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1.
Iron mobilisation from aquifer rocks in an important fractured aquifer system in South Africa is resulting in clogging of boreholes by Fe oxide minerals. Leach experiments using natural waters were conducted to determine the effects of redox conditions, pH lithology and presence of organic acids on the rate and extent of Fe dissolution from aquifer rocks, with the aim of clarifying the association of Fe clogging with geological formations that show Fe staining on weathering. The results indicate that the greatest amount of Fe (>30 mmol/kg rock) is leached from arenaceous rocks with low total Fe contents (49.0–75.0 mmol/kg) under anoxic conditions. Rocks with the highest Fe contents (>800 mmol/kg) generated low concentrations of Fe (<10 mmol/kg) even under favourable conditions of 0 mg/L DO and pH 3. The extent of Fe dissolution from the rocks was found to be most strongly dependent on the redox conditions, and the form of Fe present in the rock, with ascorbate-extracted amorphous Fe being the most mobile. The rate of dissolution is affected by pH and the presence of natural organic acids in the leachate. However, the effect of organic acids was only noticeable on arenaceous rocks.  相似文献   

2.
Previous research has shown that Cu and Fe isotopes are fractionated by dissolution and precipitation reactions driven by changing redox conditions. In this study, Cu isotope composition (65Cu/63Cu ratios) was studied in profiles through sulphide-bearing tailings at the former Cu mine at Laver and in a pilot-scale test cell at the Kristineberg mine, both in northern Sweden. The profile at Kristineberg was also analysed for Fe isotope composition (56Fe/54Fe ratios). At both sites sulphide oxidation resulted in an enrichment of the lighter Cu isotope in the oxidised zone of the tailings compared to the original isotope ratio, probably due to preferential losses of the heavier Cu isotope into the liquid phase during oxidation of sulphides. In a zone with secondary enrichment of Cu, located just below the oxidation front at Laver, δ65Cu (compared to ERM-AE633) was as low as −4.35 ± 0.02‰, which can be compared to the original value of 1.31 ± 0.03‰ in the unoxidised tailings. Precipitation of covellite in the secondary Cu enrichment zone explains this fractionation. The Fe isotopic composition in the Kristineberg profile is similar in the oxidised zone and in the unoxidised zone, with average δ56Fe values (relative to the IRMM-014) of −0.58 ± 0.06‰ and −0.49 ± 0.05‰, respectively. At the well-defined oxidation front, δ56Fe was less negative, −0.24 ± 0.01‰. Processes such as Fe(II)–Fe(III) equilibrium and precipitation of Fe-(oxy)hydroxides at the oxidation front are assumed to cause this Fe isotope fractionation. This field study provides additional support for the importance of redox processes for the isotopic composition of Cu and Fe in natural systems.  相似文献   

3.
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   

4.
Oxidizing conditions normally prevail in surface waters and near-surface groundwaters, but there is usually a change to reducing conditions in groundwater at greater depth. Dissolved O2 originally present is consumed through biogenic and inorganic reactions along the flow paths. Fracture minerals participate in these reactions and the fracture mineralogy and geochemistry can be used to trace the redox front. An important task in the safety assessment of a potential repository for the disposal of nuclear waste in crystalline bedrock, at an approximate depth of 500 m in Sweden, is to demonstrate that reducing conditions can be maintained for a long period of time. Oxygen may damage the Cu canisters that host nuclear waste; additionally, in the event of a canister failure, oxidizing conditions may increase the mobility of some radionuclides. The present study of the near-surface redox front is based on mineralogical (redox-sensitive minerals), geochemical (redox-sensitive elements) and U-series disequilibrium investigations of mineral coatings along open fractures. The fractures have been sampled along drill cores from closely spaced, 100 m deep boreholes, which were drilled during the site investigation work in the Laxemar area, south-eastern Sweden, carried out by the Swedish Nuclear Fuel and Waste Management Co. (SKB). The distribution of the redox-sensitive minerals pyrite and goethite in open fractures shows that the redox front (switch from mainly goethite to mainly pyrite in the fractures) generally occurs at about 15–20 m depth. Calcite leaching by recharging water is indicated in the upper 20–30 m and positive Ce-anomalies suggest oxidation of Ce down to 20 m depth. The U-series radionuclides show disequilibrium in most of the samples, indicating mobility of U during the last 1 Ma. In the upper 20 m, U is mainly removed (due to oxidation) or has experienced complex removal and/or deposition. At depths of 35–55 m, both deposition and removal of U are indicated. Below 55 m, recent deposition of U is generally indicated which suggests removal of U near surface (oxidation) and deposition of U below the redox front. Scattered goethite occurrences below the general redox front (down to ca 80 m) and signs of U removal at 35–55 m mostly correlate with sections of high transmissivity (and/or high fracture frequencies). This shows that highly transmissive fractures are generally required to allow oxygenated groundwaters at depth greater than ca 30 m. Removal of U (oxidation) below 55 m within the last 300 ka is not observed. Although penetration of glacial waters to great depths has been confirmed in the study area, their potential O2 load seems to have been reduced near the surface.  相似文献   

