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1.
Sulphur isotopic data for sulphides and barite from several carbonatites (Mountain Pass, Oka, Magnet Cove, Bearpaw Mountains, Phalabora) show that individual carbonatites have different mean sulphide or barite isotopic compositions which deviate from the meteoritic mean δ34S(0‰).Classification of carbonatites in terms of T,?O2 and pH during formation of the sulphur-bearing assemblages indicates that with decreasing T and increasing relative ?O2 the mean δ34S sulphide becomes increasing negative relative to the mean magma δ34S. Only barite-free high temperature carbonatites (Phalabora) in which the mean δ34S sulphide approaches the mean magmaδ34S as a consequence of the paucity of oxidized anionic sulphur species in the magma can be used to directly estimate the mean isotopic composition of the source material.Barites from the Mountain Pass carbonatite show an increase in δ34S with sequence of intrusion of the carbonatite units; dolomitic carbonatite (mean δ34S, + 5.4‰), calcitic carbonatite (+ 4.8%.), silicified carbonatite (+ 6.9‰), tabular carbonatite dikes (+ 8.7‰), mineralized shear zones (+ 9.5‰). Within each of these units a spread of 6.8%. is evident. Isotopic trends in this low temperature (300°C) carbonatite are evaluated by treating the system as a hydrothermal fluid. The observed isotopic variations can be explained by removal of large amounts of sulphur from a fluid whose mean δ34S is 0 to + 1‰  相似文献   

2.
《Applied Geochemistry》1994,9(6):609-626
The Saint-Salvy vein-hosted Zn (+Ge) deposit occurs in an E–W fault system which flanks the southern margin of the late Variscan Sidobre granite, and cross-cuts Cambrian black shales of the Palaeozoic basement. Comprehensive mineralogical and geochemical studies of vein samples have revealed four mineralizing events (M1–M4) related to late and post-Variscan tectonic events. A further late-stage event may be related to weathering.M1 (=skarn deposits) and M2 (=patchily mineralized quartz veinlets) are associated with granite emplacement. Quartz contains low salinity, H2OCO2(NaCl)-dominated fluids(⩽6wt% NaCl equiv.) of relatively high temperature (300–580°C), trapped under moderate to high pressure. Estimated M1 fluid δD and calculated fluidδ18O plot within the metamorphic water field. There appears to be no involvement of magmatic fluids.By contrast, M3 (= barren quartz) and M4 (= zinciferous economic mineralization) stages have H2OCO2NaClCaCl2 fluid inclusions with high salinities (23–25 wt% NaCl equiv.) and low temperatures(∼ 80–140°C), which were trapped under low-pressure conditions. The high salinity and NaCl + CaCl2 content of both M3 and M4 indicates that their parent fluids leached evaporitic salts. M3 fluids are meteoric water dominated, falling close to the meteoric water line (δD andδ18O averaging −64 and −8‰, respectively). M4 fluids have highly distinctive δD averaging −101‰, and calculated fluidδ18O varying from−1.2to+7.1‰. The unusually low δD composition of M4 suggests the involvement of “organic” fluids, in which H is derived directly or indirectly from organic matter. The relatively highδ18O of M4 fluids indicates that considerable isotopic exchange with sedimentary material took place, displacing theδ18O from the meteoric water line. The data imply interaction of meteoric waters with evaporite and hydrocarbon-bearing sedimentary sequences, most probably the adjacent Aquitain Basin.The main economic mineralization (M4 stage) took place during a tensional event, probably coincident with the Lias-Dogger transition.Calculatedδ34SH2S of M4 sulphide(+5.4to+8.2‰) is almost identical toδ34S of local Cambrian sulphides(+4.7to+9.4‰) suggesting a genetic link. Abundant siderite associated with M4 sphalerite hasδ13C ranging from−2.6to−4.4‰ indicating that carbon was sourced from sedimentary carbonate mobilized by, or equilibrated with the hydrothermal fluid.Late-stage sulphides exhibit extraordinary and highly distinctiveδ34S. Sphalerite has extremely low δ34S(−42.5to−50.5‰), whereas pyrite has an extraordinary large range from−33.2‰to+74.3‰. Closed system sulphate reduction is held to be responsible for the extremely highδ34S: whereas more open system reduction produces the very low values. The coincidence of isotopically lowδ13C(−7.6to−11.9‰) for co-genetic calcite suggests the involvement of organic matter in the reduction process.  相似文献   

3.
《Applied Geochemistry》1997,12(1):97-103
Analyses for δ34S of 13 bedded, marine anhydrite samples from the “C” anhydrite member of the Red River Formation (Upper Ordovician) in the North Dakota portion of the Williston basin represent an addition of δ34S data to a portion of the S isotope age curve with few data. Previously published estimates of δ34S for Upper Ordovician marine sulfates apparently are limited to 4 samples from the Saskatchewan portion of the same basin. An adjusted mean value of +25.5‰ was calculated for all known Upper Ordovician δ34S determinations. This value is approximately 2 to 3‰ lighter than the previous estimate, which suggests that δ34S of the world ocean during the Upper Ordovician may have been lighter than previously thought. However, because all δ34S data are from one sedimentary basin, additional S isotopic data from several globally-distributed evaporite basins are needed to evaluate this hypothesis and further constrain δ34S for the Upper Ordovician. Similar re-examination of other portions of the S isotope age curve with limited amounts of data may increase our understanding of the secular variation in δ34S.  相似文献   

