over a 14-month period during which 36 water samples were collected. Additional samples were collected from flooded workings within the adit. Concentrations of As and Sb at the portal range as high as 1738 and 316 μg/L, respectively, while those in the mine pool reach 3304 and 349 μg/L, respectively. Effluent chemistry is mildly alkaline (pH = 8.7) and is dominated by Na, Ca, Mg, HCO3 and SO4. Geochemical inverse modeling of effluent composition indicates weathering of albite (2515 kg/a), ferroan dolomite (718 kg/a), pyrite (456 kg/a), arsenopyrite (23 kg/a) and stibnite (2 kg/a). Modeled sulfide reaction coefficients, normalized by their corresponding host rock concentrations, suggest that oxidation of arsenopyrite is 25 times slower than that of pyrite whereas oxidation of stibnite is 1.5 times faster. Oxidative dissolution of arsenopyrite and stibnite releases 10.6 kg/a of As and 1.1 kg/a of Sb of which 57% and 46%, respectively, are sorbed to ferrihydrite and gibbsite on the bed of the shallow channel through which the mine pool drains to the portal. Although mass balance calculations predict the formation of sufficient ferrihydrite to sorb 100% of the As dissolved in the mine pool, this attenuation process was ineffective possibly because the precipitated sorbents settled to the bottom of the water column or because of competition for sorption sites from Ca and HCO3. The dissolved Sb/As molar ratio in portal effluent (0.082) is much greater than the Sb/As ratio of the mineralization (0.002) because of slower arsenopyrite oxidation and somewhat lesser sorption of Sb.

Environmental geochemistry and quality assessment of mine water of Jharia coalfield, India

A long mining history and unscientific exploitation of Jharia coalfield caused many environmental problems including water resource depletion and contamination. A geochemical study of mine water in the Jharia coalfield has been undertaken to assess its quality and suitability for domestic, industrial and irrigation uses. For this purpose, 92 mine water samples collected from different mining areas of Jharia coalfield were analysed for pH, electrical conductivity (EC), major cations (Ca2+, Mg2+, Na+, K+), anions (F−, Cl−, HCO3−, SO42−, NO3−), dissolved silica (H4SiO4) and trace metals. The pH of the analysed mine water samples varied from 6.2 to 8.6, indicating mildly acidic to alkaline nature. Concentration of TDS varied from 437 to 1,593 mg L−1 and spatial differences in TDS values reflect the variation in lithology, surface activities and hydrological regime prevailing in the region. SO42− and HCO3− are dominant in the anion and Mg2+ and Ca2+ in the cation chemistry of mine water. High concentrations of SO42− in the mine water of the area are attributed to the oxidative weathering of pyrites. Ca–Mg–SO4 and Ca–Mg–HCO3 are the dominant hydrochemical facies. The drinking water quality assessment indicates that number of mine water samples have high TDS, total hardness and SO42− concentrations and needs treatment before its utilization. Concentrations of some trace metals (Fe, Mn, Ni, Pb) were also found to be above the desirable levels recommended for drinking water. The mine water is good to permissible quality and suitable for irrigation in most cases. However, higher salinity, residual sodium carbonate and Mg-ratio restrict its suitability for irrigation at some sites.

Does the Paleoproterozoic Animikie Basin record the sulfidic ocean transition? REPLY

The Paleoproterozoic Animikie Basin in the Lake Superior region of North America is the benchmark for understanding one of the most significant changes in seawater chemistry in Earth history—the transition to a sulfidic ocean (ca. 1.84 Ga). This transition marks a dramatic increase in ocean sulfide produced by bacterial reduction of sulfate formed through the oxic chemical weathering of pyrite during the Great Oxidation Event. Such a change is thought to have caused the cessation of widespread iron formation deposition and marks the beginning of a long lull in the evolution of eukaryotes. The feasibility of using the Animikie Basin to understand this transition is re-evaluated by comparing new sulfur isotope data (δ 34 S pyrite ) from the Michigamme Formation in northern Michigan, United States, to published results from the correlative Rove Formation in Ontario, Canada. These data suggest that microbial sulfate reduction was restricted to organic-rich environments away from the influence of deltas, which delivered low-sulfate river water to the coast. Sulfur isotope data and the patchiness of sulfate reduction within the Animikie Basin suggest strong lateral and vertical gradients in seawater sulfate concentrations. When viewed in the context of the most recent tectonic and sedimentologic models, these observations are best interpreted as reflecting an evolving basin with restricted water circulation, not open circulation with the global ocean as previously postulated. Thus, the Animikie Basin does not contain an accurate record of open-ocean structure and composition during the onset of sulfidic conditions. What is clear is that marginal seas must be carefully evaluated before they are used to model the global ocean, especially given the rarity of preserved Precambrian deep-sea sediments.

