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1.
Several methods were evaluated and compared for the estimation of pyrite oxidation rates (POR) in waste rock at Mine Doyon, Quebec, Canada. Methods based on data collected in situ, such as the interpretation of temperature and oxygen concentration profiles (TOP) measured in the waste rock pile and pyrite mass balance (PMB) on solid phase samples were compared with the oxygen consumption measurements (OCM) in closed chamber in the laboratory. A 1-D analytical solution to a gas and heat transport equation used temperature and oxygen profiles (TOP) measured in the pile for the preliminary POR estimates at a site close to the slope of the pile (Site 6) and in the core of the pile (Site 7). Resulting POR values were 1.1 × 10− 9 mol(O2) kg− 1 s− 1 and 1.0 × 10− 10 mol(O2) kg− 1 s− 1 for the slope site and the core site, respectively. Oxidation rates based on pyrite mass balance (PMB) calculations for solid samples were 2.21 × 10− 9 mol(O2) kg− 1 s− 1 and 2.03 × 10− 9 mol(O2) kg− 1 s− 1, respectively, for the same slope and core sites, but the difference between sites was within the error margin. The OCM measurements in the laboratory on fresh waste rock samples yielded higher POR values than field methods, with average oxidation rate of 6.7 × 10− 8 mol(O2) kg− 1 s− 1. However, the OCM results on weathered and decomposed material from the rock stockpile (average oxidation rate 3.4 × 10− 9 mol(O2) kg− 1 s− 1) were consistent with results from the field-based estimates. When POR values based on fresh material are excluded, the remaining POR values for all methods range from 1.0 × 10− 10 to 3.4 × 10− 9 mol(O2) kg− 1 s− 1. The lowest estimated value (1.0 × 10− 10 mol(O2) kg− 1 s− 1) was based on TOP estimates in the interior of the pile where oxygen transport was limited by diffusion from the surface. These results suggest that small-scale OCM laboratory experiments may provide relatively representative values of POR in the zones of waste rock piles in which oxygen transport is not dominated by diffusion.  相似文献   

2.
The isotopic composition of Fe was determined in water, Fe-oxides and sulfides from the Tinto and Odiel Basins (South West Spain). As a consequence of sulfide oxidation in mine tailings both rivers are acidic (1.45 < pH < 3.85) and display high concentrations of dissolved Fe (up to 420 mmol l− 1) and sulphates (up to 1190 mmol l− 1).The δ56Fe of pyrite-rich samples from the Rio Tinto and from the Tharsis mine ranged from − 0.56 ± 0.08‰ to + 0.25 ± 0.1‰. δ56Fe values for Fe-oxides precipitates that currently form in the riverbed varied from − 1.98 ± 0.10‰ to 1.57 ± 0.08‰. Comparatively narrower ranges of values (− 0.18 ± 0.08‰ and + 0.21 ± 0.14‰) were observed in their fossil analogues from the Pliocene–Pleistocene and in samples from the Gossan (the oxidized layer that formed through exposure to oxygen of the massive sulfide deposits) (− 0.36 ± 0.12‰ to 0.82 ± 0.07‰). In water, δ56Fe values ranged from − 1.76 ± 0.10‰ to + 0.43 ± 0.05‰.At the source of the Tinto River, fractionation between aqueous Fe(III) and pyrite from the tailings was less than would be expected from a simple pyrite oxidation process. Similarly, the isotopic composition of Gossan oxides and that of pyrite was different from what would be expected from pyrite oxidation. In rivers, the precipitation of Fe-oxides (mainly jarosite and schwertmannite and lesser amounts of goethite) from water containing mainly (more than 99%) Fe(III) with concentrations up to 372 mmol l− 1 causes variable fractionation between the solid and the aqueous phase (− 0.98‰ < Δ56Fesolid–water < 2.25‰). The significant magnitude of the positive fractionation factor observed in several Fe(III) dominated water may be related to the precipitation of Fe(III) sulphates containing phases.  相似文献   

