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1.
《Applied Geochemistry》2006,21(3):476-491
Many mining-impacted streams in western Montana with pH near or above neutrality display large (up to 500%) diel cycles in dissolved Zn concentrations. The streams in question typically contain boulders coated with a thin biofilm, as well as black mineral crusts composed of hydrous Mn–Zn oxides. Laboratory mesocosm experiments simulating diel behavior in High Ore Creek (one of the Montana streams with particularly high Zn concentrations) show that the Zn cycles are not caused by 24-h changes in streamflow or hyporheic exchange, but rather to reversible in-stream processes that are driven by the solar cycle and its attendant influence on pH and water temperature (T). Laboratory experiments using natural Mn–Zn precipitates from the creek show that the mobilities of Zn and Mn increase nearly an order of magnitude for each unit decrease in pH, and decrease 2.4-fold for an increase in T from 5 to 20 °C. The response of dissolved metal concentration to small changes in either pH or T was rapid and reversible, and dissolved Zn concentrations were roughly an order of magnitude higher than Mn. These observations are best explained by sorption of Zn2+ and Mn2+ onto the secondary Mn–Zn oxide surfaces. From the T-dependence of residual metal concentrations in solution, approximate adsorption enthalpies of +50 kJ/mol (Zn) and +46 kJ/mol (Mn) were obtained, which are within the range of enthalpy values reported in the literature for sorption of divalent metal cations onto hydrous metal oxides. Using the derived pH- and T-dependencies from the experiments, good agreement is shown between predicted and observed diel Zn cycles for several historical data sets collected from High Ore Creek. 相似文献
2.
《Applied Geochemistry》2005,20(8):1445-1460
Changes in precipitate mineralogy, morphology, and major and trace element concentrations and associations throughout 5 coal mine drainage (CMD) remediation systems treating discharges of varying chemistries were investigated in order to determine the factors that influence the characteristics of precipitates formed in passive systems. The 5 passive treatment systems sampled in this study are located in the bituminous coal fields of western Pennsylvania and northern Maryland, and treat discharges from Pennsylvanian age coals. The precipitates are dominantly (>70%) goethite. Crystallinity varies throughout an individual system, and lower crystallinity is associated with enhanced sorption of trace metals. Degree of crystallinity (and subsequently morphology and trace metal associations) is a function of the treatment system and how rapidly Fe(II) is oxidized, forms precipitates, aggregates and settles. Precipitates formed earlier in the passive treatment systems tend to have the highest crystallinity and the lowest concentrations of trace metal cations. High surface area and cation vacancies within the goethite structure enable sorption and incorporation of metals from coal mine drainage-polluted waters. Sorption affinities follow the order of Zn > Co ≈ Ni > Mn. Cobalt and Ni are preferentially sorbed to Mn oxide phases when these phases are present. As pH increases in the individual CMD treatment systems toward the pHpzc of goethite, As sorption decreases and transition metal (Co, Mn, Ni and Zn) sorption increases. Sulfate, Na and Fe(II) concentrations may all influence the sorption of trace metals to the Fe hydroxide surface. Results of this study have implications not only for solids disposal and resource recovery but also for the optimization of passive CMD treatment systems. 相似文献
3.
《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
4.
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
5.