4.
《Applied Geochemistry》2005,20(4):789-805
Mineralogical, hydrochemical and S isotope data were used to constrain hydrogeochemical processes that produce acid mine drainage from sulfidic waste at the historic Mount Morgan Au–Cu mine, and the factors controlling the concentration of SO4 and environmentally hazardous metals in the nearby Dee River in Queensland, Australia. Some highly contaminated acid waters, with metal contents up to hundreds of orders of magnitude greater than the Australia–New Zealand environmental standards, by-pass the water management system at the site and drain into the adjacent Dee River.Mine drainage precipitates at Mt. Morgan were classified into 4 major groups and were identified as hydrous sulfates and hydroxides of Fe and Al with various contents of other metals. These minerals contain adsorbed or mineralogically bound metals that are released into the water system after rainfall events. Sulfate in open pit water and collection sumps generally has a narrow range of S isotope compositions (δ34S = 1.8–3.7‰) that is comparable to the orebody sulfides and makes S isotopes useful for tracing SO4 back to its source. The higher δ34S values for No. 2 Mill Diesel sump may be attributed to a difference in the source. Dissolved SO4 in the river above the mine influence and 20 km downstream show distinctive heavier isotope compositions (δ34S = 5.4–6.8‰). The Dee River downstream of the mine is enriched in 34S (δ34S = 2.8–5.4‰) compared with mine drainage possibly as a result of bacterial SO4 reduction in the weir pools, and in the water bodies within the river channel. The SO4 and metals attenuate downstream by a combination of dilution with the receiving waters, SO4 reduction, and the precipitation of Fe and Al sulfates and hydroxides. It is suggested here that in subtropical Queensland, with distinct wet and dry seasons, temporary reducing environments in the river play an important role in S isotope systematics.  相似文献   

5.
Eighteen basalts and some volcanic gases from the submarine and subaerial parts of Kilauea volcano were analyzed for the concentration and isotope ratios of sulfur. By means of a newly developed technique, sulfide and sulfate sulfur in the basalts were separately but simultaneously determined. The submarine basalt has 700 ± 100 ppm total sulfur with δ34SΣs of 0.7 ± 0.1 ‰. The sulfate/sulfide molar ratio ranges from 0.15 to 0.56 and the fractionation factor between sulfate and sulfide is +7.5 ± 1.5‰. On the other hand, the concentration and δ34SΣs values of the total sulfur in the subaerial basalt are reduced to 150 ± 50 ppm and ?0.8 ± 0.2‰, respectively. The sulfate to sulfide ratio and the fractionation factor between them are also smaller, 0.01 to 0.25 and +3.0‰, respectively. Chemical and isotopic evidence strongly suggests that sulfate and sulfide in the submarine basalt are in chemical and isotopic equilibria with each other at magmatic conditions. Their relative abundance and the isotope fractionation factors may be used to estimate the ?o2 and temperature of these basalts at the time of their extrusion onto the sea floor. The observed change in sulfur chemistry and isotopic ratios from the submarine to subaerial basalts can be interpreted as degassing of the SO2 from basalt thereby depleting sulfate and 34S in basalt.The volcanic sulfur gases, predominantly SO2, from the 1971 and 1974 fissures in Kilauea Crater have δ34S values of 0.8 to 0.9%., slightly heavier than the total sulfur in the submarine basalts and definitely heavier than the subaerial basalts, in accord with the above model. However, the δ34S value of sulfur gases (largely SO2) from Sulfur Bank is 8.0%., implying a secondary origin of the sulfur. The δ34S values of native sulfur deposits at various sites of Kilauea and Mauna Loa volcanos, sulfate ions of four deep wells and hydrogen sulfide from a geothermal well along the east rift zone are also reported. The high δ34S values (+5 to +6%.o) found for the hydrogen sulfide might be an indication of hot basaltseawater reaction beneath the east rift zone.  相似文献   

