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1.
《Applied Geochemistry》2005,20(8):1533-1545
Spring waters were analysed in the field by anodic stripping voltammetry, using equipment which is sufficiently portable to be useful in a remote heavily forested area accessible by foot only. The equipment and techniques are capable of producing analyses on site to the μg/L level for labile metals. Field analysis avoids issues of sample storage and transport protocols that limit confidence in laboratory measurements of labile elements. Samples were taken as a feedback to immediate analysis resulting in a fine grid map of the geological site. Acid rock drainage emanates from a New Zealand historic mine site, with elevated concentrations of metals. However, ground water and surface water discharging naturally from mineralised rocks in the same area also have elevated levels of metals. This study quantifies natural metalliferous discharges from a single site, and compares this to the overall metal flux from the mine area. Acid (pH 3) metalliferous springs emanate from colluvium and bedrock in a young (months-old) landslide. Labile Cu, Pb, Zn and Cd are the environmentally most significant metals in the studied area. Labile metal concentrations observed in the natural springs are up to 24 μg/L Cu, up to 50 μg/L Pb, up to 5 μg/L Cd and up to 9 mg/L Zn. Labile Cu and Zn concentrations are similar to laboratory-determined total concentrations, whereas labile Pb and Cd concentrations are generally distinctly lower than total Pb and Cd concentrations. Four different spring water compositions occur within metres of each other: acid metalliferous water with high Pb, acid metalliferous water with low Pb, high Cu, Pb, Zn acid water and high pH water with elevated Cu. High metal concentrations in these waters are readily attenuated by adsorption to Fe oxyhydroxides (HFO), especially when rain raises spring water pH at the surface. Copper, Pb and Cd are >99% adsorbed, and Zn >95% adsorbed, during this rainfall dilution. Natural spring waters have potential to contribute up to 10% of the total Zn flux from the catchment, but negligible proportions of Cu, Pb and Cd.  相似文献   

2.
The near-surface water cycle in a geologically complex area comprises very different sources including meteoric, metamorphic and magmatic ones. Fluids from these sources can react with sedimentary, magmatic and/or metamorphic rocks at various depths. The current study reports a large number of major, minor and trace element analyses of meteoric, mineral, thermal and mine waters from a geologically well-known and variable area of about 200 × 150 km in SW Germany. The geology of this area comprises a Variscan granitic and gneissic basement overlain in parts by Triassic and Jurassic shales, sandstones and limestones. In both the basement and the sedimentary rocks, hydrothermal mineralization occurs (including Pb, Cu, As, Zn, U, Co and many others) which were mined in former times. Mineral waters, thermal waters and meteoric waters flowing through abandoned mines (mine waters) are distributed throughout the area, although the mine waters concentrate in and around the Schwarzwald.The present analyses show, that the major element composition of a particular water is determined by the type of surrounding rock (e.g., crystalline or sedimentary rocks) and the depth from which the water originates. For waters from crystalline rocks it is the origin of the water that determines whether the sample is Na–Cl dominant (deeper origin) or Ca–HCO3 dominant (shallow origin). In contrast, compositions of waters from sedimentary rocks are determined by the availability of easily soluble minerals like calcite (Ca–HCO3 dominant), halite (Na–Cl dominant) or gypsum (Ca–SO4 dominant). Major element data alone cannot, therefore, be used to trace the origin of a water. However, the combination of major element composition with trace element data can provide further information with respect to flow paths and fluid–rock interaction processes. Accordingly, trace element analyses showed, that:
  • −Ce anomalies can be used as an indicator for the origin of a water. Whereas surface waters have negative or strongly negative Ce anomalies, waters originating from greater depths show no or only weak negative Ce anomalies.
  • −Eu anomalies can be used to differentiate between host rocks. Waters from gneisses display positive Eu anomalies, whereas waters from granites have negative ones. Waters from sedimentary rocks do not display any Eu anomalies.
  • −Rb and Cs can also be indicators for the rock with which the fluid interacted: Rb and Cs correlate positively in most waters with Rb/Cs ratios of ∼2, which suggests that these waters are in equilibrium with the clay minerals in the rocks. Rb/Cs ratios >5 indicate reaction of a water with existing clay minerals, whereas Rb/Cs ratios <2 are probably related to host rock alteration and clay mineral formation.
The chemical compositions of carbonate precipitates from thermal waters indicate that rare earth elements (REEs), Rb and Cs concentrations in the minerals are controlled by the incorporation of clay particles that adsorb these elements.  相似文献   