5.
The physicochemical processes that affect acid mine drainage (AMD) in unsaturated waste rock piles and the capabilities of small-scale laboratory experiments to predict AMD from waste rock are not well understood. An integrated laboratory and field study to measure and compare low sulfide waste rock and drainage characteristics at various scales has been initiated. This paper describes the design, construction and instrumentation of three field-scale experimental waste rock piles (test piles), and six active zone lysimeters at the Diavik diamond mine in the Northwest Territories, Canada. The test piles are comprised of granitic and sulfide-bearing metasedimentary waste rock excavated during open pit mining operations. One test pile contains waste rock with a target S content of <0.04 wt.% S; the second test pile contains waste rock with a target S content of >0.08 wt.% S; and the third test pile contains the higher sulfide waste rock (>0.08 wt.% S) and was re-sloped and capped with a low permeability till layer and a low sulfide waste rock cover. The first two test piles are approximately 15 m high with bases of 50 m by 60 m, and the re-sloped test pile has a larger base of 80 m by 125 m. Instrumentation was selected to measure matrix flow, geochemistry of pore water and drainage, gas-phase O2 concentration, temperature evolution, microbiological populations, waste rock permeability to air, and thermal conductivity, as well as to resolve mass and flow balances. Instrument locations were selected to characterize coupled physicochemical processes at multiple scales and the evolution of those processes over time. Instruments were installed at a density such that the number of instruments that survived construction (40% to >80% by instrument type) was sufficient to allow adequate characterization of the physicochemical processes occurring at various scales in the test piles.  相似文献   

6.
New fission track and Ar/Ar geochronological data provide time constraints on the exhumation history of the Himalayan nappes in the Mandi (Beas valley) – Tso Morari transect of the NW Indian Himalaya. Results from this and previous studies suggest that the SW-directed North Himalayan nappes were emplaced by detachment from the underthrusted upper Indian crust by 55 Ma and metamorphosed by ca. 48–40 Ma. The nappe stack was subsequently exhumed to shallow upper crustal depths (<10 km) by 40–30 Ma in the Tso Morari dome (northern section of the transect) and by 30–20 Ma close to frontal thrusts in the Baralacha La region. From the Oligocene to the present, exhumation continued slowly.Metamorphism started in the High Himalayan nappe prior to the Late Oligocene.High temperatures and anatexis of the subducting upper Indian crust engendered the buoyancy-driven ductile detachment and extrusion of the High Himalayan nappe in the zone of continental collision. Late extrusion of the High Himalayan nappe started about 26 Ma ago, accompanied by ductile extensional shearing in the Zanskar shear zone in its roof between 22 and 19 Ma concomitant with thrusting along the basal Main Central Thrust to the south. The northern part of the nappe was then rapidly exhumed to shallow depth (<10 km) between 20 and 6 Ma, while its southern front reached this depth at 10–5 Ma.  相似文献   

7.
《Applied Geochemistry》2004,19(11):1785-1800
Historical Au-ore exploitation at the Chéni mine in the Massif Central, France, generated 525,000 tonnes of finely ground mill tailings deposited in a heap that has spread with time into three settling basins. The tailings, which are rich in quartz (80%), mica and clay minerals (10% of illite, smectite, kaolinite and chlorite), feldspars (5%) but poor in carbonates (<1%), also contain sulphides (around 5%, mainly pyrite and arsenopyrite). Arsenic content of the tailings is around 6 g kg. This paper describes the geochemistry of drainage waters, with special attention paid to in situ values of the three major redox couples, namely Fe(II)/Fe(III), As(III)/As(V) and S(IV)/S(VI). The water samples range from acidic and oxidized (pH 2.9, Eh +700 mV) to moderate pH and weakly reducing (pH 7.6, Eh 15 mV). The waters are rich in SO4 and Ca and have variable As (0.05–95 mg L−1) and Fe concentrations (0.07–141 mg L−1). Reduced As(III) species predominate over As(V) species (As(III)/As(V) up to 21), whereas oxidized forms of Fe and S are favoured (Fe(II)/Fe(III) up to 0.5, and S(IV)/S(VI) up to 1).Thermodynamic calculations were performed with the PHREEQC and EQ3NR codes based on a revised As database to evaluate saturation indices (SI) of the waters in relation to the main minerals and define which redox couples control the redox state of the system. The important role of carbonates, though only present in small amounts, explains the acid buffering generated by the oxidation of sulphides for waters in the pH 7–7.5 range. Measured Eh appears to fall between the calculated Eh of the Fe(II)/Fe(III) couple and that of the As(III)/As(V) couple, illustrating redox disequilibrium.  相似文献   