《Applied Geochemistry》2006,21(8):1301-1321
Low-quality pore waters containing high concentrations of dissolved H+, SO4, and metals have been generated in the East Tailings Management Area at Lynn Lake, Manitoba, as a result of sulfide-mineral oxidation. To assess the abundance, distribution, and solid-phase associations of S, Fe, and trace metals, the tailings pore water was analyzed, and investigations of the geochemical and mineralogical characteristics of the tailings solids were completed. The results were used to delineate the mechanisms that control acid neutralization, metal release, and metal attenuation. Migration of the low-pH conditions through the vadose zone is limited by acid-neutralization reactions, resulting in the development of distinct pore-water pH zones at depth; the neutralization reactions involve carbonate (pH ⩾ 5.7), Al-hydroxide (pH ⩾ 4.0), and aluminosilicate solids. As the zone of low-pH pore water expands, the pH will then be primarily controlled by less soluble solids, such as Fe(III) oxyhydroxides (pH < 3.5) and the relatively more recalcitrant aluminosilicates (pH ⩾ 1.3). Precipitation/dissolution reactions involving secondary Fe(III) oxyhydroxides and hydroxysulfates control the concentrations of dissolved Fe(III). Concentrations of dissolved SO4 are principally controlled by the formation of gypsum and jarosite. Geochemical extractions indicate that the solid-phase concentrations of Ni, Co, and Zn are associated predominantly with reducible and acid-soluble fractions. The concentrations of dissolved trace metals are therefore primarily controlled by adsorption/complexation and (or) co-precipitation/dissolution reactions involving secondary Fe(III) oxyhydroxide and hydroxysulfate minerals. Concentrations of dissolved metals with relatively low mobility, such as Cu, are also controlled by the precipitation of discrete minerals. Because the major proportion of metals is sequestered through adsorption and (or) co-precipitation, the metals are susceptible to remobilization if low-pH or reducing conditions develop within the tailings. 相似文献
6.
Remediation of 56 ML of acidic, contaminant-laden Baal Gammon mine pit water was undertaken using in situ hydrotalcite formation. The pit water composition was modified via the addition of MgCl2·6H2O to form a 2.5:1 M2+:M3+ metal ion ratio followed by the addition of NaOH to increase the pH 10 to induce spontaneous hydrotalcite precipitation. As a result of the in situ hydrotalcite precipitation a broad spectrum of elements of environmental concern including Al, Cd, Co, Cr, Cu, Fe, In, Mn, Mo, Ni, V and Zn were removed from solution. Significantly, an ore grade hydrotalcite precipitate containing Cu (8.0 ± 1.0%) and Zn (3.9 ± 0.5%) was produced directly from the mine pit water column allowing for potential recovery of valuable metals to offset remediation costs. The final water quality produced after in situ remediation was of a simple Na–Cl–SO4 type. 相似文献
7.
Uranium(VI) sorption onto kaolinite was investigated as a function of pH (3–12), sorbate/sorbent ratio (1 × 10?6–1 × 10?4 M U(VI) with 2 g/L kaolinite), ionic strength (0.001–0.1 M NaNO3), and pCO2 (0–5%) in the presence or absence of 1 × 10?2–1 × 10?4 M citric acid, 1 × 10?2–1 × 10?4 M EDTA, and 10 or 20 mg/L fulvic acid. Control experiments without-solids, containing 1 × 10?6–1 × 10?4 M U(VI) in 0.01 M NaNO3 were used to evaluate sorption to the container wall and precipitation of U phases as a function of pH. Control experiments demonstrate significant loss (up to 100%) of U from solution. Although some loss, particularly in 1 × 10?5 and 1 × 10?4 M U experiments, is expected due to precipitation of schoepite, adsorption on the container walls is significant, particularly in 1 × 10?6 M U experiments. In the absence of ligands, U(VI) sorption on kaolinite increases from pH ～3 to 7 and decreases from pH ～7.5 to 12. Increasing ionic strength from 0.001 to 0.1 M produces only a slight decrease in U(VI) sorption at pH < 7, whereas 10% pCO2 greatly diminishes U(VI) sorption between pH ～5.5 and 11. Addition of fulvic acid produces a small increase in U(VI) sorption at pH < 5; in contrast, between pH 5 and 10 fulvic acid, citric acid, and EDTA all decrease U(VI) sorption. This suggests that fulvic acid enhances U(VI) sorption slightly via formation of ternary ligand bridges at low pH, whereas EDTA and citric acid do not form ternary surface complexes with the U(VI), and that all three ligands, as well as carbonate, form aqueous uranyl complexes that keep U(VI) in solution at higher pH. 相似文献
8.