3.
Chemical weathering of silicate minerals has long been known as a sink for atmospheric CO2, and feedbacks between weathering and climate are believed to affect global climate. While warmer temperatures are believed to increase rates of weathering, weathering in cool climates can be accelerated by increased mineral exposure due to mechanical weathering by ice. In this study, chemical weathering of silicate minerals is investigated in a small temperate watershed. The Jamieson Creek watershed is covered by mature coniferous forest and receives high annual precipitation (4000 mm), mostly in the form of rainfall, and is underlain by quartz diorite bedrock and glacial till. Analysis of pore water concentration gradients indicates that weathering in hydraulically unsaturated ablation till is dominated by dissolution of plagioclase and hornblende. However, a watershed scale solute mass balance indicates high relative fluxes of K and Ca, indicating preferential leaching of these solutes possibly from the relatively unweathered lodgement till. Weathering rates for plagioclase and hornblende calculated from a watershed scale solute mass balance are similar in magnitude to rates determined using pore water concentration gradients.When compared to the Rio Icacos basin in Puerto Rico, a pristine tropical watershed with similar annual precipitation and bedrock, but with dissimilar regolith properties, fluxes of weathering products in stream discharge from the warmer site are 1.8 to 16.2-fold higher, respectively, and regolith profile-averaged plagioclase weathering rates are 3.8 to 9.0-fold higher. This suggests that the Arrhenius effect, which predicts a 3.5- to 9-fold increase in the dissolution rate of plagioclase as temperature is increased from 3.4° to 22 °C, may explain the greater weathering fluxes and rates at the Rio Icacos site. However, more modest differences in K and Ca fluxes between the two sites are attributed to accelerated leaching of those solutes from glacial till at Jamieson Creek. Our findings suggest that under conditions of high rainfall and favorable topography, weathering rates of silicate minerals in warm tropical systems will tend to be higher than in cool temperate systems, even if the temperate system is has been perturbed by an episode of glaciation that deposits regolith high in fresh mineral surface area.  相似文献   

4.
Active and abandoned mine activities constitute the sources of deterioration of water and soil quality in many parts of the world, particularly in the African Copperbelt regions. The accumulation in soils and the release of toxic substances into the aquatic ecosystem can lead to water resources pollution and may place aquatic organisms and human health at risk. In this study, the impact of past mining activity (i.e., abandoned mine) on aquatic ecosystems has been studied using ICP-MS analysis for trace metals and Rare Earth Elements (REE) in sediment samples from Lubumbashi River (RL) and Tshamilemba Canal (CT), Katanga, Democratic Republic of the Congo (DRC). Soil samples from surrounding CT were collected to evaluate trace metal and REE concentrations and their spatial distribution. The extent of trace metal contamination compared to the background area was assessed by Enrichment Factor (EF) and Geoaccumulation Index (Igeo). Additionally, the trace metal concentrations probable effect levels (PELs) for their potential environmental impact was achieved by comparing the trace metal concentrations in the sediment/soil samples with the Sediment Quality Guidelines (SQGs). Spearman's Rank-order correlation was used to identify the source and origin of contaminants. The results highlighted high concentrations of trace metals in surface sediments of CT reaching the values of 40152, 15586, 610, 10322, 60704 and 15152 mg kg−1 for Cu, Co, Zn, Pb, Fe and Mn, respectively. In the RL, the concentrations reached the values of 24093, 2046, 5463, 3340, 68290 and 769 mg kg−1 for Cu, Co, Zn, Pb, Fe and Mn, respectively. The ΣREE varied from 66 to 218 and 142–331 mg kg−1 for CT and RL, respectively. The soil samples are characterized by variable levels of trace metals. The EF analysis showed “extremely severe enrichment” for Cu and Co. However, no enrichment was observed for REE. Except for Mo, Th, U, Eu, Mo, Ho and Tm for which Igeo is classified as “moderately polluted and/or unpolluted”, all elements in different sites are classified in the class 6, “extremely polluted”. The trace metal concentrations in all sampling sites largely exceeded the SQGs and the PELs for the Protection of Aquatic Life recommendation. Cu and Co had positive correlation coefficient values (r = 0.741, P < 0.05, n = 14). This research presents useful tools for the evaluation of water contamination in abandoned and active mining areas.  相似文献   