8.
Three large-scale instrumented waste rock piles were constructed at the Diavik Diamond Mine in the Northwest Territories, Canada. These experimental waste rock piles (test piles) are 15 m high and are part of an integrated field and laboratory research program to characterize and compare low-sulfide waste rock and drainage at various scales. During test pile construction, samples of the <50 mm fraction of waste rock were collected from two types of waste rock that are segregated during mining operations based on S content. The samples were analyzed for S content and particle size distribution. One test pile contained waste rock with an average of 0.035 wt.% S in the <50 mm fraction, within the operational S target of <0.04 wt.% S for the lower S waste rock type. The second test pile contained waste rock with an average of 0.053 wt.% S in the <50 mm fraction, lower than the operational S target of >0.08 wt.% S for the higher S waste rock type. The third test pile has a low permeability till layer and a low sulfide waste rock thermal layer covering a core of waste rock with average 0.082 wt.% S in the <50 mm fraction, which is within the operational S target of >0.08 wt.% S for the higher S waste rock. Particle size distributions for the lower and higher S waste rock are similar, but the higher S waste rock has a higher proportion of fine-grained particles. Sulfur determinations for discrete particle sizes of the <50 mm fraction illustrate higher S concentrations in smaller particles for both the lower S waste rock and the higher S waste rock. Similarly, S concentrations calculated for the >10 m scale, from composite blast hole cuttings, are lower than those calculated for the <50 mm scale. Acid–base accounting using standard methods and site-specific mineralogical information was used to calculate the ratio of neutralization potential to acid generating potential. A comparison of calculation approaches to pH and alkalinity data from humidity cell and test pile effluent suggest that ratios are very sensitive to the calculation method. The preferred calculation method was selected by comparing calculation results to pH and alkalinity data from humidity cell effluent collected over 95 weeks and test pile effluent collected over five field seasons. The preferred acid–base accounting values were obtained by calculating the average neutralization potential divided by the average acid potential of a sample set. This approach indicates that waste rock with >0.05 wt.% S is of uncertain acid-generating potential and effluent data indicate this waste rock generates acidic effluent; whereas lower S waste rock does not produce acidic effluent, consistent with the acid–base accounting predictions.  相似文献   

9.
《Applied Geochemistry》2006,21(3):528-545
High mean As concentrations of up to 26.6 μmol/L (1990 μg/L) occur in ground water collected from a fractured-bedrock system composed of sulfidic schist with granitic to dioritic intrusions. Sulfides in the bedrock are the primary source of the As in the ground water, but the presence of arsenopyrite in rock core retrieved from a borehole with As concentrations in the ground water barely above the detection limit of 2.0 μmol/L, shows that there are complicating factors. Chemical analyses of water from 35 bedrock wells throughout a small watershed reveal spatial clustering of wells with high As concentrations. Stiff diagrams and box plots distinguish three distinct types; calcium-bicarbonate-dominated water with low As concentrations (CaHCO3 type), sodium-bicarbonate-dominated water with moderately high As concentrations (NaHCO3 type), and calcium-bicarbonate-dominated water with very high As concentrations (High-As type). It is proposed that differences in recharge area and ground-water evolution, and possible bedrock composition difference are responsible for the chemical distinctions within the watershed. Lack of correlation of As concentrations with pH indicates that desorption of As is an insignificant control on As concentration. Correlations of As concentrations with Fe and redox parameters indicates that reductive dissolution of Fe(III) oxyhydroxides may play a role in the occurrence of high As concentrations in the NaHCO3 and High-As type water. The oxidation of sulfide minerals occurs within the ground-water system and is ultimately responsible for the existence of As in the ground water, but there is no correlation between As and SO4 concentrations, probably due to precipitation of Fe(III) oxyhydroxides and adsorption of As under oxidizing conditions.  相似文献   