《Applied Geochemistry》2005,20(5):973-987
Due to liming of acid mine drainage, a calcite–gypsum sludge with high concentrations of Zn (24,400 ± 6900 μg g−1), Cu (2840 ± 680 μg g−1) and Cd (59 ± 20 μg g−1) has formed in a flooded tailings impoundment at the Kristineberg mine site. The potential metal release from the sludge during resuspension events and in a long-term perspective was investigated by performing a shake flask test and sequential extraction of the sludge. The sequentially extracted carbonate and oxide fractions together contained ⩾97% of the total amount of Cd, Co, Cu, Ni, Pb and Zn in the sludge. The association of these metals with carbonates and oxides appears to result from sorption and/or coprecipitation reactions at the surfaces of calcite and Fe, Al and Mn oxyhydroxides forming in the impoundment. If stream water is diverted into the flooded impoundment, dissolution of calcite, gypsum and presumably also Al oxyhydroxides can be expected during resuspension events. In the shake flask test (performed at a pH of 7–9), remobilisation of Zn, Cu, Cd and Co from the sludge resulted in dissolved concentrations of these metals that were significantly lower than those predicted to result from dissolution of the carbonate fraction of the sludge. This may suggest that cationic Zn, Cu, Cd and Co remobilised from dissolving calcite, gypsum and Al oxyhydroxides were readsorbed onto Fe oxyhydroxides remaining stable under oxic conditions. In a long-term perspective (≳102 a), ⩾97% of the Cd, Co, Cu, Ni, Pb and Zn content of the sludge potentially is available for release by dissolution of calcite and reductive dissolution of Fe oxyhydroxides if the sludge is subject to a soil environment with lower dissolved Ca concentrations, pH and redox than in the impoundment. 相似文献
9.
《Applied Geochemistry》2005,20(1):193-205
Sorption and precipitation of Co(II) in simplified model systems related to the Hanford site high-level nuclear waste tank leakage were investigated through solution studies, geochemical modeling, and X-ray absorption fine structure (XAFS) spectroscopy. Studies of Co(II) sorption to pristine Hanford sediments (ERDF and Sub), which consist predominantly of quartz, plagioclase, and alkali feldspar, show an adsorption edge centered at pH ≈ 8.0 for both sediments studied, with sorption >99% above pH ≈ 9.0. Aqueous SiO2 resulting from dissolution of the sediments increased in concentration with increasing pH, though the systems remained undersaturated with respect to quartz. XAFS studies of Co(II) sorption to both sediment samples reveal the oxidation of Co(II) to Co(III), likely by dissolved O2, although this oxidation was incomplete in the Sub sediment samples. The authors propose that Fe(II) species, either in aqueous solution or at mineral surfaces, partially inhibited Co(II) oxidation in the Sub sediment samples, as these sediments contain significantly higher quantities of Fe(II)-bearing minerals which likely partially dissolved under the high-pH solution conditions. In alkaline solutions, Al precipitated as bayerite, gibbsite, or a mixture of the two at pH > 7; an amorphous gel formed at pH values less than 7. Aqueous Co concentrations were well below the solubility of known Co-bearing phases at low pH, suggesting that Co was removed from solution through an adsorption mechanism. At higher pH values, Co concentrations closely matched the solubility of a Co-bearing hydrotalcite-like solid. XAFS spectra of Co(II) sorbed to Al-hydroxide precipitates are similar to previously reported spectra for such hydrotalcite-like phases. The precipitation processes observed in this study can significantly reduce the environmental hazard posed by 60Co in the environment. 相似文献
10.
The application of As-based herbicides at several industrial sites has resulted in numerous localized areas of As-contaminated soil. In this study, an As-contaminated soil (As = 278 mg/kg) collected from an industrial site located in the southeastern USA was subjected to inorganic phosphate (Pi) treatments. Although Pi treatments have been previously used for flushing As from contaminated soils, in this study, contaminated soil was amended with Pi to study the possible immobilization of As through a co-precipitation mechanism. Specifically, the Pi amendment was aimed at simultaneous flushing of As from the soil with orthophosphoric acid and co-precipitating it as Ca–phosphate–arsenate phases. Bench-scale Pi treatment experiments were performed at different pH conditions, with and without the addition of Ca. Sorption of Pi on BH soil in the presence or absence of additional Ca was determined, along with the associated mobilization of As from the soil. A significant amount of the HNO3-digestible As (up to 55% at pH 4, 10–15% at pH 8, and ∼30% at pH 11) was released from the contaminated soil during the Pi sorption experiments. This increased mobility of As after the addition of Pi resulted from the competitive desorption of As from the soil. Although Pi sorption at high pH (>8) was largely controlled by precipitation, As did not co-precipitate with Pi. Aqueous geochemical modeling indicated that the lack of As co-precipitation during Pi-only treatment primarily resulted from the deficiency of Ca in the system. When additional Ca (16.9 mmol) was supplied along with Pi (3.38 mmol), the mobility of As decreased significantly at circum-neutral to high solution pH. Geochemical modeling suggested that the leachable As in the soil was potentially precipitated as As-bearing Ca–Pi phases. X-ray diffraction analysis of precipitates separated from the treated soil and from the synthetic leachate confirmed that the formation of a poorly crystalline carbonate apatite phase occurred as a consequence of the treatment. The results of this study support the potential application of Ca–Pi treatment for remediation of As-contaminated soil at environmentally relevant pH conditions. 相似文献
11.