3.
The objectives of this study were to partition out the predominant anaerobic respiration pathways coupled to C oxidation and to further elucidate the controls of anaerobic C respiration in three major saltmarsh habitats at Skidaway Island, GA; the short form of Spartina alterniflora (SS), the tall form of S. alterniflora (TS), and unvegetated, bioturbated creekbank (CB). Geochemical analysis of pore water and solid phase constituents revealed that the SS site experienced highly reducing conditions with two orders of magnitude higher pore water sulfide inventories (1.884 mmol m−2) than TS (0.003 mmol m−2) and CB (0.005 mmol m−2), respectively. Conversely, reactive Fe(III) inventories at TS (2208 mmol m−2) and CB (2881 mmol m−2) were up to 7–9 times higher than at SS (338 mmol m−2). Incubations and intact core experiments indicated that reduction accounted for 95% (SS), 37% (TS) and 66% (CB) of total anaerobic respiration. There was no detectable Fe(III) reduction at SS, while Fe(III) reduction accounted for up to 70% of C oxidation in the 3–6 cm depth interval at TS and 0–3 cm depth of CB, and on average, approximately 55% of C oxidation over two-thirds of marsh surface area. Laboratory manipulations provided further evidence for the importance of Fe(III) reduction as the accumulation rates of fermentation products were high when Fe(III) reduction was inhibited by removing the Fe(III) minerals from highly bioturbated CB sediments with higher Fe(III) mineral contents. Anaerobic C oxidation, - and Fe(III)-reduction rates appeared to be highest at the TS site during active plant growth in summer. Overall results suggest that bioturbation by macrofauna is the overriding factor in modulating the pathway of C mineralization in the saltmarsh, whereas availability of organic substrates from plants is a key factor in controlling the C oxidation rate.  相似文献   

4.
Cinnabar (α-HgS) and metacinnabar (β-HgS) dissolved at environmentally significant rates in oxygenated slurry experiments simulating a low-flow fluvial system. Based on SO42− production, cinnabar dissolution rates were 2.64 to 6.16 μmol (SO42−) m− 2 day− 1, and metacinnabar dissolution rates were 1.20 to 1.90 μmol (SO42−) m− 2 day− 1. Monodentate-bound thiosulfate (S2O32−) was identified as an oxidation product on the HgS surface by ATR-IR spectroscopy based on strong infrared absorption bands in the 1140–1145 cm− 1 and 1006–1014 cm− 1 regions. The presence of sulfide oxidation intermediates on the HgS surface indicates that SO42− concentration underestimates α-HgS and β-HgS dissolution in this setting. Mercury release rates during dissolution were more than two orders of magnitude less than SO42− production, but were significant: 0.47 mg (Hg) m− 2 y− 1 from cinnabar [6.45 nmol (Hg) m− 2 day− 1], and 0.17 mg (Hg) m− 2 y− 1 from metacinnabar [2.29 nmol (Hg) m− 2 day− 1]. The Hg mobilized during α-HgS and β-HgS dissolution is sufficient to form natural Au–Hg amalgam in downstream placer settings. The proportion of mercury that is not remobilized during α-HgS and β-HgS dissolution likely adsorbs to the dissolving mercuric sulfide. Adsorption of Hg2+ to cinnabar was detected in situ by anodic stripping voltammetry using a cinnabar-modified carbon paste electrode following accumulation of Hg2+ on the electrode at open circuit potential.  相似文献   

5.
Secondary reactions occurring in pyrite-containing sediments from open cut coal mines are complex and not fully understood. In this study, the changes in seepage water composition in a column experiment with a sediment containing pyrite (5.6 g kg−1) were evaluated using a chemical equilibrium model. A column experiment with artificial irrigation (730 mm water yr−1) was carried out for 2 yr with a sediment from the open pit mine Garzweiler, Germany, at the Institute of Applied Geology. Tracer (LiCl) was added to the sediment. Seepage water composition at 52 cm depth was sampled weekly. Redox potential and the water potential were also recorded weekly. Sulphate and Fe(II) were the dominant ions in the seepage water with concentration maxima of 500 and 350 mmol l−1 after 50 days (0.7 pore volumes (PV)). Minimum pH values were around 0.8 after 100 days (1.4 PV), but increased subsequently and reached 2.4 after 700 days (9.5 PV). Ion activity product calculations indicated the intermediate formation of gypsum (19th–480th day of the experiment). Solutions were undersaturated with respect to alunite, jarosite, jurbanite, schwertmannite, melanterite, gibbsite and goethite during the whole experiment. The model of coupled equilibria which included inorganic complexation, precipitation/dissolution of gypsum and multiple cation exchange was tested. Pyrite oxidation and pH-dependent silicate weathering were considered using simple input functions. Transport was modelled using a field capacity cascade submodel. Model results showed satisfactory agreement with measured values for pH and concentrations of SO4, Fe, Mg, Ca and Al. Correlation coefficients lay between 0.7 and 0.9 and linear regression coefficients (modelled against measured) were 1.5 (Ca), 1.0 (Fe, SO4), 0.8 (Mg), 0.7 (pH) and 0.6 (Al). The results showed that the protons produced during pyrite oxidation (94 mmolc H+ kg−1) were mainly released into seepage water (as HSO4− and H+). Cation exchange reactions buffered 20 mmolc of H+ kg−1 sediment, and Al released by silicate weathering accounted for 3.6 mmolc H+ kg−1. Modelling was useful to further understand the significance of different pH buffer reactions.  相似文献   