10.
Rapid weathering and erosion rates in mountainous tropical watersheds lead to highly variable soil and saprolite thicknesses which in turn impact nutrient fluxes and biological populations. In the Luquillo Mountains of Puerto Rico, a 5-m thick saprolite contains high microorganism densities at the surface and at depth overlying bedrock. We test the hypotheses that the organisms at depth are limited by the availability of two nutrients, P and Fe. Many tropical soils are P-limited, rather than N-limited, and dissolution of apatite is the dominant source of P. We document patterns of apatite weathering and of bioavailable Fe derived from the weathering of primary minerals hornblende and biotite in cores augered to 7.5 m on a ridgetop as compared to spheroidally weathering bedrock sampled in a nearby roadcut.Iron isotopic compositions of 0.5 N HCl extracts of soil and saprolite range from about δ56Fe = 0 to ? 0.1‰ throughout the saprolite except at the surface and at 5 m depth where δ56Fe = ? 0.26 to ? 0.64‰. The enrichment of light isotopes in HCl-extractable Fe in the soil and at the saprolite–bedrock interface is consistent with active Fe cycling and consistent with the locations of high cell densities and Fe(II)-oxidizing bacteria, identified previously. To evaluate the potential P-limitation of Fe-cycling bacteria in the profile, solid-state concentrations of P were measured as a function of depth in the soil, saprolite, and weathering bedrock. Weathering apatite crystals were examined in thin sections and an apatite dissolution rate of 6.8 × 10? 14 mol m? 2 s? 1 was calculated. While surface communities depend on recycled nutrients and atmospheric inputs, deep communities survive primarily on nutrients released by the weathering bedrock and thus are tightly coupled to processes related to saprolite formation including mineral weathering. While low available P may limit microbial activity within the middle saprolite, fluxes of P from apatite weathering should be sufficient to support robust growth of microorganisms in the deep saprolite.  相似文献   

11.
Upper-mantle xenoliths in Cenozoic basalts of northwestern Spitsbergen are rocks of peridotite (spinel lherzolites) and pyroxenite (amphibole-containing garnet and garnet-free clinopyroxenites, garnet clinopyroxenites, and garnet and garnet-free websterites) series. The upper-mantle section in the depth range 50–100 km is composed of spinel peridotites; at depths of 80–100 km pyroxenites (probably, dikes or sills) appear. The equilibrium conditions of parageneses are as follows: in the peridotites—730–1180 °C, 13–27 kbar, and oxygen fugacity of − 1.5 to + 0.3 log. un.; in the pyroxenites—1100–1310 °C, 22–33 kbar. The pyroxenite minerals have been found to contain exsolved structures, such as orthopyroxene lamellae in clinopyroxene and, vice versa, clinopyroxene lamella in orthopyroxene. The formation temperatures of unexsolved phases in orthopyroxene and clinopyroxene are nearly 100–150 °C higher than the temperatures of the lamellae–matrix equilibrium and the equilibrium of minerals in the rock. The normal distribution of cations in the spinel structure and the equilibrium distribution of Fe2 + between the M1 and M2 sublattices in the orthopyroxenes point to the high rate of xenolith ascent from the rock crystallization zone to the surface. All studied Spitsbergen rock-forming minerals from mantle xenoliths contain volatiles in their structure: OH−, crystal hydrate water H2Ocryst, and molecules with characteristic CH and CO groups. The first two components are predominant, and the total content of water (OH– + H2Ocryst) increases in the series olivine → garnet → orthopyroxene → clinopyroxene. The presence of these volatiles in the nominally anhydrous minerals (NAM) crystallized at high temperatures and pressures in the peridotites and pyroxenites testifies to the high strength of the volatile–mineral bond. The possibility of preservation of volatiles is confirmed by the results of comprehensive thermal and mass-spectral analyses of olivines and clinopyroxene, whose structures retain these components up to 1300 °C. The composition of hypothetic C–O–H fluid in equilibrium (in the presence of free carbon) with the underlying mantle rocks varies from aqueous (> 80% H2O) to aqueous–carbonic (~ 60% H2O). The fluid becomes essentially aqueous when the oxygen activity in the system decreases. However, there is no strict dependence of the redox conditions on the depth of formation of xenoliths.  相似文献   

12.
Authigenesis of iron-rich phosphate nodules occurs in iron-rich cold-seep sediments (MD052911 core) at Yung-An Ridge offshore southwestern Taiwan. Raman, FTIR, and quantitative X-ray energy-dispersive spectroscopic analyses indicate that the phosphate mineral is vivianite (or barićite) and shows Fe/Mg molar ratios spanning from ca. 0.6 to 4.0 and a general down core trend of increasing Fe/Mg ratios. The formation of vivianite is limited to a depth interval of 13–17 mbsf (meters below seafloor) and is most prominent at ∼16 mbsf in association with high dissolved iron concentrations and depleted dissolved sulfide below a peak sulfidization zone (enriched in mackinawite and greigite). Alternate growths of vivianite and iron monosulfides and compositional zoning with Mg enriched towards the peripheries of individual nodules occur in the transition from the zone of vivianite mineralization to the sulfidization zone. The crystallization of vivianite below the sulfidization front could have been favored by scavenging of downward diffusive dissolved sulfide from pore waters in the sulfidization zone. Alternate growths and overlapping of the zones of iron monosulfides and vivianite can be attributed to fluctuations of the sulfidization front and methane flux. The discovery of vivianite in the Yung-An Ridge sediments implies that authigenic vivianite can be an important sink for phosphorus burial in cold-seep sediments that have high reactive-iron contents and high sedimentation rates.  相似文献   