《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
12.
The historical (1932–1971) Bralorne mine produced over 87 million grams of Au from an archetypal orogenic lode gold deposit in southwest British Columbia. High concentrations of As in mine drainage, however, represent an on-going environmental concern prompting a detailed study of effluent chemistry. The discharge rate at the mine portal was monitored continuously over a fourteen-month period during which effluent samples were collected on a quasi-weekly basis. Water samples were also collected on synoptic surveys of the adit between the portal and the main source of flow in the flooded workings. Total concentrations of As in the mildly alkaline (pH = 8.7) portal drainage average 3034 μg/L whereas at the source they average 5898 μg/L. As emergent waters from the flooded workings flow toward the portal, their dissolved oxygen content and pH increase from 0 to 10 mg/L and from 7.7 to 9, respectively. Near the emergence point, dissolved Fe precipitates rapidly, sorbing both As(III) and As(V). With increasing distance from the emergence point, dissolved As(III) concentrations drop to detection limits through sorption on hydrous ferric oxide and through oxidation to As(V). Concentrations of dissolved As(V), on the other hand, increase and stabilize, reflecting lower sorption at higher pH and the lack of available sorbent. Nonetheless, based on synoptic surveys, approximately 35% of the source As load is sequestered in the adit resulting in As sediment concentrations averaging 8.5 wt%. The remaining average As load of 1.34 kg/d is discharged from the portal. Partitioning of As(V) between dissolved and particulate phases in portal effluent is characterized by a sorption density of 0.37 mol As (mol Fe)−1 and by a distribution coefficient (Kd) of 130 L/g HFO. The relatively high sorption density may reflect co-precipitation of As with Fe oxyhydroxides rather than a purely adsorption-controlled process. Results of this study show that the As self-mitigating capacity of drainage from orogenic lode gold deposits may be poor in high-pH and Fe-limited settings. 相似文献
13.
The partitioning of trace metal(oid)s between colloidal and “truly” dissolved fractions in sediment pore waters is often overlooked due to the analytical challenge; indeed, only small volumes are available and filtration membranes are rapidly clogged. Moreover, metal(oid)s are subject to co-precipitate with Fe. In this study, tangential flow filtration (TFF) was assessed for the fractionation of Fe, Mn, Cu, As, Co, Ni, Zn and Cd in sediment pore waters with a 5 kDa cut-off size membrane. Five natural sediments were collected and used for different tests. Results on blank samples showed that this technique was appropriate for Fe, Mn, Co, Zn, As and Cd. Although the applied concentration factors (CF) were low (<7.4) due to the small available volume of pore waters (50 mL), it was shown that colloidal concentrations obtained from the TFF procedure were similar whatever the applied concentration factor. The mass balance approach showed satisfying results (100 ± 25%) for Mn, Co, Zn and As. Mass balances were higher than 130% and highly variable for Cd, Ni and Cu. For Fe, mass balance was reproducible but low (71 ± 10%), probably due to sorption of positively charged Fe oxides on the membrane. Applying this method to five contrasting metal(oid)-contaminated sediments, it was shown that Mn, As, Co and Fe were mainly present in the “truly” dissolved phase (<5 kDa). This technique is a necessary step to assess sediment toxicity and bioavailability of metal(oid)s and could be of great interest for emergent pollutants such as nanometals. 相似文献
14.