6.
Groundwaters and surface water in the Shihongtan sandstone-hosted U ore district, Xinjiang, NW China, were sampled and analyzed for their major-, and trace element concentrations and oxygen, hydrogen, boron and strontium isotope compositions in order to assess the possible origins of the waters and water–rock interactions that occurred in the deep aquifer system. The waters in the study district have been grouped into three hydrochemical facies: Facies 1, potable spring-water, is a pH neutral (7.0), Na–Ca–HCO3 type water with low total dissolved solids (TDS; 0.2 g/l, fresh) and has δ18O of − 8.3‰, δD of − 48.2‰,δ11B of 1.5‰, and 87Sr/86Sr of 0.70627. Facies 2 groundwaters are mildly acidic to mildly alkaline (pH of 6.5–8.0, mean 7.3), Na–Ca–Mg–Cl–SO4 type waters with moderate TDS (8.2 g/l–17.2 g/l, mean 9.3 g/l, brackish) and haveδ18O values in the − 5.8‰ to − 9.3‰ range (mean − 8.1‰), δD values in the − 20.8‰ to − 85.5‰ range (mean − 47.0‰),δ11B values in the + 9.5‰ to + 39.1‰ range (mean + 17.1‰), and 87Sr/86Sr values in the 0.70595 to 0.70975 range (mean 0.70826). Facies 3, Aiting Lake water, is a mildly alkaline (pH = 7.4), Na–Ca–Mg–Cl–SO4 type water with the highest TDS (249.1 g/l, brine) and has δ18O of − 2.8‰, δD of − 45.8‰,δ11B of 21.2‰, and 87Sr/86Sr of 0.70840. The waters from the study district show a systematic increase in major, trace element and TDS concentrations and δ11B values along the pathway of groundwater migration which can only be interpreted in terms of water–rock interaction at depth and strong surface evaporation. The hydrochemical and isotopic data presented here confirm that the groundwaters in the Shihongtan ore district are the combined result of migration, water–rock interaction and mixing of meteoric water with connate waters contained in sediments.  相似文献   

7.
The possible contamination of a groundwater system with industrial wastewater originating from a paper mill factory has been investigated in Piteå, N. Sweden. Six samples were collected from the wastewater in the waste dump and twelve samples from the adjacent groundwater were analyzed for chemistry and sulfur isotopes. The industrial wastewater is a saline water consisting mainly of Na–HCO3–SO4, having a high pH and showing δ34S values between 7‰ and 9‰ affected by bacterial sulfate reduction. The groundwaters are relatively dilute, dominated by Na+, Ca2+ and HCO3−, but with varying concentrations as exemplified by sulfate with concentrations varying between 3 and 69 mg L− 1 while the δ34S values range from − 0.5‰ to 14.3‰. The data suggest that the main S sources in the waters are the bedrock sulfides and/or atmospheric deposition, which, sometimes, are overlapped by bacterial sulfate reduction. Contamination from the waste dump does not occur.  相似文献   

8.
The geochemistry of dissolved and suspended loads in river catchments of two low mountain ranges in Central Europe allows comparison of pertinent chemical weathering rates. Distinct differences in lithology, i.e. granites prevailing in the Black Forest compared to Palaeozoic sediments in the Rhenish Massif, provide the possibility to examine the influence of lithology on weathering. Here we determine the origin of river water using the stable isotope ratio δ18OH2O and we quantify the geogenic proportions of sulphate from stable isotope ratios δ34SSO4 and δ18OSO4. Particularly in catchments with abundant pyrite, determination of the geogenic amount of sulphate is important, since oxidation of pyrite leads to acidity, which increases weathering. Our results show that spatially averaged silicate weathering rates are higher for the river catchments Acher and Gutach in the Black Forest (10–12 t/km2/yr) compared to the river catchments of the Möhne dam and the Aabach dam in the Rhenish Massif (2–6 t/km2/yr). Correspondingly, the CO2 consumption by silicate weathering in the Black Forest (334–395 × 103 mol/km2/yr) is more than twice as high as in the Rhenish Massif (28–151 × 103 mol/km2/yr). These higher rates for watersheds of the Black Forest are likely due to steeper slopes leading to higher mechanical erosion with respective higher amounts of fresh unweathered rock particulates and due to the fact that the sediments in the Rhenish Massif have already passed through at least one erosion cycle. Carbonate weathering rates vary between 12 and 38 t/km2/yr in the catchments of the Rhenish Massif. The contribution of sulphuric acid to the silicate weathering is higher in the catchments of the Rhenish Massif (9–16%) than in the catchments of the Black Forest (5–7%) due to abundant pyrite in the sediments of the Rhenish Massif. Three times higher long-term erosion rates derived from cosmogenic nuclides compared to short-term erosion rates derived from river loads in Central Europe point to three times higher CO2 consumption during the past 103 to 104 years.  相似文献   