5.
《Applied Geochemistry》2006,21(7):1093-1108
Peña del Hierro is an abandoned mine site located in the catchment area of the Tinto river (Pyrite Belt, SW Spain). As leaching from the spoils affect the quality of the stream water, the waste dumps have been characterized for mineralogy, geochemistry and granulometry to obtain an estimate of the potential pollution. Waste rock dumps in Peña del Hierro are very heterogeneous and are mainly composed of acid volcanic tuffs > gossan > shales > roasted pyrite ashes > floated pyrite. The volcanic tuffs, the gossan and the shales coexist in the same piles. The roasted pyrite ashes and the floated pyrite form more homogeneous dumps. The dissolution of pyrite concentrated in pyrite ashes and floated pyrite units can generate acid mine drainage. Nevertheless, acid volcanic tuffs, which are rich in pyrite and have no neutralizing minerals, are the main source of these acidic effluents. Only muscovite might partially neutralize the acidity, but the dissolution of this mineral is too slow to compensate for acidity. The occurrence of jarosite in the <2 mm fraction indicates that extreme acid mine drainage occurs. The gossan and roasted pyrite ashes have high contents of trace elements. According to their concentration, As (46–1710 ppm), Pb (113–3455 ppm) and Hg (0–53) are some of the most important toxic trace elements in these wastes. In dumps mainly composed of volcanic tuffs most of the trace elements derive from the gossan mixed in the piles. Gossan is stable in an oxidizing environment, but acidic effluents (pH < 2) can dissolve Fe oxyhydroxides from them and release high amounts of trace elements to the stream water. This research contributes to estimating the production of acid mine drainage and the actual contamination risk of potentially toxic elements in soils and waters of this area, and could be the base for possible future mitigation actions in other areas affected by mining wastes.  相似文献   

6.
《Applied Geochemistry》2006,21(8):1347-1361
The relationships between factors that control subsurface flow and the timing, duration, and intensity of acidity generation and leaching of metals from waste-rock dumps are investigated. A 12 m high waste-rock pile that had been constructed in 1994 at Key Lake, Saskatchewan, Canada was disassembled, sampled and characterized in 2000. Physical properties that control water flow were characterized by measuring soil–water suction, volumetric water content, and the grain-size distribution at 60 randomized sites within the pile. Grain-size distribution was also measured at an additional 20 grid locations within the pile. Paste pH, pore-water geochemistry, mineralogy, and water-soluble extractions were used to investigate geochemical processes and sulfide oxidation at each of the 20 grid locations. A field-based soil–water characteristic curve could not be developed from the spatially variable and hysteretic field data; consequently, the grain-size distribution was used as a relative measure of subsurface flow and of the tendency to contain water under unsaturated conditions. The geochemical characterization demonstrated that marcasite underwent preferential weathering relative to pyrite and chalcopyrite, that dolomite was the main buffering carbonate mineral, and that gypsum, jarosite, and Fe oxyhydroxides were the main secondary (supergene) minerals. The pore waters contained up to 78,000 mg L−1 SO4, 690 mg L−1 Ni and 1400 mg L−1 U (800, 11.7 and 6 mM, respectively), suggesting that significant weathering had occurred. The pore water chemistry varied considerably between sampling sites. However, neither a correlation of pore-water chemistry with grain-size distribution nor a spatial relationship within the sampled grid was discernible.  相似文献   

7.
Trace element geochemistry was studied in geothermal fluids in Iceland. The major and trace element compositions of hot springs, sub-boiling, and two-phase (liquid and vapor) wells from 10 geothermal areas were used to reconstruct the fluid composition in the aquifers at depth. Aquifer fluid temperatures ranged from 4 to 300 °C, pH values between 4.5 and 9.3, and fluids typically contained total dissolved solids <1000 ppm, except in geothermal areas that have seawater and seawater-meteoric water mixtures. Trace alkali elements Li, Rb and Cs are among the most mobile elements in aquifer fluids, with concentrations in the range of <1 ppb to 3.49 ppm Li, <0.01 to 57 ppb Cs, and <1 ppb to 3.77 ppm Rb. Their chemistry is thought to be dominated by rock leaching and partitioning into Na- and K-containing major alteration minerals. Arsenic, Sb, Mo and W are typically present in concentrations in the range of 1–100 ppb. They are relatively mobile, yet Mo may be limited by molybdenite solubility. The alkaline earth elements Ba and Sr are quite immobile with concentrations in the range of <0.1–10 ppb Ba and <1–100 ppb Sr in the dilute fluids, but up to 5.9 ppm Ba and 8.2 ppm Sr in saline fluids. These elements show a systematic relationship with Ca, possibly due to substitution for Ca in Ca-containing major alteration minerals like calcite, epidote and anhydrite. Incorporation into major Ca-minerals may also be important for Mn. Many metals including Fe, Cr, Ni, Zn, Cu, Co, Pb and Ag have low mobility and concentrations, typically <1 ppb for Ag, Cd, Co, Cr, Cu, Ni, and Pb, <10 ppb for Zn and < 100 ppb for Fe, although for some metals higher concentrations are associated with saline fluids. Based on the metals assessed, saturation is approached with respect to many sulfide minerals and in some cases oxide minerals but Cu, Ni and Pb minerals are slightly but systematically undersaturated, and Ag phases significantly undersaturated. Evaluation of mineral-fluid equilibria for these metals is problematic due to their low concentrations, problems associated with assessing the aqueous species distribution by thermodynamic calculations, and uncertainties concerning the exact minerals possibly involved in such reactions. Reaction path calculations, poor comparison of concentrations measured in the samples collected at the wellhead and published downhole data as well as boiling, cooling and mass precipitation calculations suggest removal of many metals due to changes upon depressurization boiling and conductive cooling of the aquifer fluids as they ascend in wells. These results imply that processes such as mass precipitation upon fluid ascent may be highly important and emphasize the importance of considering mass movement in geothermal systems.  相似文献   