Contaminated drainage related to the leaching of soluble metals under near-neutral conditions, known as contaminated neutral drainage (CND), may arise when metal species are soluble at neutral pH. Such a phenomenon has been sporadically observed in effluent from the Tio mine waste-rock pile in Quebec, Canada, particularly from older sections of the pile, where Ni concentrations are increasing with time. It has been postulated that Ni is retained within the fresh waste rock as sorbed species, but as the rock ages, sorption sites become saturated and more Ni is released to the effluent. A field test program was initiated to evaluate the geochemical behavior of the waste rock. This paper presents a numerical analysis of CND generation from waste-rock field test cells including water flow and multi-component transport with geochemical reactions (e.g. sulfide oxidation, pH neutralization, and Ni sorption), using the code MIN3P. The model was able to represent the delay before Ni is seen in the effluent, as caused by sorption of Ni onto Fe-oxide particles. Once the sorption sites are saturated, the model allows Ni release into the effluent by millerite dissolution, expressed by the shrinking core model. A sensitivity analysis indicated that sorption parameters significantly affected the simulated results, so their selection should be based on sound independent field or experimental data. 相似文献
15.
The Weilasituo and Bairendaba Zn–Pb–Ag–Cu–(Sn–W) sulphide deposits are located in the southern part of Great Xing'an Range of Inner Mongolia in China. The deposits are located at shallow depths in the newly discovered Weilasituo porphyry hosting Sn–W–Rb mineralization. The mineralization at Weilasituo and Bairendaba consist of zoned massive sulphide veins within fractures cutting the Xilinhot Metamorphic Complex and quartz diorite. The Weilasituo deposit gradually zones from the Cu-rich Zn–Cu sulphide mineralization in the west to Zn-rich Zn–Cu sulphide mineralization in the east. The Bairendaba deposit has a Cu-bearing and Zn-rich core through a transitional zone devoid of copper to an outer zone of Zn–Pb–Ag mineralization. Three main veins contain more than 50 wt.% of the contained metal in the two deposits with their metal ratios displaying a systematic and gradual increase in Zn/Cu, Pb/Zn and Ag/Zn ratios from the western part of Weilasituo to the eastern part of Bairendaba.Three stages of vein-type mineralization are recognized. Early, sub-economic mineralization consists of a variable proportion of euhedral arsenopyrite, pyrite, quartz, and rare wolframite, scheelite, cassiterite, magnetite and cobaltite. This was succeeded by main stage mineralization with economic concentration of zoned Cu, Zn, Pb and Ag sulphide minerals along strike within the veins. The zones consist of the assemblages: (1) pyrrhotite–Fe-rich sphalerite–chalcopyrite(–quartz–fluorite) at west Weilasituo; (2) pyrrhotite–Fe-rich sphalerite–chalcopyrite(–galena–tetrahedrite–quartz–fluorite) at east Weilasituo; (3) pyrrhotite–Fe-rich sphalerite–chalcopyrite(–galena–tetrahedrite–quartz–fluorite) in the centre of Bairendaba; (4) pyrrhotite–Fe-rich sphalerite–galena(–chalcopyrite–tetrahedrite–quartz–fluorite) in the transition zone of Bairendaba; and (5) pyrrhotite–Fe-rich sphalerite–galena–tetrahedrite(–chalcopyrite–falkmanite–argentite–pyrargyrite–quartz–fluorite) in the outer zone at Bairendaba. Post-main ore stage is devoid of sulphides and characterized overprinting of fluorite, sericite, chlorite, illite, kaolinite and calcite.Zircon SHRIMP U–Pb dating, Zircon LA–ICP–MS U–Pb dating, molybdenite Re–Os isochron dating, and muscovite Ar–Ar dating indicate the Beidashan granitic batholith was intruded at 140 ± 3 Ma (MSWD = 3.3), the porphyritic monzogranite from marginal facies of the Beidashan batholith was intruded at 139 ± 2 Ma (MSWD = 0.75), the