9.
The carbonate-hosted Kabwe Pb–Zn deposit, Central Zambia, has produced at least 2.6 Mt of Zn and Pb metal as well as minor amounts of V, Cd, Ag and Cu. The deposit consists of four main epigenetic, pipe-like orebodies, structurally controlled along NE–SW faults. Sphalerite, galena, pyrite, minor chalcopyrite, and accessory Ge-sulphides of briartite and renierite constitute the primary ore mineral assemblage. Cores of massive sulphide orebodies are surrounded by oxide zones of silicate ore (willemite) and mineralized jasperoid that consists largely of quartz, willemite, cerussite, smithsonite, goethite and hematite, as well as numerous other secondary minerals, including vanadates, phosphates and carbonates of Zn, Pb, V and Cu.Galena, sphalerite and pyrite from the Pb–Zn rich massive orebodies have homogeneous, negative sulphur isotope ratios with mean δ34SCDT permil (‰) values of − 17.75 ± 0.28 (1σ), − 16.54 ± 0.0.27 and − 15.82 ± 0.25, respectively. The Zn-rich and Pb-poor No. 2 orebody shows slightly heavier ratios of − 11.70 ± 0.5‰ δ34S for sphalerite and of − 11.91 ± 0.71‰ δ34S for pyrite. The negative sulphur isotope ratios are considered to be typical of sedimentary sulphides produced through bacterial reduction of seawater sulphate and suggest a sedimentary source for the sulphur.Carbon and oxygen isotope ratios of the host dolomite have mean δ13CPDB and δ18OSMOW values of 2.89‰ and 27.68‰, respectively, which are typical of marine carbonates. The oxygen isotope ratios of dolomite correlate negatively to the SiO2 content introduced during silicification of the host dolomite. The depletion in 18O in dolomite indicates high temperature fluid/rock interaction, involving a silica- and 18O-rich hydrothermal solution.Two types of secondary fluid inclusions in dolomite, both of which are thought to be related to ore deposition, indicate temperatures of ore deposition in the range of 257 to 385 and 98 to 178 °C, respectively. The high temperature fluid inclusions contain liquid + vapour + solid phases and have salinities of 15 to 31 eq. wt.% NaCl, whereas the low temperature inclusions consist of liquid + vapour with a salinity of 11.5 eq. wt.% NaCl.Fluid transport may have been caused by tectonic movements associated with the early stages of the Pan-African Lufilian orogeny, whereas ore deposition within favourable structures occurred due to changes in pressure, temperature and pH in the ore solution during metasomatic replacement of the host dolomite. The termination of the Kabwe orebodies at the Mine Club fault zone and observed deformation textures of the ore sulphides as well as analysis of joint structures in the host dolomite, indicate that ore emplacement occurred prior to the latest deformation phase of the Neoproterozoic Lufilian orogeny.  相似文献   

10.
Historic Hg mining in the Cache Creek watershed in the Central California Coast Range has contributed to the downstream transport of Hg to the San Francisco Bay-Delta. Different aspects of Hg mobilization in soils, including pedogenesis, fluvial redistribution of sediment, volatilization and eolian transport were considered. The greatest soil concentrations (>30 mg Hg kg−1) in Cache Creek are associated with mineralized serpentinite, the host rock for Hg deposits. Upland soils with non-mineralized serpentine and sedimentary parent material also had elevated concentrations (0.9–3.7 mg Hg kg−1) relative to the average concentration in the region and throughout the conterminous United States (0.06 mg kg−1). Erosion of soil and destabilized rock and mobilization of tailings and calcines into surrounding streams have contributed to Hg-rich alluvial soil forming in wetlands and floodplains. The concentration of Hg in floodplain sediment shows sediment dispersion from low-order catchments (5.6–9.6 mg Hg kg−1 in Sulphur Creek; 0.5–61 mg Hg kg−1 in Davis Creek) to Cache Creek (0.1–0.4 mg Hg kg−1). These sediments, deposited onto the floodplain during high-flow storm events, yield elevated Hg concentrations (0.2–55 mg Hg kg−1) in alluvial soils in upland watersheds. Alluvial soils within the Cache Creek watershed accumulate Hg from upstream mining areas, with concentrations between 0.06 and 0.22 mg Hg kg−1 measured in soils 90 km downstream from Hg mining areas. Alluvial soils have accumulated Hg released through historic mining activities, remobilizing this Hg to streams as the soils erode.  相似文献   