13.
Karstic bauxites in western Guangxi, China, comprise two subtypes: Permian bauxite and Quaternary bauxite. The Quaternary bauxite originated from the breaking up, rolling, and accumulating of Permian bauxite in karstic depressions in Quaternary. Various types of rare earth element (REE) minerals were discovered during the formation of the Permian and Quaternary bauxites from the Xinxu, Longhe, and Tianyang bauxite deposits in this study. Five types of REE minerals, including bastnäsite, parisite, cerianite, rhabdophane, and churchite, were identified. Bastnäsite and parisite are the most abundant, and they are widely developed in the Permian ore and also present in the Quaternary ore. Obvious variations in bastnäsite and parisite REE compositions were observed, which is ascribed to distinctions in the source materials in the primary weathering profile from different areas. The mode of occurrence of bastnäsite and parisite suggests they were mainly precipitated under alkaline and reducing conditions during the Permian bauxite-forming stage and underwent intensive corrosion in the Quaternary. Churchite was formed during the Permian weathering stage under acidic condition. Both cerianite and rhabdophane occur in fractures within the Permian bauxite ore, indicating that both formed during the Quaternary weathering stage. It is considered that the rhabdophane enriched in Ce have formed locally, in the process of that the Ce3 +, released from bastnäsite rapidly, entered the rhabdophane lattice before being oxidized to Ce4 +. Cerianite was mainly found in association with Mn–Al hydroxides, suggesting that the released Ce3 + was oxidized into Ce4 + and precipitated cerianite in fractures within the Permian bauxite ore. Mass balance equations reveal a depletion in nearly all REEs during the transformation from the Permian to the Quaternary bauxite ore, mainly caused by the dissolution of bastnäsite and parisite. The genesis of the REE minerals, together with the occurrence of other minerals, indicates that intensively acidic and oxidizing conditions developed before the formation of the Permian bauxite ore. Towards the end of the Permian, the conditions became reducing and alkaline, favorable for the large-scale bauxitization. The Quaternary bauxite-forming stage was characterized by variable pH and Eh conditions, with acidic (pH = 4–6) and oxidizing (Eh > 2) conditions at the surface of the exposed Permian bauxite ore.  相似文献   

14.
Subsurface redox fronts control the mobilization and fixation of many trace elements, including potential pollutants such as certain radionuclides. Any safety assessment for a deep geological repository for radioactive wastes needs to take into account adequately the long-term redox processes in the geosphere surrounding the repository. To build confidence in understanding these processes, a redox front in a reduced siliceous sedimentary rock distributed in an uplifting area in Japan has been studied in detail. Geochemical analyses show increased concentrations of Fe and trace elements, including rare earth elements (REEs), at the redox front, even though concentrations of reduced rock matrix constituents show little change. Detailed SEM observations revealed that fossilized microorganisms composed of amorphous granules made exclusively of Fe and Si occur in the rock’s pore space. Microbial 16S rDNA analysis suggests that there is presently a zonation of different bacterial groups within the redox band, and bacterial zonation played an important role in the concentration of Fe-oxyhydroxides at the redox front. These water–rock–microbe interactions can be considered analogous to the processes occurring in the redox fronts that would develop around geological repositories for radioactive waste. Once formed, the Fe-oxyhydroxides within such a front would be preserved even after reducing conditions resume following repository closure.  相似文献   