Carbon, sulfur, and oxygen isotope evidence for a strong depth gradient and oceanic oxidation after the Ediacaran Hankalchough glaciation

In order to understand spatial variations of stable isotope geochemistry in the Quruqtagh basin (northwestern China) in the aftermath of an Ediacaran glaciation, we analyzed carbonate carbon isotopes ( δ 13 C carb), carbonate oxygen isotopes ( δ 18 O carb), carbonate associated sulfate sulfur ( δ 34 S CAS) and oxygen isotopes ( δ 18 O CAS), and pyrite sulfur isotopes ( δ 34 S py) of a cap dolostone atop the Ediacaran Hankalchough glacial diamictite at four sections. The four studied sections (YKG, MK, H and ZBS) represent an onshore–offshore transect in the Quruqtagh basin. Our data show a strong paleobathymetry-dependent isotopic gradient. From the onshore to offshore sections, δ 13 C carb values decrease from −2‰ to −16‰ (VPDB), whereas δ 18 O carb values increase from −4‰ to −1‰ (VPDB). Both δ 34 S CAS and δ 34 S py show stratigraphic variations in the two onshore sections (MK and YKG), but are more stable in the two offshore sections (H and ZBS). δ 18 O CAS values of onshore samples are consistent with terrestrial oxidative weathering of pyrite. We propose that following the Hankalchough glaciation seawater in the Quruqtagh basin was characterized by a strong isotopic gradient. The isotopic data may be interpreted using a three-component mixing model that involves three reservoirs: deep-basin water, surface water, and terrestrial weathering input. In this model, the negative δ 13 C carb values in the offshore sections are related to the upwelling of deep-basin water (where anaerobic oxidation of dissolved organic carbon resulted in 13 C-depleted DIC), whereas sulfur isotope variations are strongly controlled by surface water sulfate and terrestrial weathering input derived from oxidative weathering of pyrite. The new data provide evidence for the oceanic oxidation following the Hankalchough glaciation.

The impact of cemented layers and hardpans on oxygen diffusivity in mining waste heaps A field study of the Halsbrücke lead–zinc mine tailings (Germany)

This article reports fibre-optic oxygen measurements on a reactive mine waste heap located in the polymetallic sulphide mine district of Freiberg in south-eastern Germany. The heaped material consists of sulphide-bearing tailings from a processing plant of a lead–zinc mine. Mine waste material was deposited in the water phase after separation of mining ores in a flotation process. The tailing impoundment is partly covered with coarse sand and topsoil. Oxygen profiles were monitored during one year at eleven locations showing different physical and mineralogical compositions. At each location a borehole was drilled where the optic sensors were installed at 2–5 different depths. After installation the oxygen profiles were monitored seven times during one year from 2006–2007 and three to five oxygen profiles at each location were obtained. Oxygen measurements were accompanied by physical, chemical and mineralogical data of the tailing material. Additionally, a detailed mineralogical profile was analysed at a location representative for the central part of the heap, where the cemented layers show lateral continuity. Results showed that cemented layers have a significant influence on natural attenuation of the toxic As and Pb species owing to their capacity of water retention. The measured oxygen profiles are controlled by the zone of active pyrite weathering as well as by the higher water content in the cemented layers which reduces gaseous atmospheric oxygen supply. In contrast, gypsum bearing hardpans detected at three other locations have no detectable influence on oxygen profiles. Furthermore, the grain size distribution was proved to have a major effect on oxygen diffusivity due to its control on the water saturation. Temporal changes of the oxygen profiles were only observed at locations with coarse sediment material indicating also an important advective part of gas flux.