6.
The chemical and isotopic characteristics of the water and suspended particulate materials(SPM)in the Yellow River were investigated on the samples collected from 29 hydrological monitoring stations in the mainstem and several major tributaries during 2004 to 2007.TheδD andδ~(18)O values of the Yellow River water vary in large ranges from-32‰to-91‰and from-3.1‰to-12.5‰,respectively.The characters of H and O isotope variations indicate that the major sources of the Yellow River water are meteoric water and snow melting water,and water cycle in the Yellow River basin is affected strongly by evaporation process and human activity.The average SPM content(9.635g/L)of the Yellow River is the highest among the world large rivers.Compared with the Yangtze River,the Yellow River SPM has much lower clay content and significantly higher contents of clastic silicates and carbonates.In comparison to the upper crust rocks,the Yellow River SPM contains less SiO_2,CaO,K_2O and Na_2O,but more TFe_2O_3,Co,Ni,Cu,Zn,Pb and Cd.The abnormal high Cd contents found in some sample may be related to local industrial activity.The REE contents and distribution pattern of the Yellow River SPM are very close to the average value of the global shale.The averageδ~(30)Si_(SPM)in the Yellow River(-0.11‰)is slightly higher than the average value(-0.22‰)of the Yangtze River SPM.The major factors controlling theδ~(30)Si_(SPM)of the Yellow River are the soil supply,the isotopic composition of the soil and the climate conditions.The TDS in the Yellow River are the highest among those of world large rivers.Fair correlations are observed among Cl~-,Na~+,K~+,and Mg~(2+)contents of the Yellow River water,indicating the effect of evaporation.The Ca~(2+)and Sr~(2+)concentrations show good correlation to the SO_4~(2-)concentration rather than HCO_3~-concentration,reflecting its origin from evaporates.The NO_3~-contents are affected by farmland fertilization.The Cu,Zn and Cd contents in dissolved load of the Yellow River water are all higher than those of average world large rivers,reflecting the effect of human activity.The dissolved load in the Yellow River water generally shows a REE distribution pattern parallel to those for the Yangtze River and the Xijiang River.Theδ~(30)Si values of the dissolved silicon vary in a range from 0.4‰to 2.9‰,averaging1.34‰.The major processes controlling the D_(Si)andδ~(30)Si_(Diss)of the Yellow River water are the weathering process of silicate rocks,growth of phytolith in plants,evaporation,dissolution of phytolith in soil,growth of fresh water diatom,adsorption and desorption of aqueous monosilicic acid on iron oxide and human activities.The averageδ~(30)Si_(Diss)value of the Yellow River is significantly lower than that of the Nile River,Yangtze River and Siberia rivers,but higher than those of other rivers,reflecting their differences in chemical weathering and biological activity.Theδ~(34)S_(SO4)values of the Yellow River water range from-3.8‰to 14.1‰,averaging 7.97‰.There is some correlation between SO_4~(2-)content andδ~(34)S_(SO4).The factors controlling theδ~(34)S_(SO4)of the Yellow River water are the SO_4 in the meteoric water,the SO_4 from gypsum or anhydrite in evaporite rocks,oxidation and dissolution of sulfides in the mineral deposits,magmatic rocks and sedimentary rocks,the sulfate reduction and precipitation process and the sulfate from fertilizer.The~(87)Sr/~(86)Sr ratios of all samplesrange from 0.71041 to 0.71237,averaging 0.71128.The variations in the~(87)Sr/~(86)Sr ratio and Sr concentration of river water are primarily caused by mixing of waters of various origins with different~(87)Sr/~(86)Sr ratios and Sr contents resulting from water-rock interaction with different rock types.  相似文献   

7.
The reported source rocks for the abundant petroleum in the Tarim Basin, China range from Cambrian to Lower Ordovician and/or Upper Ordovician in age. However, the difference between the two groups of source rocks is not well characterized. In this study, pyrite was removed from eleven mature to over mature kerogen samples from source rocks using the method of CrCl2 reduction and grinding. The kerogen and coexisting pyrite samples were then analyzed for δ34S values. Results show that the kerogen samples from the Cambrian have δ34S values between +10.4‰ and +19.4‰. The values are significantly higher than those from the Lower Ordovician kerogen (δ34S of between +6.7‰ and +8.7‰), which in turn are generally higher than from the Upper Ordovician kerogen samples (δ34S of between ?15.3 and +6.8‰). The associated pyrite shows a similar trend but with much lower δ34S values. This stratigraphically controlled sulfur isotope variation parallels the evolving contemporary marine sulfate and dated oil δ34S values from other basins, suggesting that seawater sulfate and source rock age have an important influence on kerogen and pyrite δ34S values. The relatively high δ34S values in the Cambrian to Lower Ordovician source rocks are associated with abundant aryl isoprenoids, gammacerane and C35 homohopanes in the extractable organic matter, indicating that these source rocks were deposited in a bottom water euxinic environment with water stratification. Compared with the Upper Ordovician, the Cambrian to Lower Ordovician source rocks show abundance in C28 20R sterane, C23 tricyclic terpanes, 4,23,24-trimethyl triaromatic dinosteroids and depletion in C24 tetracyclic terpane, C29 hopane. Thus, δ34S values and biomarkers of source rock organic matter can be used for distinguishing the Cambrian and Upper Ordovician source rocks in the Tarim Basin.  相似文献   