11.
Dissolution of the synthetic hydroxylapatite (HAP) and fluorapatite (FAP) in pure water was studied at 25 °C and 45 °C in a series of batch experiments. The XRD, FT-IR and SEM analyses indicated that the synthetic, microcrystalline HAP and FAP with apatite structure used in the experiments were found to have no obvious variation after dissolution except that the existence of OH groups in FT-IR spectra for FAP after 2880 h dissolution was observed. During the HAP dissolution (0–4320 h), the aqueous calcium and phosphate concentrations reached the maxima after 120 h and then decreased slowly with time. For the FAP dissolution in pure water, after a transient time of 1440 h (< 60 d), element concentrations and pH became constant suggesting attainment of a steady-state between the solution and solid. During early stages of the FAP dissolution reaction (< 72–120 h), mineral components were released in non-stoichiometric ratios with reacted solution ratios of dissolved Ca:P, Ca:F and P:F being lower than mineral stoichiometric ratios of Ca5(PO4)3F, i.e., 1.67, 5.0 and 3.0, respectively. This indicated that F were preferentially released compared to Ca from the mineral structure. The mean Ksp values were calculated by using PHREEQC for HAP of 10− 53.28 (10− 53.02–10− 53.51) and for FAP of 10− 55.71 (10− 55.18–10− 56.13) at 25 °C, the free energies of formation ΔGfo[HAP] and ΔGfo[FAP] were calculated to be − 6282.82 kJ/mol and − 6415.87 kJ/mol, respectively.  相似文献   

12.
When pyrite oxidizes at near neutral pH in the presence of sufficient alkalinity, Fe oxyhydroxide coatings develop on the surface. As these coatings grow thicker and denser they block oxidant transport from the solution to the pyrite surface and reduce the rate of pyrite oxidation. The authors’ measurements of pyrite oxidation rates in a NaHCO3 solution show that the coating grows in two stages. In the first stage Fe oxyhydroxide colloids form and then attach to the pyrite surface to produce a slight reduction in oxidant transport. In the second stage interstitial precipitation of Fe oxyhydroxide material between the colloidal particles reduces the oxidant’s diffusion coefficient by more than five orders of magnitude. This causes the pyrite oxidation rate to decline as the square root of time. The kinetic predominance diagram, which compares the rates of Fe transformation reactions, shows that when pyrite oxidation releases Fe quickly enough for the total Fe concentration to rise to about 10−8 m, ferrihydrite forms but lower rates of Fe release will not produce coatings. Extrapolation of the results to longer times predicts that pyrite-bearing materials need to be treated with an extra source of alkalinity for several decades to produce coatings that are thick enough to be sustained by alkalinity levels typical of groundwater. However, once the coatings develop no additional treatment is needed and further pyrite oxidation simply causes the coating to grow thicker and denser until the entire pyrite grain is pseudomorphically replaced by goethite.  相似文献   

13.
The Yueshan mineral belt is geotectonically located at the centre of the Changjiang deep fracture zone or depression of the lower Yangtze platform. Two main types of ore deposits occur in the Yueshan orefield: Cu–Au–(Fe) skarn deposits and Cu–Mo–Au–(Pb–Zn) hydrothermal vein-type deposits. Almost all deposits of economic interest are concentrated within and around the eastern and northern branches of the Yueshan dioritic intrusion. In the vicinity of the Zongpu and Wuhen intrusions, there are many Cu–Pb–Zn–Au–(S) vein-type and a few Cu–Fe–(Au) skarn-type occurrences.Fluid inclusion studies show that the ore-forming fluids are characterised by a Cl−(S)–Na+–K+ chemical association. Hydrothermal activity associated with the above two deposit types was related to the Yueshan intrusion. The fluid salinity was high during the mineralisation processes and the fluid also underwent boiling and mixed with meteoric water. In comparison, the hydrothermal activity related to the Zongpu and Wuhen intrusions was characterised by low salinity fluids. Chlorine and sulphur species played an important role in the transport of ore-forming components.Hydrogen- and oxygen-isotope data also suggest that the ore-forming fluids in the Yueshan mineral belt consisted of magmatic water, mixed in various proportions with meteoric water. The enrichment of ore-forming components in the magmatic waters resulted from fluid–melt partitioning. The ore fluids of magmatic origin formed large Cu–Au deposits, whereas ore fluids of mixed magmatic-meteoric origin formed small- to medium-sized deposits.The sulphur isotopic composition of the skarn- and vein-type deposits varies from − 11.3‰ to + 19.2‰ and from + 4.2‰ to + 10.0‰, respectively. These variations do not appear to have been resulted from changes of physicochemical conditions, rather due to compositional variation of sulphur at the source(s) and by water–rock interaction. Complex water–rock interaction between the ore-bearing magmatic fluids and sedimentary wall rocks was responsible for sulphur mixing. Lead and silicon isotopic compositions of the two deposit types and host rocks provide similar indications for the sources and evolution of the ore-forming fluids.Hydrodynamic calculations show that magmatic ore-forming fluids were channelled upwards into faults, fractures and porous media with velocities of 1.4 m/s, 9.8 × 10− 1 to 9.8 × 10− 7 m/s and 3.6 × 10− 7 to 4.6 × 10− 7 m/s, respectively. A decrease of fluid migration velocity in porous media or tiny fractures in the contact zones between the intrusive rocks and the Triassic sedimentary rocks led to the deposition of the ore-forming components. The major species responsible for Cu transport are deduced to have been CuCl, CuCl2−, CuCl32− and CuClOH, whereas Au was transported as Au2(HS)2S2−, Au(HS)2−, AuHS and AuH3SiO4 complexes. Cooling and a decrease in chloride ion concentration caused by fluid boiling and mixing were the principal causes of Cu deposition. Gold deposition was related to decrease of pH, total sulphur concentration and fO2, which resulted from fluid boiling and mixing.Geological and geochemical characteristics of the two deposit types in the Yueshan mineral belt suggest that there is a close genetic relationship with the dioritic magmatism. Geochronological data show that the magmatic activity and the mineralisation took place between 130 and 136 Ma and represent a continuous process during the Yanshanian time. The cooling of the intrusions and the mineralisation event might have lasted about 6 Ma. The cooling rate of the magmatic intrusions was 80 to 120 °C my− 1, which permitted sufficient heat supply by magma to the ore-forming system.  相似文献   