mineralized quartz porphyry was intruded at 135 ± 2 Ma (MSWD = 0.91), the greisen mineralization occurred at 135 ± 11 Ma (MSWD = 7.2), and the post-main ore stage muscovite deposited at 129.5 ± 0.9 Ma. The new geochronology data show the porphyry Sn–W–Rb and vein-type sulphide mineralization are contemporaneous with granitic magmatism in the region.The metal zonation at the Weilasituo and Bairendaba deposits is a result of progressive metal deposition. This was during the evolution of a metal-bearing fluid along the strike of the veins and during the main stage of ore formation at the upper part of the deep-seated porphyry Sn–W–Rb system. This progressive zonation indicates that the deposits represent end-numbers formed from one ore-forming fluid, which moved from west to east from the porphyry. The metal zonation patterns of the major veins are consistent with metal-bearing fluid entering the system with the precipitation of chalcopyrite proximally and sphalerite, galena and Ag-bearing minerals more distally. We show that the mechanism of metal deposition is therefore controlled by thermodynamic conditions resulting in the progressive separation of sulphides from the metal-bearing fluid. The temperature gradient between the inflow zone and the outflow zone appears to be one of the key parameters controlling the formation of the metal zonation pattern. The sulphide precipitation sequence is consistent with a low fS2 and low fO2 state of the acidic metal-bearing fluid. The metal zonation pattern provides helpful clues from which it is possible to establish the nature of fluid migration and metal deposition models to locate a possible porphyry mineralization at depth in the Great Xing'an Range, which is consistent with the geology of the newly discovered porphyry Sn–W–Rb system. 相似文献
16.
Pristine diorite drill cores, obtained from the Äspö Hard Rock Laboratory (HRL, Sweden), were used to study the retention properties of fresh, anoxic crystalline rock material towards the redox-sensitive uranium. Batch sorption experiments and spectroscopic methods were applied for this study. The impact of various parameters, such as solid-to-liquid ratio (2–200 g/L), grain size (0.063–0.2 mm, 0.5–1 mm, 1–2 mm), temperature (room temperature and 10 °C), contact time (5–108 days), initial U(VI) concentration (3 × 10−9 to 6 × 10−5 M), and background electrolyte (synthetic Äspö groundwater and 0.1 M NaClO4) on the U(VI) sorption onto anoxic diorite was studied under anoxic conditions (N2). Comparatively, U(VI) sorption onto oxidized diorite material was studied under ambient atmosphere (pCO2 = 10−3.5 atm). Conventional distribution coefficients, Kd, and surface area normalized distribution coefficients, Ka, were determined. The Kd value for the U(VI) sorption onto anoxic diorite in synthetic Äspö groundwater under anoxic conditions by investigating the sorption isotherm amounts to 3.8 ± 0.6 L/kg which corresponds to Ka = 0.0030 ± 0.0005 cm (grain size 1–2 mm). This indicates a weak U sorption onto diorite which can be attributed to the occurrence of the neutral complex Ca2UO2(CO3)3(aq) in solution. This complex was verified as predominating U species in synthetic Äspö groundwater by time-resolved laser-induced fluorescence spectroscopy (TRLFS). Compared to U sorption at room temperature under anoxic conditions, U sorption is further reduced at decreased temperature (10 °C) and under ambient atmosphere. The U species in aqueous solution as well as sorbed on diorite were studied by in situ time-resolved attenuated total reflection Fourier-transform infrared (ATR FT-IR) spectroscopy. A predominant sorbing species containing a UO2(CO3)34− moiety was identified. The extent of U sorption onto diorite was found to depend more on the low sorption affinity of the Ca2UO2(CO3)3(aq) complex than on reduction processes of uranium. 相似文献
17.