15.
The Damiao type iron deposit is hosted in a typical Proterozoic anorthosite complex in the northern North China Craton. The types of ores in Damiao mainly comprise massive Fe ores, massive Fe–P ores, and disseminated Fe and Fe–P ores. The disseminated Fe and Fe–P ores formed by fractional crystallization are generally hosted in oxide-apatite gabbronorite and account for 70% of the proven reserve of the Damiao type iron ore. The massive Fe and Fe–P ores account for 30% of the proven reserve of the Damiao type deposit iron ore and generally occur as irregular dykes or veins filling vertical fractures of the previously consolidated anorthosite, showing typical features of hydrothermal mineralization. The contact between the massive orebodies and wall rocks is sharp and straight. The anorthosite comprises white and dark varieties, with the former resulted by the alteration of the latter that occurs as relicts. Petrographic observation and electron microprobe analyses show abundant Fe–Ti oxide inclusions in plagioclase which impart the dark color to the rock. The similar spider diagram patterns between fresh and altered plagioclase and between dark- and white-colored anorthosite imply a genetic relationship between the dark and white types. During the alteration of anorthosite, CaO and MgO were slightly decreased, the SiO2, Al2O3 and Na2O were significantly increased, and the TFe2O3 and TiO2 were significantly decreased. The TFe2O3 and TiO2 in the dark-colored anorthosite have a range of 4.86–12.18 wt.% and 0.37–1.65 wt.%, respectively. However, The TFe2O3 and TiO2 in the white-colored anorthosite have a range of 1.67–3.1 wt.% and 0.14–0.31 wt.%, respectively. These features suggest that the alteration of the anorthosite led the Fe element by leaching from the dark-colored anorthosite at highly oxidized condition, and then precipitated within the fractures of the anorthosite, thus forming the massive Fe and Fe–P orebodies. Because the estimated amount of transported Fe is much more abundant than the proven ore reserve, we infer that there should be huge potential for prospecting Damiao type iron ores.  相似文献   

16.
Most of the hydrothermal uranium (U) deposits from the European Hercynian belt (EHB) are spatially associated with Carboniferous peraluminous leucogranites. In the southern part of the Armorican Massif (French part of the EHB), the Guérande peraluminous leucogranite was emplaced in an extensional deformation zone at ca. 310 Ma and is spatially associated with several U deposits and occurrences. The apical zone of the intrusion is structurally located below the Pen Ar Ran U deposit, a perigranitic vein-type deposit where mineralization occurs at the contact between black shales and Ordovician acid metavolcanics. In the Métairie-Neuve intragranitic deposit, uranium oxide-quartz veins crosscut the granite and a metasedimentary enclave.Airborne radiometric data and published trace element analyses on the Guérande leucogranite suggest significant uranium leaching at the apical zone of the intrusion. The primary U enrichment in the apical zone of the granite likely occurred during both fractional crystallization and the interaction with magmatic fluids. The low Th/U values (< 2) measured on the Guérande leucogranite likely favored the crystallization of magmatic uranium oxides. The oxygen isotope compositions of the Guérande leucogranite (δ18Owhole rock = 9.7–11.6‰ for deformed samples and δ18Owhole rock = 12.2–13.6‰ for other samples) indicate that the deformed facies of the apical zone underwent sub-solidus alteration at depth with oxidizing meteoric fluids. Fluid inclusion analyses on a quartz comb from a uranium oxide-quartz vein of the Pen Ar Ran deposit show evidence of low-salinity fluids (1–6 wt.% NaCl eq.), in good agreement with the contribution of meteoric fluids. Fluid trapping temperatures in the range of 250–350 °C suggest an elevated geothermal gradient, probably related to regional extension and the occurrence of magmatic activity in the environment close to the deposit at the time of its formation. U-Pb dating on uranium oxides from the Pen Ar Ran and Métairie-Neuve deposits reveals three different mineralizing events. The first event at 296.6 ± 2.6 Ma (Pen Ar Ran) is sub-synchronous with hydrothermal circulations and the emplacement of late leucogranitic dykes in the Guérande leucogranite. The two last mineralizing events occur at 286.6 ± 1.0 Ma (Métairie-Neuve) and 274.6 ± 0.9 Ma (Pen Ar Ran), respectively. Backscattered uranium oxide imaging combined with major elements and REE geochemistry suggest similar conditions of mineralization during the two Pen Ar Ran mineralizing events at ca. 300 Ma and ca. 275 Ma, arguing for different hydrothermal circulation phases in the granite and deposits. Apatite fission track dating reveals that the Guérande granite was still at depth and above 120 °C when these mineralizing events occurred, in agreement with the results obtained on fluid inclusions at Pen Ar Ran.Based on this comprehensive data set, we propose that the Guérande leucogranite is the main source for uranium in the Pen Ar Ran and Métairie-Neuve deposits. Sub-solidus alteration via surface-derived low-salinity oxidizing fluids likely promoted uranium leaching from magmatic uranium oxides within the leucogranite. The leached out uranium may then have been precipitated in the reducing environment represented by the surrounding black shales or graphitic quartzites. As similar mineralizing events occurred subsequently until ca. 275 Ma, meteoric oxidizing fluids likely percolated during the time when the Guérande leucogranite was still at depth. The age of the U mineralizing events in the Guérande region (300–275 Ma) is consistent with that obtained on other U deposits in the EHB and could suggest a similar mineralization condition, with long-term upper to middle crustal infiltration of meteoric fluids likely to have mobilized U from fertile peraluminous leucogranites during the Late Carboniferous to Permian crustal extension events.  相似文献   