8.
Unplugged abandoned oil and gas wells in the Appalachian region can serve as conduits for the movement of waters impacted by fossil fuel extraction. Strontium isotope and geochemical analysis indicate that artesian discharges of water with high total dissolved solids (TDS) from a series of gas wells in western Pennsylvania result from the infiltration of acidic, low Fe (Fe < 10 mg/L) coal mine drainage (AMD) into shallow, siderite (iron carbonate)-cemented sandstone aquifers. The acidity from the AMD promotes dissolution of the carbonate, and metal- and sulfate-contaminated waters rise to the surface through compromised abandoned gas well casings. Strontium isotope mixing models suggest that neither upward migration of oil and gas brines from Devonian reservoirs associated with the wells nor dissolution of abundant nodular siderite present in the mine spoil through which recharge water percolates contribute significantly to the artesian gas well discharges. Natural Sr isotope composition can be a sensitive tool in the characterization of complex groundwater interactions and can be used to distinguish between inputs from deep and shallow contamination sources, as well as between groundwater and mineralogically similar but stratigraphically distinct rock units. This is of particular relevance to regions such as the Appalachian Basin, where a legacy of coal, oil and gas exploration is coupled with ongoing and future natural gas drilling into deep reservoirs.  相似文献   

9.
《Applied Geochemistry》2005,20(3):639-659
The oxidation of sulfide minerals from mine wastes results in the release of oxidation products to groundwater and surface water. The abandoned high-sulfide Camp tailings impoundment at Sherridon, Manitoba, wherein the tailings have undergone oxidation for more than 70 a, was investigated by hydrogeological, geochemical, and mineralogical techniques. Mineralogical analysis indicates that the unoxidized tailings contain nearly equal proportions of pyrite and pyrrhotite, which make up to 60 wt% of the total tailings, and which are accompanied by minor amounts of chalcopyrite and sphalerite, and minute amounts of galena and arsenopyrite. Extensive oxidation in the upper 50 cm of the tailings has resulted in extremely high concentrations of dissolved SO4 and metals and As in the tailings pore water (pH < 1, 129,000 mg L−1 Fe, 280,000 mg L−1 SO4, 55,000 mg L−1 Zn, 7200 mg L−1 Al, 1600 mg L−1 Cu, 260 mg L−1 Mn, 110 mg L−1 Co, 97 mg L−1 Cd, 40 mg L−1 As, 15 mg L−1 Ni, 8 mg L−1 Pb, and 3 mg L−1 Cr). The acid released from sulfide oxidation has been extensive enough to deplete carbonate minerals to 6 m depth and to partly deplete Al-silicate minerals to a 1 m depth. Below 1 m, sulfide oxidation has resulted in the formation of a continuous hardpan layer that is >1 m thick. Geochemical modeling and mineralogical analysis indicate that the hardpan layer consists of secondary melanterite, rozenite, gypsum, jarosite, and goethite. The minerals indicated mainly control the dissolved concentrations of SO4, Fe, Ca and K. The highest concentrations of dissolved metals are observed directly above and within the massive hardpan layer. Near the water table at a depth of 4 m, most metals and SO4 sharply decline in concentration. Although dissolved concentrations of metals and SO4 decrease below the water table, these concentrations remain elevated throughout the tailings, with up to 60,600 mg L−1 Fe and 91,600 mg L−1 SO4 observed in the deeper groundwater. During precipitation events, surface seeps develop along the flanks of the impoundment and discharge pore water with a geochemical composition that is similar to the composition of water directly above the hardpan. These results suggest that shallow lateral flow of water from a transient perched water table is resulting in higher contaminant loadings than would be predicted if it were assumed that discharge is derived solely from the deeper primary water table. The abundance of residual sulfide minerals, the depletion of aluminosilicate minerals in the upper meter of the tailings and the presence of a significant mass of residual sulfide minerals in this zone after 70 a of oxidation suggest that sulfide oxidation will continue to release acid, metals, and SO4 to the environment for decades to centuries.  相似文献   