8.
《地学前缘(英文版)》2020,11(4):1369-1380
This paper reports new geochronological (U–Pb) and isotope (C, O, and S) data to investigate the timing of mineralization and mode of ore genesis for the recently discovered Changtuxili Mn–Ag–Pb–Zn deposit, located on the western slopes of the southern Great Hinggan Range in NE China. The mineralization is hosted by intermediate–acidic lavas and pyroclastic rocks of the Baiyingaolao Formation. Three stages of mineralization are identified: quartz–pyrite (Stage I), galena–sphalerite–tetrahedrite–rhodochrosite (Stage II), and quartz–pyrite (Stage III). δ13C and δ18O values for carbonate from the ore vary from −8.51‰ to −4.96‰ and 3.97‰ to 15.90‰, respectively, which are indicative of a low-temperature alteration environment. δ34SV-CDT values of sulfides range from −1.77‰ to 4.16‰ and show a trend of equilibrium fractionation (δ34SPy ​> ​δ34SSp ​> ​δ34SGn). These features indicate that pyrite, sphalerite, and galena precipitated during the period of mineralization. The alteration mineral assemblage and isotope data indicate that the weakly acidic to weakly alkaline ore-forming fluid was derived largely from meteoric water and the ore-forming elements C and S originated from magma. During the mineralization, a geochemical barrier was formed by changes in the pH of the ore-forming fluid, leading to the precipitation of rhodochrosite. On the basis of the mineralization characteristics, new isotope data, and comparison with adjacent deposits, we propose that the Changtuxili Mn–Ag–Pb–Zn deposit is an intermediate-to low-sulfidation epithermal deposit whose formation was controlled by fractures and variability in the pH of the ore-forming fluid. The surrounding volcanic rocks yield zircon U–Pb ages of 160−146 ​Ma (Late Jurassic), indicating that the mineralization is younger than 146 ​Ma.  相似文献   

9.
δ 34S-values have been determined in 248 sulfide samples from different profiles through the ore bodies of the Sulitjelma pyrite-copper deposits. The values range for pyrite from ?4,1‰ to +9,2‰, but for an individual orebody the spread is generally much lower. Some profiles exhibit a systematic δ 34S decrease from the footwall to the hanging wall of the ore bodies, whereas laterally the S isotope composition in a distinct layer is rather uniform. Another trend from heavier to lighter sulfur exists from the center towards the margin of large porphyroblastic pyrite crystalls. Among the trace elements only the Co concentration in pyrite appears to be correlated with the δ-values. The sulfur-isotopic fractionation between coexisting sulfides is in agreement with the experience from other deposits, namely δ34Spyrite>δ34Spyrrhotite≈δ34Ssphalerite>δ34Schalcopyite  相似文献   

10.
《Applied Geochemistry》2005,20(1):23-39
Hydrothermal alteration at Los Azufres geothermal field is mostly propylitic with a progressive dehydration with depth and temperature increase. Argillic and advanced argillic zones overlie the propylitic zone owing to the activity of gases in the system. The deepest fluid inclusions (proto-fluid) are liquid-rich with low salinity, with NaCl dominant fluid type and ice melting temperatures (Tmi) near zero (0 °C), and salinities of 0.8 wt% NaCl equivalent. The homogenization temperature (Th)  = 325 ± 5 °C. The boiling zone shows Th = ±300 °C and apparent salinities between 1 and 4.9 wt% NaCl equivalent, implying a vaporization process and a very important participation of non-condensable gases (NCGs), mostly CO2. Positive clathrate melting temperatures (fusion) with Th = 150 °C are observed in the upper part of the geothermal reservoir (from 0 to 700 m depth). These could well be the evidence of a high gas concentration. The current water produced at the geothermal wells is NaCl rich (geothermal brine) and is fully equilibrated with the host rock at temperatures between T = 300 and 340 °C. The hot spring waters are acid-sulfate, indicating that they are derived from meteoric water heated by geothermal steam. The NCGs related to the steam dominant zone are composed mostly of CO2 (80–98% of all the gases). The gases represent between 2 and 9 wt% of the total mass of the fluid of the reservoir.The authors interpret the evolution of this system as deep liquid water boiling when ascending through fractures connected to the surface. Boiling is caused by a drop of pressure, which favors an increase in the steam phase within the brine ascending towards the surface. During this ascent, the fluid becomes steam-dominant in the shallowest zone, and mixes with meteoric water in perched aquifers. Stable isotope compositions (δ18O–δD) of the geothermal brine indicate mixing between meteoric water and a minor magmatic component. The enrichment in δ18O is due to the rock–water interaction at relatively high temperatures. δ13C stable isotope data show a magmatic source with a minor meteoric contribution for CO2. The initial isotopic value δ34SRES = −2.3‰, which implies a magmatic source. More negative values are observed for shallow pyrite and range from δ34S (FeS2) = −4‰ to −4.9‰, indicating boiling. The same fractionation tendencies are observed for fluids in the reservoir from results for δ18O.  相似文献   

11.
Concentration and isotope ratios (δ34SSO4 and δ18OSO4) of dissolved sulfate of groundwater were analyzed in a very large anaerobic aquifer system under the Lower Central Plain (LCP) (25,000 km2) in Thailand. Groundwater samples were collected in two different kinds of aquifers; type 1 with a saline water contribution and type 2 lateritic aquifers with no saline water contribution. Two different isotopic compositional trends were observed: in type 1 aquifers sulfate isotope ratios range from low values (+2.2‰ for δ34SSO4 and +8.0‰ for δ18OSO4) to high values (+49.9‰ for δ34SSO4 and +17.9‰ for δ18OSO4); in type 2 aquifers sulfate isotope ratios range from low values (−0.1‰ for δ34SSO4 and +12.2‰ for δ18OSO4) to high δ18OSO4 ratios (+18.4‰) but with low δ34SSO4 ratios (<+12.9‰). Isotopic comparison with possible source materials and theoretical geochemical models suggests that the sulfate isotope variation for type 1 aquifer groundwater can be explained by two main processes. One is the contribution of remnant seawater, which has experienced dissimilatory sulfate reduction in the marine clay, into recharge water of freshwater origin. This process accounts for the high salinity groundwater. The other process, explaining for the modest salinity groundwater, is the bacterial sulfate reduction of the mixture water between high salinity water and fresh groundwater. Isotopic variation of type 2 aquifer groundwater may also be explained by bacterial sulfate reduction, with slower reduction rate than that of the groundwater with saline water effect. The origin of groundwater sulfate with low δ34SSO4 but high δ18OSO4 is recognized as an important topic to be examined in a future investigation.  相似文献   