17.
The relationship among subducted oxidized oceanic crust and oxidation state of the subarc mantle, and arc magmas is one of the important aspects to evaluate convergent margin tectonics. However details of the oxidized mass transferred from buried oceanic crust to the overlying subarc mantle wedge remain obscure. Here we investigate the Songduo eclogites from south Tibet formed by the subduction of the paleo-Tethyan oceanic crust, and identify an abrupt decrease in pyrope and increase in almandine contents from the mantle to rim of garnet grains. This is coupled with a decrease in the Fe3 + content of epidote and Fe3 +/(Fe2 ++ Fe3 +) ratios from garnet core to rim domains, as well as speciation of calcite, a new mineral phase, in the rock matrix. Minor sulfates occur only as inclusions in garnet core domains, whereas sulfides are confined to the matrix as an accessory mineral phase. Aegirine augite occurs as relics or inclusions in garnet and omphacite. These features clearly suggest that oxidized components, Fe3 + and S6 +, were reduced as Fe2 + and S2 −, respectively, at the subduction zone. Thermodynamic modeling in the P–T-log10fO2 space using updated Perplex_X programs further revealed that the Songduo eclogites experienced oxygen fugacity variation of up to 8 log10 units, with decreasing pressure. Petrological observations further suggest that the strong redox processes took place, after breaking of garnet, during the initial exhumation of the eclogites. CO2 and minor sulfur are subsequently transferred from the cold oceanic subduction zone to the overlying mantle wedge, partially released by arc volcanoes to atmosphere. Our study presents a case of C and S recycling between the Earth's exterior and interior.  相似文献   

18.
This study reports on the seepage of metals, metalloids and radionuclides from the Mary Kathleen uranium mill tailings repository. Since rehabilitation in the 1980s, the capped tailings have developed a stratified hydrochemistry, with acid (pH 3.7), saline, metal-rich (Fe, Mn, Ni, U ± As, Pb, Zn), oxygenated (1.05 mg L−1 DO), radioactive waters in the upper tailings pile and near-neutral pH (pH 7.57), metal-poor, reduced (0.08 mg L−1 DO) waters at depth. Seepage (∼0.5 L s−1) of acid (pH 5.5), metal-rich (Fe, Mn ± Ni, U, Zn), radioactive (U-235, U-238, Ra-226, Ra-228, Ac-227) waters occurs from the base of the tailings dam retaining wall into the former evaporation pond and local drainage system. Oxygenation of the seepage waters causes the precipitation of Fe and coprecipitation and adsorption of other metals (U, Y), metalloids (As), rare earth elements (Ce, La) and radionuclides (U-235, U-238). By contrast, alkalis and alkaline–earth elements (Ca, K, Mg, Na, Sr), Mn, sulfate and to some degree metals (U, Zn, Ni), rare earth elements (Ce, La) and radionuclides (U-235, U-238, Ra-226, Ra-228) remain in solution until pH neutralisation and evaporation lead to their precipitation in efflorescences and sulfate-rich evaporative sediments. While the release of contaminant loads from the waste repository through seepage is insignificant (e.g. ∼5 kg of U per year), surface waters downstream of the tailings impoundment possess TDS, U and SO4 concentrations that exceed Australian water quality guideline values in livestock drinking water. Thus, in areas with a semi-arid climate, even insignificant load releases of contaminants from capped tailings repositories can still cause the deterioration of water quality in ephemeral creek systems.  相似文献   