14.
The Daduhe gold field comprises several shear-zone-controlled Tertiary lode gold deposits distributed at the eastern margin of the Tibetan Plateau. The deposits are hosted in a Precambrian granite–greenstone terrane within the Yangtze Craton. The gold mineralization occurs mainly as auriferous quartz veins with minor sulphide minerals. Fluid inclusions in pyrite have 3He/4He ratios of 0.16 to 0.86 Ra, whereas their 40Ar/36Ar ratios range from 298 to 3288, indicating a mixing of fluids of mantle and crust origins. The δ34S values of pyrite are of 0.7–4.2‰ (n = 12), suggesting a mantle source or leaching from the mafic country rocks. δ18O values calculated from hydrothermal quartz are between − 1.5‰ and + 6.0‰ and δD values of the fluids in the fluid inclusions in quartz are − 39‰ and − 108‰. These ranges demonstrate a mixing of magmatic/metamorphic and meteoric fluids. The noble gas isotopic data, along with the stable isotopic data suggest that the ore-forming fluids have a dominantly crustal source with a significant mantle component.  相似文献   

15.
The Changkeng Au and Fuwang Ag deposits represent an economically significant and distinct member of the Au–Ag deposit association in China. The two deposits are immediately adjacent, but the Au and Ag orebodies separated from each other. Ores in the Au deposit, located at the upper stratigraphic section and in the southern parts of the orefield, contain low Ag contents (< 11 ppm); the Ag orebodies, in the lower stratigraphic section, are Au-poor (< 0.2 ppm). Changkeng is hosted in brecciated cherts and jasperoidal quartz and is characterized by disseminated ore minerals. Fuwang, hosted in the Lower Carboniferous Zimenqiao group bioclastic limestone, has vein and veinlet mineralization associated with alteration comprised of quartz, carbonate, sericite, and sulfides. Homogenization temperatures of fluid inclusions from quartz veinlets in the Changkeng and Fuwang deposits are in the range of 210 ± 80 °C and 230 ± 50 °C, respectively. Salinities of fluid inclusions from the two deposits range from 1.6 to 7.3 wt.% and 1.6 to 2.6 wt.% equiv. NaCl, respectively. The δDH2O, δ18OH2O, δ13CCO2 and 3He/4He values of the fluid inclusions from the Changkeng deposit range from − 80‰ to − 30‰, − 7.8‰ to − 3.0‰, − 16.6‰ to − 17.0‰ and 0.0100 to 0.0054 Ra, respectively. The δDH2O, δ18OH2O, δ13CCO2 and 3He/4He values of fluid inclusions from the Fuwang deposit range from − 59‰ to − 45‰, − 0.9‰ to 4.1‰, − 6.7‰ to − 0.6‰ and 0.5930 to 0.8357 Ra, respectively. The δDH2O, δ18OH2O, δ13CCO2 and 3He/4He values of the fluid inclusions suggest the ore fluids of the Changkeng Au-ore come from the meteoric water and the ore fluids of the Fuwang Ag-ore are derived from mixing of magmatic water and meteoric water. The two deposits also show different Pb-isotopic signatures. The Changkeng deposit has Pb isotope ratios (206Pb/204Pb: 18.580 to 19.251, 207Pb/204Pb: 15.672 to 15.801, 208Pb/204Pb: 38.700 to 39.104) similar to those (206Pb/204Pb: 18.578 to 19.433, 207Pb/204Pb: 15.640 to 15.775, 208Pb/204Pb: 38.925 to 39.920) of its host rocks and different from those (206Pb/204Pb: 18.820 to 18.891, 207Pb/204Pb: 15.848 to 15.914, 208Pb/204Pb: 39.579 to 39.786) of the Fuwang deposit. The different signatures indicate different sources of ore-forming material. Rb–Sr isochron age (68 ± 6 Ma) and 40Ar–39Ar age (64.3 ± 0.1 Ma) of the ore-related quartz veins from the Ag deposit indicate that the Fuwang deposit formed during the Cenozoic Himalayan tectonomagmatic event. Crosscutting relationships suggests that Au-ore predates Ag-ore. The adjacent Changkeng and Fuwang deposits could, however, represent a single evolved hydrothermal system. The ore fluids initially deposited Au in the brecciated siliceous rocks, and then mixing with the magmatic water resulted in Ag deposition within fracture zones in the limestone. The deposits are alternatively the product of the superposition of two different geological events. Age evidence for the Fuwang deposit, together with the Xiqiaoshan Tertiary volcanic-hosted Ag deposit in the same area, indicates that the Pacific Coastal Volcanic Belt in the South China Fold Belt has greater potential for Himalayan precious metal mineralization than previous realized.  相似文献   