12.
《Applied Geochemistry》1997,12(4):483-496
The34S-to-32S ratio in dissolved SO4 has been studied in the Kalix River, Northern Sweden, and its catchment. Weekly sampling over 17 months revealed temporal variations from +5.3‰ up to +7.4‰ in the δ34S values in the river. Snow and rain samples showed lower δ34S values (average +5.6‰ and +5.0‰, respectively). The atmosphere is the major source for S in surface waters in the catchment, and the heavier δ34S values in the river are a result of SO4 reduction within the catchment.Most of the temporal variations in the δ34S value in the river are caused by a mixing of water from the mountain areas (relatively light δ34S) and the woodland. The δ34S value is relatively heavy in the woodland tributaries because of bacterial SO4 reduction in peatland areas influenced by groundwater.The highest δ34S values were measured during the spring flood, in June and in November. These heavy δ34S values are related to different types of water with diverse origins.The heavy δ34S values coinciding with the early spring flood originate from peatland areas in the woodland. Relatively heavy δ34S values (up to +14.4‰) were registered in mire water. Smaller variations of the δ34S value during summer and early autumn most likely were caused by the input of ground-mire water during heavy rains. A correlation between increased TOC concentrations and increased δ34S values was observed.The heavy δ34S values in June and November probably originate from SO4 reduction in bottom water and sediments in lakes within the catchment. Bottom water, enriched in34SSO4, was transported in the river during the spring and autumn overturn.  相似文献   

13.
Statistical evaluation of 3056 δ13C measurements in carbonate rocks and fossils shows that they record a 2‰ 13C depletion from the late Proterozoic to the early Paleozoic, a 2.5‰ enrichment to the Permian, and a 1.5‰ depletion to the Cenozoic. These variations, not controlled primarily by facies or alteration phenomena, correlate negatively with the δ34S sulfate secular trend, as confirmed by collation of 1083 δ34S measurements. The correlation suggests that the biologically mediated redox fluxes of the C and S cycles have been approximately balanced through this long span of geological time, generally levelling available oxygen. Such a redox system is consistent with the controlling mechanism proposed by Garrels and Perry (1974). Consequently, the sedimentary reservoirs of Corganic as well as Sbacteriological'have varied through geological time.  相似文献   

14.
Evaporite outcrops are rare in the Basque Cantabrian basin due to a rainy climate, but saline springs with total dissolved solids ranging from 0.8 to 260 g/L are common and have long been used to supply spas and salterns. New and existing hydrochemistry of saline springs are used to provide additional insight on the origin and underground extent of their poorly known source evaporites. Saline water hydrochemistry is related to dissolution of halite and gypsum from two evaporitic successions (Triassic “Keuper” and Lower Cretaceous “Wealden”), as supported by rock samples from outcrops and oil exploration drill cuttings. The δ34S value of gypsum in the Keuper evaporites and sulfate in the springs is δ34SSO4 = 14.06 ± 1.07‰ and δ18OSO4 = 13.41 ± 1.44‰, and the relationship between Cl/Br ratio of halite and water shows that waters have dissolved halite with Br content between 124 and 288 ppm. The δ34S value of gypsum in the Wealden evaporites and sulfate in the springs is δ34SSO4 = 19.66 ± 1.76‰, δ18OSO4 = 14.93 ± 2.35‰, and the relationship between Cl/Br ratio of halite and water shows that waters have dissolved halite with Br content between 15 and 160 ppm. Wealden evaporites formed in a continental setting after the dissolution of Keuper salt. Gypsum δ34SSO4 and δ18OSO4 modification from Keuper to Wealden evaporites was due mainly to bacterial SO4 reduction in an anoxic, organic matter-rich environment. Saline springs with Wealden δ34SSO4 values are present in a 70 × 20 km wide area. Saline water temperatures, their δ2HH2O and δ18OH2O values, and the geological structure defines a hydrogeological model, where meteoric water recharges at heights up to 620 m above spring levels and circulates down to 720 m below them, thereby constraining the height range of evaporite dissolution. Groundwater flow towards saline springs is driven by gravity and buoyancy forces constrained by a thrust and fault network.  相似文献   