19.
The Prominent Hill deposit is a world-class iron oxide copper–gold (IOCG) deposit in South Australia, characterized by a high Cu/S ratio of the dominant Cu-(Fe) sulfides hosted by hematite breccias. It contains a total resource of 278 Mt of ore at 0.98% Cu and 0.75 g/t Au. Prominent Hill is one of several IOCG deposits and numerous prospects in the Olympic IOCG province that are temporally associated with the 1603–1575 Ma Gawler Range Volcanics, a large igneous province including co-magmatic granitoid intrusions of the Hiltaba Suite. Globally, IOCG deposits share many similar features in terms of their geological environment and mineral association. However, it is not yet clear whether sulfur and copper originate from the same source rocks and which hydrothermal redox processes created the characteristic iron oxide enrichment. Highly variable sulfur isotope compositions of sulfides and sulfates in IOCG deposits have previously been interpreted in terms of diverse sulfur sources that may include contributions from magmatic, sedimentary, seawater or evaporitic sulfur. In order to test these alternatives, we performed a detailed sulfur isotope study of Cu-(Fe) sulfides from Prominent Hill and IOCG prospects nearby. The Prominent Hill deposit shows a wide range in δ34SV-CDT between − 33.5‰ and 29.9‰ for Cu-(Fe) sulfides, and a narrower range of 4.3‰ to 15.8‰ for barite. Iron sulfides (pyrite, pyrrhotite) show a narrow range in sulfur isotope composition, whereas Cu-bearing sulfides show a much wider range, and more negative δ34SV-CDT values on average. We propose a two-stage sulfide mineralization model for the IOCG system in the Prominent Hill area, in which all hydrothermal sulfur is ultimately derived from a magmatic source that had a composition of 4.4 ± 2‰. The diversity in sulfur isotope composition can be produced by different fluid evolution pathways along reducing or oxidizing trajectories. A reduced sulfur evolution pathway is responsible for stage I mineralization, when intrusion-derived magmatic-hydrothermal fluids produced early pyrite and minor chalcopyrite at Prominent Hill, and iron ± copper sulfides in regional magnetite skarns and in some pervasively altered volcanic rocks of the Gawler Range Volcanics. Shallow-venting magmatic-hydrothermal fluids and subaerial volcanic gases that became completely oxidized by reaction with atmospheric oxygen produced sulfate and sulfuric acid with a sulfur isotope composition equal to their magmatic source. This highly oxidized ore fluid probably consisted dominantly of water from the hydrosphere, but contained magmatic solute components, notably sulfate, acidity and Cu. Sulfate reduction produced hydrothermal Cu sulfides with a wide range in sulfur isotope compositions from very negative to moderately positive values. Partial reaction of the Cu-rich stage II fluid with earlier stage I sulfides resulted in mixing of sulfur derived from sulfate reduction and from sulfides deposited during stage I. Modeling of the sulfur isotope fractionation processes in response to reducing and oxidizing pathways demonstrates that the entire spectrum of sulfur isotope data from stage I and stage II mineralization can be explained with a single, ultimately magmatic sulfur source. Such a magmatic sulfur source is also adequate to explain the complete spectrum of sulfur isotope data of other IOCG prospects and deposits in the Olympic province, including Olympic Dam. The results of our study challenge the conventional model that suggests the requirement of multiple and compositionally diverse sulfur sources in hematite-breccia hosted IOCG style mineralization.  相似文献   

20.
Three large-scale experimental waste rock piles (test piles) were constructed and instrumented at the Diavik Diamond Mine in the Northwest Territories, Canada, as part of an integrated field and laboratory study to measure and compare physical and geochemical characteristics of experimental, low sulfide waste rock piles at various scales. This paper describes the geochemical response during the first season from a test pile containing 0.053 wt.% S. Bulk drainage chemistry was measured at two sampling points for pH, Eh, alkalinity, dissolved cations and anions, and nutrients. The geochemical equilibrium model MINTEQA2 was used to interpret potential mineral solubility controls on water chemistry. The geochemical response characterizes the initial flushing response of blasting residues and oxidation products derived from sulfides in waste rock exposed to the atmosphere for less than 1 year. Sulfate concentrations reached 2000 mg L−1 when ambient temperatures were >10 °C, and decreased as ambient temperatures declined to <0 °C. The pH decreased to <5, concomitant with an alkalinity minimum of <1 mg L−1 (as total CaCO3), suggesting all available alkalinity is consumed by acid-neutralizing reactions. Concentrations of Al and Fe were <0.36 and <0.11 mg L−1, respectively. Trends of pH and alkalinity and the calculated saturation indices for Al and Fe (oxy)hydroxides suggest that dissolution of Al and Fe (oxy)hydroxide phases buffers the pH. The effluent water showed increased concentrations of dissolved Mn (<13 mg L−1), Ni (<7.0 mg L−1), Co (<1.5 mg L−1), Zn (<0.5 mg L−1), Cd (<0.008 mg L−1) and Cu (<0.05 mg L−1) as ambient temperatures increased. Manganese is released by aluminosilicate weathering, Ni and Co by pyrrhotite [Fe1−xS] oxidation, Zn and Cd by sphalerite oxidation, and Cu by chalcopyrite [CuFeS2] oxidation. No dissolved metals appear to have discrete secondary mineral controls. Changes in SO4, pH and metal concentrations indicate sulfide oxidation is occurring and effluent concentrations are influenced by ambient temperatures and, possibly, increasing flow path lengths that transport reaction products from previously unflushed waste rock.  相似文献   

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