We report the presence of greenockite from the chromite–PGE–base metal sulfide association in the Bangur Gabbro, Baula-Nuasahi mafic–ultramafic complex. The CdS phase occurs, sans any precursor Cd-bearing phase, as minute grains within siderite micro-veins in close proximity to chlorite in the chalcopyrite + pyrrhotite + pentlandite + violarite assemblage. Using various calibrations, chlorite compositions yielded temperature ranges of 245 to 325 °C. The associated siderite might have formed at or little below the above temperature. Electron probe micro-analyses (EPMA) of greenockite reveal small amounts of Fe (1.01–1.61 wt.%), Zn (1.89–4.54 wt.%), and substitution of Zn for Cd. Laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis of chalcopyrite nearer to and away from siderite micro-veins that host greenockite confirms maximum Cd concentrations of 78 and 144 ppm, respectively, entailing possible derivation of Cd from chalcopyrite. We propose the transport of Cd as bisulfide complex in a low temperature alkaline and reducing fluid and the simultaneous precipitation of greenockite and siderite by reaction with Fe-rich minerals, aided by decrease in pH and/or increase in fO2. 相似文献
18.
Toxic metal(loid) speciation during weathering of iron sulfide mine tailings under semi-arid climate
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
19.
《Applied Geochemistry》2006,21(7):1135-1151
Trace metal adsorption to suspended particulate matter (SPM) influences bioavailability and toxicity of trace metals in natural waters. For highly contaminated urban catchments in the greater Auckland (New Zealand) area, trace metal adsorption to SPM was assessed and compared to similar data from non-urban catchments in the Auckland region, to determine whether there was any difference in the ability of the SPM to adsorb Cu, Pb and Zn. The degree of trace metal adsorption onto the SPM was assessed by way of adsorption edge experiments. It was found that the ability of the Auckland urban SPM to adsorb trace metals decreased in the order Pb > Cu > Zn. Little difference in adsorption was observed between the non-urban Waikato and Kaipara River SPM and urban SPM, or between urban SPM from different flow regimes and seasons, despite some compositional differences in the SPM. This suggests that on the basis of a single surface-binding site, metal adsorption onto SPM could be readily predicted across a range of urban and non-urban catchments in the Auckland region. Adsorption edges were modelled with a diffuse layer, surface complexation model to assess the role of Fe-oxide in adsorption. The MINTEQA2 model was used, assuming Fe-oxide (as HFO) was the only adsorbing surface. There was generally good agreement between observed and modelled adsorption for Pb, indicating the importance of Fe-oxide surfaces for Pb adsorption. However, the model did not predict Zn or Cu adsorption as well. The TOC content of the SPM, and presence of dissolved ligands and organic matter in the water column, appeared to play an important role in Cu adsorption to the SPM. For Zn, the presence of adsorbing surfaces other than HFO appeared to influence adsorption. 相似文献
20.
Dissolved and particulate Zn and Ni concentrations were determined at 76 locations along the Yangtze River basin from the headwaters to the estuary during flood and dry seasons. Spatial and temporal variations of Zn and Ni were investigated and six major source zones were identified. The Three Gorges Dam (TGD) blocked most of the suspended loads and extremely low concentration of Zn and Ni were observed downstream of the dam. Dissolved (ranging from 0.062 to 8.0 μg L−1) and particulate (ranging from 12 to 110 mg kg−1) Ni showed similar levels of concentrations during flood and dry seasons, whereas dissolved (ranging from 0.43 to 49 μg L−1) and particulate (ranging from 54 to 1100 mg kg−1) Zn were slightly and much lower in the flood season than dry season, respectively. This was attributed to the increased water discharge during the flood season causing a dilution effect and sediment resuspension. In the flood season, average concentrations of Zn and Ni were higher in the main channel than in tributaries, due to soil erosion and mining activities providing the dominant inputs. The situation was opposite in the dry season, attributed to the contribution of municipal sewage, industrial activities, and waste disposal. During the flood season, dissolved Zn and Ni concentrations were negatively correlated with pH. Water and suspended particulate matter (SPM) from the upper reaches, middle reaches, and lower reaches of the Yangtze River were characterized by their Zn and Ni concentrations. The Panzhihua, Nanling and Tongling mining areas were considered as the most important source zones of particulate Zn and Ni. The Chongqing region, Wuhan region and the Yangtze River Delta provided most of the dissolved Zn and Ni inputs into the river. Annual net flux of Zn (10–72 × 105 kg a−1) and Ni (5.0–19 × 105 kg a−1) in each source zone were estimated according to their respective influent and effluent fluxes. Contributions of the source zones to Zn and Ni transport decreased from the upper reaches to the lower reaches. 相似文献