34S and 18O in dissolved sulfate as tracers of hydrogeochemical evolution of the Triassic carbonate aquifer exposed to intense groundwater exploitation (Olkusz–Zawiercie region, southern Poland)

Abstract The objective of this study was to determine the sources of SO 4 2 - in groundwater of the Olkusz–Zawiercie Major Groundwater Body. The quality of groundwater was relatively good in the past, but fluctuations of the water table level have caused degradation of water quality. Variations in the water table level and the formation of the depression cone have resulted from both groundwater withdrawal and Zn–Pb mine dewatering. As a result within the extended vadose zone of the aquifer, weathering of pyrite and accompanying sulfides has taken place. Since 1992 the water table has risen and this process has been associated with an increase in concentrations of SO 4 2 - , Ca and Mg. At the same time, the pH has decreased and periodically high Fe concentrations have been detected. High concentrations of Mg and Sr have been observed and, since gypsum layers are known to be present, a de-dolomitisation process has been hypothesized. The PHREEQC program for Windows was used to estimate saturation indices for calcite, dolomite, gypsum and epsomite. Isotopic data for SO 4 2 - dissolved in the groundwater and archival data on isotopic composition of ore sulfides were used to solve the isotope balance equation and to estimate the fraction of dissolved SO 4 2 - that originated from pyrite oxidation and gypsum dissolution. The results have shown that dissolution of pyrite oxidation products has a significant influence on chemical composition of groundwater, especially in the southern part of the cone of depression. By solving the additional, combined mass transfer and isotope balance equations it was inferred that a variation in isotopic composition of weathered sulfides must also occur.

Mineralogy of selected geological deposits from the United Kingdom and the Republic of Ireland as possible capping material for low-level radioactive waste disposal facilities

Solid low-level radioactive waste (LLW) is currently being disposed at a number of facilities in the United Kingdom (UK). The safety of these facilities relies to some extent on the use of engineered barriers, such as a cap and a liner, to isolate the waste and protect the environment. Generally, the material used as the barrier layer within such a cap should be of low permeability and it should retain this property over long timescales (beyond a few decades normally required for facilities containing non-radioactive wastes). The objective of this research is to determine the mineralogy of selected geological deposits from the UK and Republic of Ireland as part of a larger project to examine their suitability as a capping material, particularly on LLW sites. Mineral transformations, from weathering, may impact on the long-term performance of the cap and even the disposal facility. These transformations could be brought on or enhanced by climate change. X-ray diffraction (XRD) was carried-out on the sand, silt and clay fractions of the London Clay, Belfast Upper Boulder Clay, Irish Glacial Till, Belfast Sleech, and Ampthill Clay geological deposits. Minerals were present that could pose both positive and negative effects on the long-term performance of the cap. Smectite, which has a high shrink swell potential, may produce cracks in London Clay, Belfast Upper Boulder Clay and Ampthill Clay capping material during dry, hotter periods as a possible consequence of future climate change; thus, resulting in higher permeability. Ampthill Clay and Belfast Sleech had elevated amounts of organic matter (OM) at 5.93% and 5.88%, respectively, which may also contribute to cracking. Over time, this OM may decompose and result in increased permeability. Gypsum [CaSO 4] in the silt and sand fractions of Ampthill Clay may reduce the impact of erosion during wetter periods if it is incorporated into the upper portion of the cap. There are potential negative effects from the acidity created by the weathering of pyrite [FeS 2] present in the silt and sand fractions of Belfast Sleech and Ampthill Clay that could impede the growth of grasses used to stabilize the surface of the capping material if this material is used as part of the vegetative soil layer. Additionally, acidic waters generated from pyrite weathering could negatively impact the lower lying capping material and the disposal facility in general, because they could react with contaminants and weaken vessels storing contaminants. However, calcium carbonate [CaCO 3] present in the silt and sand fractions of these deposits, and dolomite [CaMg(CO 3) 2] in Belfast Sleech, may counter act the acidity.