10.
The Great Falls-Lewistown Coal Field (GFLCF) in central Montana contains over 400 abandoned underground coal mines, many of which are discharging acidic water with serious environmental consequences. Areas of the mines that are completely submerged by groundwater have circum-neutral pH and relatively low concentrations of metals, whereas areas that are only partially flooded or freely draining have acidic pH (< 3) and high concentrations of metals. The pH of the mine drains either decreases or increases after discharging to the surface, depending on the initial ratio of acidity (mainly Al and Fe2+) to alkalinity (mainly HCO3?). In acidic, Fe-rich waters, oxidation of Fe2+ after exposure to air is microbially catalyzed and follows zero-order kinetics, with computed rate constants falling in the range of 0.97 to 1.25 mmol L? 1 h? 1. In contrast, Fe2+ oxidation in near-neutral pH waters appears to be first-order with respect to Fe2+ concentration, although insufficient data were collected to constrain the rate law expression. Rates of Fe2+ oxidation in the field are dependent on temperature such that lower Fe2+ concentrations were measured in down-gradient waters during the day, and higher concentrations at night. Diel cycles in dissolved concentrations of Zn and other trace metals (Mn, Ni) were also noted for down-gradient waters that were net alkaline, but not in the acidic drains.The coal seams of the GFLCF and overlying Cretaceous sandstones form a perched aquifer that lies ~ 50 m above the regional water table situated in the underlying Madison Limestone. The δD and δ18O values of flooded mine waters suggest local derivation from meteoric water that has been partially evaporated in agricultural soils overlying the coal mines. The S and O isotopic composition of dissolved sulfate in the low pH mine drains is consistent with oxidation of biogenic pyrite in coal under aerated conditions. A clear distinction exists between the isotopic composition of sulfate in the acid mine waters and sulfate in the adjacent sedimentary aquifers, making it theoretically possible to determine if acid drainage from the coal mines has leaked into the underlying Madison aquifer.  相似文献   

11.
This study investigates the post-mining evolution of S-type granitic waste rocks around a former uranium mine, Vieilles Sagnes (Haute Vienne, NW Massif Central, France). This mine was operated between 1957 and 1965 in the La Crouzille former world-class uranium mining district and is representative of intra-granitic vein-type deposits. 50 years after mine closure and the construction and subsequent re-vegetation of the granitic waste rock pile, we evaluate the environmental evolution of the rock pile, including rock alteration, neo-formation of U-bearing phases during weathering, and U migration. Vertical trenches have been excavated through the rock pile down to an underlying paleo-soil, allowing the investigation of the vertical differentiation of the rock pile and its influence on water pathways, weathering processes and U migration and retention. Arenization dominantly drives liberation of U, by dissolution of uraninite inclusions in the most alterable granitic minerals (i.e. K-feldspar and biotite). Retention of U in the matrix at the base of the waste rock pile, and in the underlying paleo-soil most likely occurs by precipitation of (nano-) uranyl phosphates or a combination of co-precipitation and adsorption reactions of U onto Fe (oxy)hydroxides and/or clay minerals. Even though U-migration was observed, U is retained in stable secondary mineral phases, provided the current conditions will not be modified.  相似文献   

12.
《Applied Geochemistry》2004,19(12):1891-1904
A mineralogical study of 3 samples of municipal solid waste incineration bottom ash collected from different storage sites and with storage times varying from 3 weeks to 2 years, has enabled identification of the main secondary mineral species formed during weathering. The frequencies of the secondary phases were determined and a diagram is proposed for the relative distribution of the newly formed mineral phases: calcite  Fe oxides quartz  sulphates and/or ettringite (depending on the amount of reactive Al present in the bottom ash). This approach, involving careful sampling, sample preparation and the combined use of various analytical techniques, also showed the high frequency of Al hydroxides and amorphous phases and helped to identify more than 30 sulphates s.l. (sulphates, chromates, vanadates, etc.). Most of the secondary minerals (carbonates and sulphates s.l.) have broad metal trapping capacities for heavy element uptake (Pb, Zn, Cd, As, V, Cr, etc.) due to their crystal-chemistry characteristics. Ca-oxalates were also identified. Mineralogical data from the study provide new input for thermochemical models. The relative stability of metal uptake and the extent of associated neogenesis occurring during bottom-ash decomposition is discussed. Sulphate minerals (and certain heavy metal oxides (zincite)), which are extremely sensitive to environmental conditions, can trap metals only temporarily, as opposed to Fe oxyhydroxides (As, etc.) and carbonates (Pb, Zn, Cd), which are more stable under atmospheric conditions and constitute more sustainable trapping media with higher liquid/solid (L/S) ratios. Finally, a composite predictive diagram is proposed for the mineralogical evolution of bottom ash that accounts for variations in L/S ratios.  相似文献   

13.
This study was conducted to assess the anthropogenic impact on metal concentrations in the bottom sediments of the Juam reservoir, Korea, and in stream sediments in its catchment, and to estimate the potential mobility of selected metals (Fe, Mn, Cu, Ni, Pb and Zn) using sequential extraction. A comparison of the metal concentrations in the stream sediments with mean background values in sediments collected from first- or second-order creeks shows that Pb, Cu and Ni are the most affected by anthropogenic inputs. The 206Pb/207Pb ratios of the bottom and core sediments (means: 1.2320 ± 0.0502 and 1.2212 ± 0.0040, respectively) suggest that Pb contamination is mainly due to the waste discharge of abandoned coal and metal mines rather than industrial and airborne sources. Considering the proportion of metals bound to the exchangeable, carbonate and reducible fractions, the comparative mobility of metals is suggested to decrease in the order Mn > Pb > Zn > Ni > Fe  Cu.  相似文献   