15.
This paper investigated the sources and behaviors of sulfate in groundwater of the western North China Plain using sulfur and oxygen isotopic ratios. The groundwaters can be categorized into karst groundwater (KGW), coal mine drainage (CMD) and pore water (subsurface saturated water in interstices of unconsolidated sediment). Pore water in alluvial plain sediments could be further classified into unconfined groundwater (UGW) with depth of less than 30 m and confined groundwater (CGW) with depth of more than 60 m. The isotopic compositions of KGW varied from 9.3‰ to 11.3‰ for δ34SSO4 with the median value of 10.3‰ (n = 4) and 7.9‰ to 15.6‰ for δ18OSO4 with the median value of 14.3‰ (n = 4) respectively, indicating gypsum dissolution in karst aquifers. δ34SSO4 and δ18OSO4 values of sulfate in CMD ranged from 10.8‰ to 12.4‰ and 4.8‰ to 8.7‰ respectively. On the basis of groundwater flow path and geomorphological setting, the pore water samples were divided as three groups: (1) alluvial–proluvial fan (II1) group with high sulfate concentration (median values of 2.37 mM and 1.95 mM for UGW and CGW, respectively) and positive δ34SSO4 and δ18OSO4 values (median values of 8.8‰ and 6.9‰ for UGW, 12.0‰ and 8.0‰ for CGW); (2) proluvial slope (II2) group with low sulfate concentration (median values of 1.56 mM and 0.84 mM for UGW and CGW, respectively) and similar δ34SSO4 and δ18OSO4 values (median values of 9.0‰ and 7.4‰ for UGW, 10.2‰ and 7.7‰ for CGW); and (3) low-lying zone (II3) group with moderate sulfate concentration (median values of 2.13 mM and 1.17 mM for UGW and CGW, respectively) and more positive δ34SSO4 and δ18OSO4 values (median values of 10.7‰ and 7.7‰ for UGW, 20.1‰ and 8.8‰ for CGW). In the present study, three major sources of sulfate could be differentiated as following: sulfate dissolved from Ordovician to Permian rocks (δ34SSO4 = 10–35‰ and δ18OSO4 = 7–20‰), soil sulfate (δ34SSO4 = 5.9‰ and δ18OSO4 = 5.8‰) and sewage water (δ34SSO4 = 10.0‰ and δ18OSO4 = 7.6‰). Kinetic fractionations of sulfur and oxygen isotopes as a result of bacterial sulfate reduction (BSR) were found to be evident in the confined aquifer in stagnant zone (II3), and enrichment factors of sulfate–sulfur and sulfate–oxygen isotopes calculated by Rayleigh equation were −12.1‰ and −4.7‰ respectively along the flow direction of groundwater at depths of 60–100 m. The results obtained in this study confirm that detailed hydrogeological settings and identification of anthropogenic sources are critical for elucidating evolution of δ34SSO4 and δ18OSO4 values along with groundwater flow path, and this work also provides a useful framework for understanding sulfur cycling in alluvial plain aquifers.  相似文献   