Response of lake chemistry to changes in atmospheric deposition and climate in three high-elevation wilderness areas of Colorado

Trends in precipitation chemistry and hydrologic and climatic data were examined as drivers of long-term changes in the chemical composition of high-elevation lakes in three wilderness areas in Colorado during 1985–2008. Sulfate concentrations in precipitation decreased at a rate of −0.15 to −0.55 μeq/l/year at 10 high-elevation National Atmospheric Deposition Program stations in the state during 1987–2008 reflecting regional reductions in SO2 emissions. In lakes where sulfate is primarily derived from atmospheric inputs, sulfate concentrations also decreased although the rates generally were less, ranging from −0.12 to −0.27 μeq/l/year. The similarity in timing and sulfur isotopic data support the hypothesis that decreases in atmospheric deposition are driving the response of high-elevation lakes in some areas of the state. By contrast, in lakes where sulfate is derived primarily from watershed weathering sources, sulfate concentrations showed sharp increases during 1985–2008. Analysis of long-term climate records indicates that annual air temperatures have increased between 0.45 and 0.93°C per decade throughout most mountainous areas of Colorado, suggesting climate as a factor. Isotopic data reveal that sulfate in these lakes is largely derived from pyrite, which may indicate climate warming is preferentially affecting the rate of pyrite weathering.

Composition, spatial distribution, and environmental significance of water ions in Pumayum Co catchment, southern Tibet

The chemistry of major cations (Mg2+, Ca2+, Na+, and K+) and anions (HCO3−, SO42−, and Cl−) in the water of Lake Pumayum Co and its inflow river was studied, revealing the obvious ionic difference among various inflow rivers and the lake. The chemical type of the lake water was Mg2+-Ca2+-HCO3−-SO42+, but the major ions of the main inflow rivers were Ca2+-Mg2+-HCO3−. In the lake inlet of Jiaqu River, the main inflow river, there was significant variance of water chemistry within the depth less than 2 m. However, it was almost homogeneous at other area of the lake. Therefore, with the evidence of distribution of water chemistry and oxygen isotope of lake water, a conclusion can be outlined that Jiaqu River had a distinct effect on the hydrochemistry of the water on the submerged delta, whereas this is not the case for other rivers. The Gibbs plot revealed that the dominant mechanism responsible for controlling chemical compositions of the lake water was rocks weathering in the drainage area. Ion ratios and ternary plots further explored the main processes controlling the water chemistry of the catchment, i.e., carbonate weathering, pyrite weathering, and silicate weathering. The different hydrochemistry characteristics between river water and lake water may result from the CaCO3 precipitation. The findings will benefit the explanation of the environmental significance of carbonate in paleolimnological studies in the lake.

Geochemical Evolution of a High Arsenic, Alkaline Pit-Lake in the Mother Lode Gold District, California

The Harvard orebody at the Jamestown gold mine, located along the Melones fault zone in the southern Mother Lode gold district, California, was mined in an open-pit operation from 1987 to 1994. Dewatering during mining produced a hydrologic cone of depression; recovery toward the premining ground-water configuration produced a monomictic pit lake with alkaline Ca-Mg-HCO3-SO4–type pit water, concentrations of As up to 1,200 μ g/L, and total dissolved solids (TDS) up to 2,000 mg/L. In this study, pit-wall rocks were mapped and chemically analyzed to provide a context for evaluating observed variability in the composition of the pit-lake waters in relationship to seasonal weather patterns. An integrated hydrogeochemical model of pit-lake evolution based on observations of pit-lake volume, water composition (samples collected between 1998–2000, 2004), and processes occurring on pit walls was developed in three stages using the computer code PHREEQC. Stage 1 takes account of seasonally variable water fluxes from precipitation, evaporation, springs, and ground water, as well as lake stratification and mixing processes. Stage 2 adds CO2 fluxes and wall-rock interactions, and stage 3 assesses the predictive capability of the model. Two major geologic units in fault contact comprise the pit walls. The hanging wall is composed of interlayered slate, metavolcanic and metavolcaniclastic rocks, and schists; the footwall rocks are chlorite-actinolite and talc-tremolite schists generated by metasomatism of greenschist-facies mafic and ultramafic igneous rocks. Alteration in the ore zone provides evidence for mineralizing fluids that introduced CO2, S, and K2O, and redistributed SiO2. Arsenian pyrite associated with the alteration weathers to produce goethite and jarosite on pit walls and in joints, as well as copiapite and hexahydrite efflorescences that accumulate on wall-rock faces during dry California summers. All of these pyrite weathering products incorporate arsenic at concentrations from <100 up to 1,200 ppm. In the pit lake, pH and TDS reach seasonal highs in the summer epilimnion; pH is lowest in the summer hypolimnion. Arsenic and bicarbonate covary in the hypolimnion, rising as stratification proceeds and declining during winter rains. The computational model suggests that water fluxes alone do not account for this seasonal variability. Loss of CO2 to the atmosphere, interaction with pit walls including washoff of efflorescent salts during the first flush and seasonal rainfall, and arsenic sorption appear to contribute to the observed pit-lake characteristics.