14.
Lithium isotope signatures of whole rock pegmatite samples and mineral separates from the rare element-bearing Little Nahanni Pegmatite Group, NWT, and whole rock samples from nearby granitic intrusions were measured. Correlation of the Li isotopic values from the pegmatite dikes with whole rock trace element geochemistry, mineralogy and primary textural evidence reflect mechanisms of Li isotopic fractionation during pegmatite formation. The heavier δ7Li signatures within the broad range measured from whole rock LNPG samples (? 0.94‰ to + 11.36‰) are related to the consolidation of the final ~ 15% melt fraction of a volatile-rich peraluminous magma in the late stages of magmatic fractionation. Rock-forming minerals (quartz, albite, spodumene and mica) display δ7Li signatures that indicate consolidation of the dikes under variable, non-equilibrium conditions. Lithium isotope signatures of relatively cool, highly evolved peraluminous magmas reflect the build-up of fluxes (e.g., H2O and F) and provide a qualitative assessment of the state of mineral/melt chemical equilibrium.  相似文献   

15.
Serpentinite rocks, high in Mg and trace elements including Ni, Cr, Cd, Co, Cu, and Mn and low in nutrients such as Ca, K, and P, form serpentine soils with similar chemical properties resulting in chemically extreme environments for the biota that grow upon them. The impact of parent material on soil characteristics is most important in young soils, and therefore the incipient weathering of serpentinite rock likely has a strong effect on the development of serpentine soils and ecosystems. Additionally, porosity generation is a crucial process in converting rock into a soil that can support vegetation. Here, the important factors affecting the incipient weathering of serpentinite rock are examined at two sites in the Klamath Mountains, California. Serpentinite-derived soils and serpentinite rock cores were collected in depth profiles from each sampling location. Mineral dissolution in weathered serpentinite samples, determined by scanning electron microscopy, energy dispersive spectrometry, electron microprobe analyses, and synchrotron microXRD, is consistent with the order, from most weathered to least weathered: Fe-rich pyroxene > antigorite > Mg-rich lizardite > Al-rich lizardite. These results suggest that the initial porosity formation within serpentinite rock, impacting the formation of serpentine soil on which vegetation can exist, is strongly affected both by the presence of non-serpentine primary minerals as well as the composition of the serpentine minerals. In particular, the presence of ferrous Fe appears to contribute to greater dissolution, whereas the presence of Al within the parent rock appears to contribute to greater stability. Iron-oxidizing bacteria present at the soil–rock interface have been shown in previous studies to contribute to the transition from rock to soil, and soils and rock cores in this study were therefore tested for iron-oxidizing bacteria. The detection of biological iron oxidation in this study indicates that the early alteration of these Fe-rich minerals may be mediated by iron-oxidizing bacteria. These findings help provide insight into the incipient processes affecting serpentinite rock weathering, important to the development of extreme serpentine soils and the biota that grow on them.  相似文献   

16.
River water composition (major ion and 87Sr/86Sr ratio) was monitored on a monthly basis over a period of three years from a mountainous river (Nethravati River) of southwestern India. The total dissolved solid (TDS) concentration is relatively low (46 mg L−1) with silica being the dominant contributor. The basin is characterised by lower dissolved Sr concentration (avg. 150 nmol L−1), with radiogenic 87Sr/86Sr isotopic ratios (avg. 0.72041 at outlet). The composition of Sr and 87Sr/86Sr and their correlation with silicate derived cations in the river basin reveal that their dominant source is from the radiogenic silicate rock minerals. Their composition in the stream is controlled by a combination of physical and chemical weathering occurring in the basin. The molar ratio of SiO2/Ca and 87Sr/86Sr isotopic ratio show strong seasonal variation in the river water, i.e., low SiO2/Ca ratio with radiogenic isotopes during non-monsoon and higher SiO2/Ca with less radiogenic isotopes during monsoon season. Whereas, the seasonal variation of Rb/Sr ratio in the stream water is not significant suggesting that change in the mineral phase being involved in the weathering reaction could be unlikely for the observed molar SiO2/Ca and 87Sr/86Sr isotope variation in river water. Therefore, the shift in the stream water chemical composition could be attributed to contribution of ground water which is in contact with the bedrock (weathering front) during non-monsoon and weathering of secondary soil minerals in the regolith layer during monsoon. The secondary soil mineral weathering leads to limited silicate cation and enhanced silica fluxes in the Nethravati river basin.  相似文献   