16.
Fourteen stratiform, stratabound and vein-type sulphide occurrences in the Upper Allochthon of the Central–North Norwegian Caledonides have been studied for their sulphur, oxygen and hydrogen isotope composition. Depositional ages of host rocks to the stratabound and stratiform sulphide occurrences range from 590 to 640?Ma. The sulphides and their host rocks have been affected by polyphase deformation and metamorphism with a peak temperature of 650?°C dated to 432?Ma. A total of 104 sulphide and 2 barite samples were analysed for δ34S, 16 whole-rock and quartz samples for δ18O and 12 samples of muscovite for δD. The overall δ34S values range from ?14 to +31‰ with the majority of sampled sulphides lying within a range of +4 to +15‰. In most cases δ34S within each hand specimen behaves in accordance with the equilibrium fractionation sequence, δ34Sgn<δ34Scp<δ34Ssph<δ34Spy. A systematic increase in δ34S from the vein sulphides (?8‰) through schist/amphibolite-hosted (+6‰) and schist-hosted (+7 to +12‰) to dolomite-hosted (+12 to +31‰) occurrences is documented. The δ34S averages of the stratiform schist-hosted sulphides are 17 to 22‰ lower than in the penecontemporaneous seawater sulphate. The Bjørkåsen (+4 to +6‰) occurrence is a volcanogenic massive sulphide (VMS) transitional to sedimentary massive sulphide (SMS), exhalative, massive, pyritic deposit of Cu–Zn–Pb sulphides formed by fluids which obtained H2S via high-temperature reduction of seawater sulphate by oxidation of Fe2+ during the convective circulation of seawater through underlying rock sequences. The Raudvatn, volcanic-hosted, disseminated Cu sulphides (+6 to +8‰) obtained sulphur via a similar process. The Balsnes, stratiform, ‘black schist’-hosted, pyrite–pyrrhotite occurrence (?6 to ?14‰) is represented by typical diagenetic sulphides precipitated via bacteriogenic reduction of coeval (ca. 600?Ma) seawater sulphate (+25 to +35‰) in a system open to sulphate supply. The δ34S values of the Djupvik–Skårnesdalen (+7 to +12‰), Hammerfjell (+5 to 11‰), Kaldådalen (+10 to +12‰) and Njallavarre (+7 to +8‰) stratiform, schist-hosted, massive and disseminated Zn–Pb (±Cu) sulphide occurrences, as well as the stratabound, quartzite-hosted, Au-bearing arsenopyrite occurrence at Langvatnet (+7 to +11‰), suggest that thermochemically reduced connate seawater sulphate was a principal sulphur source. The Sinklien and Tårstad, stratabound, dolomite- and dolomite collapse breccia-hosted, Zn (±Cu–Pb) sulphides are marked by the highest enrichment in 34S (+20 to +31‰). The occurrences ?are?assigned to the Mississippi-Valley-type deposits.?High δ34S values require reduction/replacement of contemporaneous (ca. 590?Ma) evaporitic sulphate (+23 to +34‰) with Corg-rich fluids in a closed system. The Melkedalen (+12 to +15‰), stratabound, fault-controlled, Cu–Zn sulphide deposit is hosted by the ca. 595?Ma dolomitised Melkedalen marble. The deposit is composed of several generations of ore minerals which formed by replacement of host dolomite. Polyphase hydrothermal fluids were introduced during several reactivation episodes of the fault zone. The positive δ34S values with a very limited fractionation (<3‰) are indicative of the sulphide-sulphur generated through abiological, thermochemical reduction of seawater sulphate by organic material. The vein-type Cu (±Au–W) occurrences at Baugefjell, Bugtedalen and Baugevatn (?8 to ?4‰) are of hydrothermal origin and obtained their sulphur from igneous sources with a possible incorporation of sedimentary/diagenetic sulphides. In a broad sense, all the stratiform/stratabound, sediment-hosted, sulphide occurrences studied formed by epigenetic fluids within two probable scenarios which may be applicable separately or interactively: (1) expulsion of hot metal-bearing connate waters from deeper parts of sedimentary basins prior to nappe translation (late diagenetic/catagenetic/epigenetic fluids) or (2) tectonically driven expulsion in the course of nappe translation (early metamorphic fluids). A combination of (1) and (2) is favoured for the stratabound, fault-controlled, Melkedalen and Langvatnet occurrences, whereas the rest are considered to have formed within option (1). The sulphides and their host rocks were transported from unknown distances and thrust on to the Fennoscandian Shield during the course of the Caledonian orogeny. The displaced/allochthonous nature of the Ofoten Cu–Pb–Zn ‘metallogenetic province’ would explain the enigmatically high concentration of small-scale Cu–Pb–Zn deposits that occur only in this particular area of the Norwegian Caledonides.  相似文献   

17.
The S and O isotopic composition of dissolved SO4, used as a tracer for SO4 sources, was applied to the water of the Llobregat River system (NE Spain). The survey was carried out at 30 sites where surface water was sampled on a monthly basis over a period of 2a. The concentration of dissolved SO4 varied from 20 to 1575 mg L−1. Sulphur isotopic compositions clustered in two populations: one – 93% of the samples – had positive values with a mode of +9‰; the other had negative values and a mode of −5‰. Data for δ18OSO4 showed a mean value of +11‰, with no bi-modal distribution, though lower values of δ18O corresponded to samples with negative δ34S. These values can not be explained solely by the contribution of bedrock SO4 sources: that is, sulphide oxidation and the weathering of outcrops of sulphates, though numerous chemical sediments exist in the basin. Even in a river with a high concentration of natural sources of dissolved SO4, such as the Llobregat River, the δ34S values suggest that dissolved SO4 is controlled by a complex mix of both natural and anthropogenic sources. The main anthropogenic sources in this basin are fertilizers, sewage, potash mine effluent and power plant emissions. Detailed river water sampling, together with the chemical and isotopic characterisation of the main anthropogenic inputs, allowed determination of the influence of redox processes, as well as identification of the contribution of natural and anthropogenic SO4 sources and detection of spatial variations and seasonal changes among these sources. For instance, in the Llobregat River the input of fertilisers is well marked seasonally. Minimum values of δ34S are reported during fertilization periods – from January to March – indicating a higher contribution of this source. The dual isotope approach, δ34S and δ18O, is useful to better constrain the sources of SO4. Moreover, in small-scale studies, where the inputs are well known and limited, the mixing models can be enhanced and the contribution of the different sources can be quantified to some extent.  相似文献   

18.
《Applied Geochemistry》2005,20(7):1427-1444
Very high S oils (up to 14.7%) with H2S contents of up to 92% in the associated gas have been found in the Tertiary in the Jinxian Sag, Bohai Bay Basin, PR China. Several oil samples were analyzed for C and S stable isotopes and biomarkers to try to understand the origin of these unusual oil samples.The high S oils occur in relatively shallow reservoirs in the northern part of the Jinxian Sag in anhydrite-rich reservoirs, and are characteristic of oils derived from S-rich source rocks deposited in an enclosed and productive stratified hypersaline water body. In contrast, low S oils (as low as 0.03%) in the southern part of the Jinxian Sag occur in Tertiary lacustrine reservoirs with minimal anhydrite. These southern oils were probably derived from less S-rich source rocks deposited under a relatively open and freshwater to brackish lake environment that had larger amounts of higher plant inputs.The extremely high S oil samples (>10%) underwent biodegradation of normal alkanes resulting in a degree of concentration of S in the residual petroleum, although isoprenoid alkanes remain showing that biodegradation was not extreme. Interestingly, the high S oils occur in H2S-rich reservoirs (H2S up to 92% by volume) where the H2S was derived from bacterial SO4 reduction, most likely in the source rock prior to migration. Three oils in the Jinxian Sag have δ34S values from +0.3‰ to +16.2‰ and the oil with the highest S content shows the lightest δ34S value. This δ34S value for that oil is close to the δ34S value for H2S (∼0‰). It is possible that H2S was incorporated into functionalized compounds within the residual petroleum during biodegradation at depth in the reservoir thus accounting for the very high concentrations of S in petroleum.  相似文献   