16.
Groundwater down-gradient from a mine rock dump in Dalarna, Sweden was sampled from the onset of snowmelt runoff (April) until October in order to investigate seasonal variations in groundwater composition. The results demonstrate that considerable variation in solute concentration (Al, Cu, Fe, SO42−, Zn) and acidity occurs in groundwater; the greatest change in solute concentrations occurs during the melting of the snow cover, when sulfide oxidation products are flushed from the rock dump. During this period, groundwater flow is concentrated near the soil surface with an estimated velocity of 1 m/day. Groundwater acidity varied by a factor of four closest to the rock dump during the sampling period, but these variations were attenuated with distance from the rock dump. Over a distance of 145 m, groundwater pH increases from 2.5 to 4.0 and acidity decreases from 3–13 to 0.8–1.1 meq/L, which is the combined effect of ferric iron precipitation and aluminosilicate weathering. As a result of flushing from the upper soil horizons, peaks in total organic carbon and ammonium concentrations in groundwater are observed at the end of snowmelt. In soils impacted by acidic surface runoff, the sequential extraction of C horizon soils indicates the accumulation of Cu in well-crystallized iron oxyhydroxides in the upper C horizon, while Cu, Fe, Ni and Zn accumulate in a well-crystallized iron oxyhydroxide hardpan that has formed 2.5m below the ground surface. Surface complexation modeling demonstrates that SO42− and Cu adsorb to the abundant iron oxyhydroxides at pH < 4, while Zn adsorption in this pH range is minimal.  相似文献   

17.
Heterogeneous shallow Plio-Quaternary formations of the Souss Plain represent the most important aquifer in southern High Atlas Mountains in Morocco. The present work was conducted in the Souss Upstream Basin to identify the chemical characteristics and the origin of groundwater in an aquifer under semi-arid climate. Isotopic and hydrochemical compositions combined with geological and hydrogeological data were used for this purpose. The total dissolved solids vary from 239 to 997 mg l−1, and the following groundwater types are recognized: Ca2+–Mg2+–HCO3−, Ca2+–Mg2+–SO42− and Ca2+–Mg2+–Cl−. The groundwater is saturated and slightly supersaturated with respect to carbonate minerals and undersaturated with respect to evaporite minerals, which means that the groundwater composition is largely controlled by the dissolution of carbonate rocks known in the basin. The isotopic contents of groundwaters ranged from −8‰ to −5.2‰ for δ18O, from −52‰ to −34‰ for δD, and from 0 to 5.5 TU for tritium. The hydrogen (δD) and oxygen (δ18O) isotope signatures reveal a significant infiltration before evaporation takes place, indicating a major recharge directly from fractures in the crystalline and limestone formations of Atlas Mountains (above 800 m a.s.l.) and infiltration of surface water in the alluvial cones at the border of the Atlas basins. The very low tritium values suggest that the groundwater recharge follows a long flow path and a mixing between old and modern water is shown. However, a slight evaporation effect is noted in the southern part of the basin close to the Anti-Atlas Mountains.  相似文献   