17.
Toxic metalliferous mine-tailings pose a significant health risk to ecosystems and neighboring communities from wind and water dispersion of particulates containing high concentrations of toxic metal(loid)s (e.g., Pb, As, Zn). Tailings are particularly vulnerable to erosion before vegetative cover can be reestablished, i.e., decades or longer in semi-arid environments without intervention. Metal(loid) speciation, linked directly to bioaccessibility and lability, is controlled by mineral weathering and is a key consideration when assessing human and environmental health risks associated with mine sites. At the semi-arid Iron King Mine and Humboldt Smelter Superfund site in central Arizona, the mineral assemblage of the top 2 m of tailings has been previously characterized. A distinct redox gradient was observed in the top 0.5 m of the tailings and the mineral assemblage indicates progressive transformation of ferrous iron sulfides to ferrihydrite and gypsum, which, in turn weather to form schwertmannite and then jarosite accompanied by a progressive decrease in pH (7.3–2.3).Within the geochemical context of this reaction front, we examined enriched toxic metal(loid)s As, Pb, and Zn with surficial concentrations 41.1, 10.7, 39.3 mmol kg−1 (3080, 2200, and 2570 mg kg−1), respectively. The highest bulk concentrations of As and Zn occur at the redox boundary representing a 1.7 and 4.2-fold enrichment relative to surficial concentrations, respectively, indicating the translocation of toxic elements from the gossan zone to either the underlying redox boundary or the surface crust. Metal speciation was also examined as a function of depth using X-ray absorption spectroscopy (XAS). The deepest sample (180 cm) contains sulfides (e.g., pyrite, arsenopyrite, galena, and sphalerite). Samples from the redox transition zone (25–54 cm) contain a mixture of sulfides, carbonates (siderite, ankerite, cerrusite, and smithsonite) and metal(loid)s sorbed to neoformed secondary Fe phases, principally ferrihydrite. In surface samples (0–35 cm), metal(loid)s are found as sorbed species or incorporated into secondary Fe hydroxysulfate phases, such as schwertmannite and jarosites. Metal-bearing efflorescent salts (e.g., ZnSO4·nH2O) were detected in the surficial sample. Taken together, these data suggest the bioaccessibility and lability of metal(loid)s are altered by mineral weathering, which results in both the downward migration of metal(loid)s to the redox boundary, as well as the precipitation of metal salts at the surface.  相似文献   

18.
The basalt-hosted Wocan Hydrothermal Field (WHF), located on the NW slope of an axial volcanic ridge at a depth of ∼3000 m at 6°22′N on the slow-spreading Carlsberg Ridge, northwest Indian Ocean, was discovered in 2013 during Chinese DY28th cruise. Preliminary investigations show that the field consists of two hydrothermal sites: Wocan-1, which shows indications for recent high-temperature hydrothermal activity, is located near the peak of the axial volcanic ridge at a water depth of 2970–2990 m, and Wocan-2 site, located at a water depth of 3100 m, ∼1.7 km to the northwest of Wocan-1. The recovered hydrothermal precipitates can be classified into four groups: (i) Cu-rich chimneys; (ii) Cu-rich massive sulfides; (iii) Fe-rich massive sulfides; and (iv) silicified massive sulfides. We conducted mineral texture and assemblage observation and Laser-ablation ICP-MS analyses of the hydrothermal precipitates to study the mineralization processes. Our results show that there are distinct systematic trace element distributions throughout the different minerals in the four sample groups. In general, chalcopyrite from the group (i) is enriched in Pb, As, Mo, Ga, Ge, V, and Sb, metals that are commonly referred to as medium- to low-temperature elements. In contrast these elements are present in low contents in the chalcopyrite grains from other sample groups. Selenium, a typical high-temperature metal, is enriched in chalcopyrite from groups (ii) and (iv), whereas Ag and Sn are enriched only in some silicified massive sulfides. As with chalcopyrite, pyrite also shows distinct trace element associations in grains with different habitus. The low-temperature association of elements (Pb, Mo, Mn, U, Mg, Ag, and Tl) is typically present in colloform/framboidal pyrite, whereas the high-temperature association (Se, Co, and Bi) is enriched in euhedral pyrite. Sphalerite in the groups (i) and (iii) at Wocan-1 is characterized by high concentrations of Ga, Ge, Pb, Cd, As, and Sb, indicating that sphalerite in these sample groups likely precipitated at intermediate temperatures. Early bornite, which mainly occurs in the central part of the Cu-rich chimney, is typically enriched in Sn and In compared to the other minerals. In contrast, late bornite that likely formed during increasing interaction of hydrothermal fluids with cold, oxygenated seawater has low Sn and In, but significantly higher concentrations of Ag, Au, Mo and U. Digenite, also forming in the exterior parts of the samples during the late stages of hydrothermal fluid venting, is poor in most trace elements, except Ag and U. The notable Ag enrichment in the late-stage mineral assemblages at both Wocan-1 and Wocan-2 may therefore be related to lower temperatures and elevated pH. Our results indicate that Wocan-1 has experienced a cycle of heating with Cu-rich chimney growth and subsequent cooling, followed by late seafloor weathering, while Wocan-2 has seen intermediate- to high-temperature mineralization followed by intense silicification of sulfides. Seafloor weathering processes or mixing of hydrothermal fluids with seawater during the waning stages of hydrothermal fluid flow result in significant redistributions of trace elements in sulfide minerals.  相似文献   