19.
Greenstone belts contain several clues about the evolutionary history of primitive Earth. Here, we describe the volcano-sedimentary rock association exposed along the eastern margin of the Gavião Block, named the Northern Mundo Novo Greenstone Belt (N-MNGB), and present data collected with different techniques, including U–Pb–Hf–O isotopes of zircon and multiple sulfur isotopes (32S, 33S, 34S, and 36S) of pyrite from this supracrustal sequence. A pillowed metabasalt situated in the upper section of the N-MNGB is 3337 ± 25 Ma old and has zircon with εHf(t) =  ?2.47 to ?1.40, Hf model ages between 3.75 Ga and 3.82 Ga, and δ18O = +3.6‰ to +7.3‰. These isotopic data, together with compiled whole-rock trace element data, suggest that the mafic metavolcanic rocks formed in a subduction-related setting, likely a back-arc basin juxtaposed to a continental arc. In this context, the magma interacted with older Eoarchean crustal components from the Gavião Block. Detrital zircons from the overlying quartzites of the Jacobina Group are sourced from Paleoarchean rocks, in accordance with previous studies, yielding a maximum depositional age of 3353 ± 22 Ma. These detrital zircons have εHf(t) =  ?5.40 to ?0.84, Hf model ages between 3.66 Ga and 4.30 Ga, and δ18O = +4.8‰ to +6.4‰. The pyrite multiple sulfur isotope investigation of the 3.3 Ga supracrustal rocks from the N-MNGB enabled a further understanding of Paleoarchean sulfur cycling. The samples have diverse isotopic compositions that indicate sulfur sourced from distinct reservoirs. Significantly, they preserve the signal of the anoxic Archean atmosphere, expressed by MIF-S signatures (Δ33S between ?1.3‰ to +1.4‰) and a Δ36S/Δ33S slope of ?0.81 that is indistinguishable from the so-called Archean array. A BIF sample has a magmatic origin of sulfur, as indicated by the limited δ34S range (0 to +2‰), Δ33S ~ 0‰, and Δ36S ~ 0‰. A carbonaceous schist shows positive δ34S (2.1‰–3.5‰) and elevated Δ33S (1.2‰–1.4‰) values, with corresponding negative Δ36S between ?1.2‰ to ?0.2‰, which resemble the isotopic composition of Archean black shales and suggest a source from the photolytic reduction of elemental sulfur. The pillowed metabasalt displays heterogeneous δ34S, Δ33S, and Δ36S signatures that reflect assimilation of both magmatic sulfur and photolytic sulfate during hydrothermal seafloor alteration. Lastly, pyrite in a massive sulfide lens is isotopically similar to barite of several Paleoarchean deposits worldwide, which might indicate mass dependent sulfur processing from a global and well-mixed sulfate reservoir at this time.  相似文献   

20.
Stable SO4 isotopes (δ34S-SO4 and δ18O-SO4), and more occasionally δ15N-NO3 were studied in groundwater from seven hard-rock aquifer catchments. The sites are located in Brittany (France) and all are characterized by intensive agricultural activity. The purpose of the study was to investigate the potential use of these isotopes for highlighting the fate of both SO4 and NO3 in the different aquifer compartments. Nitrate-contaminated groundwater occurs in the regolith; δ34S fingerprints the origin of SO4, such as atmospheric deposition and fertilizers, and δ18O-SO4 provides evidence of the cycling of S within soil. The correlation between the δ18O-SO4 of sulfates and the δ15N-NO3 of nitrates suggests that S and N were both cycled in soil before being leached to groundwater. Autotrophic and heterotrophic denitrification was noted in fissured aquifers and in wetlands, respectively, the two processes being distinguished on the basis of stable SO4 isotopes. During autotrophic denitrification, both δ34S-SO4 and δ18O-SO4 decrease due to the oxidation of pyrite and the incorporation of O from the NO3 molecule in the newly formed SO4. Within wetlands, fractionation occurs of O isotopes on SO4 in favour of lighter isotopes, probably through reductive assimilation processes. Fractionation of S isotopes is negligible as the redox conditions are not sufficiently reductive for dissimilatory reduction. δ34S-SO4 and δ18O-SO4 data fingerprint the presence of a NO3-free brackish groundwater in the deepest parts of the aquifer. Through mixing with present-day denitrified groundwater, this brackish groundwater can contribute to significantly increase the salinity of pumped water from the fissured aquifer.  相似文献   

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