Schwertmannite in wet, acid, and oxic microenvironments beneath polar and polythermal glaciers

Glacial and iceberg sediments contain nanoparticulates of schwert-mannite, ferrihydrite, and goethite formed where pyrite was oxidized by dissolved oxygen in aqueous subglacial environments. Schwertmannite, typically found in acid mine drainage, only forms at low pH by the oxidative weathering of pyrite. Stoichiometric models show that these conditions can be created in closed-system microenvironments containing at least 10−4 M dissolved oxygen, where volume ratios of water/pyrite are ~105 to 106. Ferrihydrite is the only product at higher and lower volume ratios. In these microenvironments the oxidation of pyrite to form schwertmannite is possible in several decades. Schwertmannite and ferrihydrite are metastable in contact with water and are transformed to goethite in <100 yr unless preserved in ice. The presence of these nanoparticulates demonstrates the existence of transient, acidic, and oxic aqueous microenvironments where enhanced biochemical and/or geochemical activity occurs beneath glaciers and ice sheets.

The impact of pyrite variability, dispersive transport and precipitation of secondary phases on the sulphate release due to pyrite weathering

The objective of this study was to investigate the impact of flow, transport and geochemical parameters in the unsaturated and saturated zones on the release of SO4 from overburden lignite spoil piles into the adjacent lake. A vertical one-dimensional model was set up using the reactive transport simulator SULFIDOX in order to account for the unsaturated zone. The SULFIDOX model was calibrated for effective diffusion using measured O2 in the gas phase and SO4 concentrations in the liquid phase from the unsaturated zone of the heap. The results show high sensitivity to O2 supply and initially present gypsum, but the inclusion of secondary mineral precipitation in equilibrium is of minor importance for the results. To account for the transport of released SO4 from the saturated zone into the surface water, scenarios were performed by using SULFIDOX results as input concentration for a two-dimensional vertical model set up with PROCESSING MODFLOW and MT3D. These scenarios indicate a rising discharge of SO4 into the adjacent lake due to continued pyrite weathering for 80 a. Results are highly sensitive to dispersivity, whereas the spatial variability of pyrite distribution did not show any influence on the results. The consideration of initially present gypsum shows a major effect on the modelled SO4 release.

Evidence of aerial volcanic activity during the Valanginian along the northern Tethys margin

Stratigraphic measurement and sampling on three sections (Vergol, La Charce, and Montclus) through Valanginian deposits from the Vocontian Basin (southeastern France) reveals the occurrence of centimetre thick ochre-coloured layers, which can be correlated from one section to another. At least twelve of these are identified in sediments dated from the Pertransiens to Furcillata ammonite Zones. These horizons appear similar to previously described Oxfordian and Aptian bentonites, also from the Vocontian Basin. Clay-mineralogical and geochemical data are similar in the Valanginian ochre horizons and their enclosing marls except in one of these that shows a clay fraction mainly composed of smectite and which exhibits an enrichment in trace elements (Zr, Ba, Th, Y, Hf, U, Pb, Nb, Ta). This horizon occurs in sediments attributed to the Campylotoxus Zone and is interpreted as a bentonite while the other ochre horizons were derived from the meteoric weathering of pyrite, which probably developed in oxygen-depleted environments. Volcanic ash was presumed to be transported westward by trade winds from volcanic centres located along the northern active margin of the Tethys.