19.
In the Urals, a wide range of well-preserved chimneys are found in VMS deposits, which are associated with ultramafic (Atlantic type: Dergamysh), mafic (Cyprus type: Buribay), bimodal mafic (Uralian type: Yubileynoye, Sultanovskoye, Yaman-Kasy, Molodezhnoye, Uzelga-4, Valentorskoye) and bimodal felsic (Kuroko or Baymak type: Oktyabrskoye, Tash-Tau, Uselga-1, Talgan, Alexandrinskoye) sequences. Chimneys have also been found in the Safyanovskoye deposit (Altay type) that is hosted by intercalated felsic lavas and carbonaceous shales. A combination of geological, mineralogical and trace element data provide a general outline for comparison between chimneys from the Urals deposits and modern vent sites. The chimneys from the Dergamysh deposit show a broad affinity with those from the Rainbow and other vent sites associated with serpentinites of the Mid-Atlantic Ridge. The chimneys from the Buribay deposit are similar to the black smokers of the EPR vent sites including the scarcity of rare minerals. The chimneys from the Urals type of the VMS deposits show some similarities with grey smokers from the Brother Volcano and PACMANUS sites. The chimneys from the Baymak type of the VMS deposits resemble grey and white smokers of the PACMANUS and grey smokers of the Suiyo vent sites. The chimneys from the Safyanovskoye deposit are similar to the black and clear smokers from the Okinawa Trough. Mineral assemblages are controlled by the combination of host rock composition and physico-chemical conditions of the ore-forming processes. Amount of colloform pyrite, isocubanite and pseudomorphic pyrite and marcasite after pyrrhotite decreases in the chimneys across the range from ultramafic and mafic to felsic-hosted deposits and is concomitant with increase in the contents of sphalerite, galena, bornite, fahlores, native gold and barite across this range. The chimneys from the Urals type contain abundant tellurides and sulfoarsenides, while these minerals are rare (except for hessite) in the Baymak type deposits. In the same range, the buffering capacity of host rocks decreases in contrast to the increase in ƒS2 and ƒO2. With the exception of the Safyanovskoye deposit, trace element assemblages in chalcopyrite vary to reflect the host rock: ultramafic (high Se, Sn, Co, Ni, Ag and Au)  mafic (high Co, Se, Mo and low Bi, Au and Pb)  bimodal mafic (high Te, Au, Ag, Bi, Pb, Co, moderate Se, and variable As and Sb)  bimodal felsic (high As, Sb, Mo, Pb, moderate Bi, and low Co, Te and Se). In sphalerite of the same range, the contents of Bi, Pb, Ag, Au and Sb increase versus Fe, Se and Сo. The variations in trace elements in colloform pyrite coincide with these changes. The specific mineral changes in the local ranges from Cu- to Zn-rich chimneys in each VMS deposit are similar to the general changes in the range of host rock classes of the deposits. However, the local T, ƒS2 and ƒO2 changes can broadly be interpreted in terms of contribution of variable oxygenated cold seawater to the subseafloor and seafloor hydrothermal processes.  相似文献   

20.
We conducted CO2–water–rock interaction experiments to elucidate the dissolution characteristics and geochemical trapping potential of three different altered andesitic to rhyolitic tuffaceous rocks (Tsugawa, Ushikiri and Daijima tuffaceous rock) relative to fresh mid-ocean ridge basalt. The experiments were performed under 1 MPa CO2 pressure to reproduce the water–rock–CO2 interactions in CO2 storage situations. Basalt showed high acid neutralization potential and rapid dissolution of silicate minerals. Two of the tuffaceous rocks (Ushikiri and Daijima) showed relatively high solubility trapping potential, mainly due to the dissolution of carbonate minerals in the andesitic Ushikiri tuffaceous rock and the ion-exchange reaction with zeolite minerals in the rhyolitic Daijima tuffaceous rock. The mineral trapping potential of the Ushikiri tuffaceous rock was found to be relatively high, due to the rapid dissolution of Mg- and Ca-bearing silicate minerals. Our experimental results suggest that regions of porous and andesitic tuffaceous rock hold global promise as CO2 storage sites.  相似文献   

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