18.
Mercury contamination in aquatic environments is of worldwide concern because of its high biomagnification factor in food chains and long-range transport. The rivers, estuary and the bay along the northwestern Bohai Sea coast, northeastern China have been heavily contaminated by Hg due to long-term Zn smelting and chlor-alkali production. This work investigated the distributions of total Hg (THg) and monomethylmercury (MMHg) in the water, sediment and hydrophytes from this area. Concentrations of THg in sediment (0.5–64 mg kg−1) and water (39–2700 ng L−1) were elevated by 1–3 orders of magnitude compared to background concentrations, which induced high concentrations of MMHg in these media. The highest concentration of MMHg in sediment reached 35 μg kg−1, which was comparable to that in the Hg mining area, Wanshan, China, and the highest MMHg concentration of 3.0 ng L−1 in the water sample exceeded the MMHg Chinese drinking water guideline of 1.0 ng L−1. Concentrations of THg in a sediment profile from Jinzhou Bay were found to be consistent with annual Hg emission flux from a local Zn smelter (r = 0.74, p < 0.01), indicating that Hg contamination was mainly caused by Zn smelting locally. For some freshwater hydrophytes, concentrations of THg and MMHg ranged from 5.2 to 100 μg kg−1 and 0.15 to 12 μg kg−1, respectively. Compared to sediment, concentrations of THg in hydrophytes were 2–3 orders of magnitude lower but MMHg was comparable or higher, indicating that the bioaccumulation in plants was distinct for the two Hg species studied. The data suggest that a significant load of Hg has been released into the northwestern coastal region of the Bohai Sea.  相似文献   

19.
Tunnel excavation at Äspö Island, Sweden, has caused severe groundwater disturbance, gradually extending deeper into the tunnel as present-day Baltic seawater intrudes through fractures connecting to the surface. However, the paleo-hydrogeochemical conditions have remained in the deep highly saline waters that have avoided mixing. A correlation has been observed between dissolved 4He concentration and Cl− ion concentration, measured every two years from 1995 to 2001 at Äspö. Groundwater mixing conditions can be examined by the correlations between 1/Cl, 36Cl/Cl, and 3H concentrations. Subsurface production is responsible for the majority of the 36Cl and excess dissolved 4He of interstitial groundwater in fractures. The secular equilibrium ratio of 36Cl/Cl in rock was theoretically estimated to be (5.05 ± 0.82) × 10−14 based on the neutron flux intensity, a value comparable to the measured 36Cl/Cl ratio in rock and groundwater. The degassing crustal 4He flux was estimated to be 2.9 × 10−8  1.3 × 10−6 (ccSTP/cm2a) using the HTO diffusion coefficient for the Äspö diorite. The 4He accumulation rate ranges from 6.8 × 10−10 (for the in situ accumulation rate) to 7.0 × 10−9 (ccSTP/(gwater · a) considering both 4He in situ production and the degassing flux, assuming 4He is accumulated constantly in groundwater. By comparing the subsurface 36Cl increase with 4He concentrations in groundwater, the 4He accumulation rate was determined from data for groundwater arriving at the secular equilibrium of 36Cl/Cl. The 4He accumulation rate was found to be (1.83 ± 0.72) × 10−8 ccSTP/(gwater · a) without determining the magnitude of degassing 4He flux.  相似文献   

20.
The Minqin Basin is a type area for examining stress on groundwater resources in the Gobi Desert, and has been investigated here using a combination of isotopic, noble gas and chemical indicators. The basin is composed of clastic sediments of widely differing grain size and during the past half century over 10 000 boreholes have been drilled with a groundwater decline of around 1 m a−1. Modern diffuse recharge is unlikely to exceed 3 mm a−1, as determined using unsaturated zone profiles and Cl− mass balance. A small component of modern (<50 a) groundwater is identified in parts of the basin from 3H–3He data, probably from irrigation returns. A clear distinction is found between modern waters with median δ18O values of 6.5 ± 0.5‰ and most groundwaters in the basin with more depleted isotopic signatures. Radiocarbon values as pmc range from 0.6% to 85% modern, but it is difficult to assign absolute ages to these, although a value of 20% modern C probably represents the late Pleistocene to Holocene transition. The δ13C compositions remain near-constant throughout the basin (median value of −8.1‰ δ13C) and indicate that carbonate reactions are unimportant and also that little reaction takes place. There is a smooth decrease in 14C activity accompanied by a parallel increase in 4He accumulations from S–N across the basin, which define the occurrence of a regional flow system. Noble gas temperatures indicate recharge temperatures of about 5.6 °C for late Pleistocene samples, which is some 2–3 °C cooler than the modern mean annual air temperature and the recharge temperature obtained from several Holocene samples. Groundwaters in the Minqin Basin have salinities generally below 1 g/L and are aerobic, containing low Fe but elevated concentrations of U, Cr and Se (mean values of 27.5, 5.8 and 5.3 μg L−1, respectively). Nitrate is present at baseline concentrations of around 2 mg L−1 but there is little evidence of impact of high NO3 from irrigation returns. Strontium isotope and major ion ratios suggest that silicate reactions predominate in the aquifer. The results have important implications for groundwater management in the Minqin and other water-stressed basins in NW China – a region so far destined for rapid development. The large proportion of the water being used at present is in effect being mined and significant changes are urgently needed in water use strategy.  相似文献   

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