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1.
Despite reduced anthropogenic deposition during the last decades, deposition sulphate may still play an important role in the biogeochemical cycles of S and many catchments may act as net sources of S that may remain for several decades. The aim of this study is to elucidate the temporal and spatial dynamics of both SO42− and δ34SSO4 in stream water from catchments with varying percentage of wetland and forest coverage and to determine their relative importance for catchment losses of S. Stream water samples were collected from 15 subcatchments ranging in size from 3 to 6780 ha, in a boreal stream network, northern Sweden. In forested catchments (<2% wetland cover) S-SO42− concentrations in stream water averaged 1.7 mg L−1 whereas in wetland dominated catchments (>30% wetland cover) the concentrations averaged 0.3 mg L−1. A significant negative relationship was observed between S-SO42− and percentage wetland coverage (r2 = 0.77, p < 0.001) and the annual export of stream water SO42− and wetland coverage (r2 = 0.76, p < 0.001). The percentage forest coverage was on the other hand positively related to stream water SO42− concentrations and the annual export of stream water SO42− (r2 = 0.77 and r2 = 0.79, respectively). The annual average δ34SSO4 value in wetland dominated streams was +7.6‰ and in streams of forested catchments +6.7‰. At spring flood the δ34SSO4 values decreased in all streams by 1‰ to 5‰. The δ34SSO4 values in all streams were higher than the δ34SSO4 value of +4.7‰ in precipitation (snow). The export of S ranged from 0.5 kg S ha−1 yr−1 (wetland headwater stream) to 3.8 kg S ha−1 yr−1 (forested headwater stream). With an average S deposition in open field of 1.3 kg S ha−1 yr−1 (2002-2006) the mass balance results in a net export of S from all catchments, except in catchments with >30% wetland. The high temporal and spatial resolution of this study demonstrates that the reducing environments of wetlands play a key role for the biogeochemistry of S in boreal landscapes and are net sinks of S. Forested areas, on the other hand were net sources of S.  相似文献   

2.
Sulfur isotopic compositions were determined by ion microprobe for 36 spots on anhydrite crystals in trachyandesitic pumices erupted from El Chichón Volcano in 1982. Individual anhydrite crystals are homogeneous in δ34S, within the ±1‰ (2σ) uncertainty of the method, but crystal-to-crystal variations are large (+2.5 to +10.9‰). The mean δ34S for anhydrite (+6.4 ± 2.1‰, 1σ) is significantly lower than earlier results for bulk anhydrite separates (+9.0 to +9.2‰). The difference between the mean δ34S values in these two populations may reflect a grain-size effect, with heavier sulfur concentrated in smaller anhydrite crystals, few of which were analyzed by ion microprobe. Variations in δ34S show no correlation with complex textures in anhydrite revealed by cathodoluminescence color. Ion-microprobe analyses of δ34S were also obtained on six ovoid-shaped inclusions of pyrrhotite, chalcopyrite, and/or intermediate sulfide solid solution hosted by silicate or oxide crystals, interpreted to be magmatic (δ34S = −0.1 to +2.7‰; mean +0.7‰), and on four irregularly shaped multiphase sulfide fragments in the matrix, interpreted as xenocrystic, which range widely in δ34S (−3.7 to +5.5‰). We evaluate four different mixing scenarios involving (1) magmatic anhydrite and sedimentary sulfate, (2) magmatic anhydrite and hydrothermal anhydrite, and anhydrite and coexisting sulfide crystals precipitated in different domains of a common magma reservoir that were affected by (3) different degrees of degassing or (4) different degrees of crustal sulfur contamination. The model involving physical contamination of sedimentary sulfate is considered untenable. The other three models are considered to be viable, but none of them can explain all observations. The results of this study and other recent investigations prompt a re-evaluation of the sulfur budget for the 1982 El Chichón eruption. We estimate that 2.2 × 1013 g of S was emitted, and that 58 wt.% of the sulfur was present as anhydrite prior to eruption, with the remainder in a vapor phase, with H2S/SO2 ≈ 9. The bulk magmatic δ34S value for the 1982 El Chichón trachyandesite is estimated as +4.1 to +5.8‰, typical of the relatively heavy sulfur isotopic compositions that characterize subduction-related magmas.  相似文献   

3.
Sulfur isotope compositions of pumice and adsorbed volatiles on ash from the first historical eruption of Anatahan volcano (Mariana arc) are presented in order to constrain the sources of sulfur erupted during the period 10-21 May, 2003. The isotopic composition of S extracted from erupted pumice has a narrow range, from δ34SV-CDT +2.6‰ to +3.2‰, while the composition of sulfur adsorbed onto ash has a larger range (+2.8‰ to +5.3‰). Fractionation modeling for closed and open system scenarios suggests that degassing of SO2 raised the δ34SV-CDT value of S dissolved in the melt from an initial composition of between +1.6‰ and +2.6‰ for closed-system degassing, or between −0.5‰ and +1.5‰ for open-system degassing, however closed-system degassing is the preferred model. The calculated values for the initial composition of the magma represent a MORB-like (δ34SV-CDT ∼ 0‰) mantle source with limited contamination by subducted seawater sulfate (δ34SV-CDT +21‰). Modeling also suggests that the δ34SV-CDT value of SO2 gas in closed-system equilibrium with the degassed magma was between +0.9‰ and +2.5‰. The δ34SV-CDT value of sulfate adsorbed onto ash in the eruption plume (+2.8‰ to +5.1‰) is consistent with sulfate formation by oxidation of magmatic SO2 in the eruption column. The sulfur isotope composition of sulfate adsorbed to ash changes from lower δ34S values for ash erupted early in the eruption to higher δ34S values for ash erupted later in the eruption. We interpret the temporal/stratigraphic change in sulfate isotopic composition to primarily reflect a change in the isotopic composition of magmatic SO2 released from the progressively degassing magma and is attributed to the expulsion of an accumulated gas phase at the beginning of the eruption. More efficient oxidation of magmatic SO2 gas to sulfate in the early water-rich eruption plume probably contributed to the change in S isotope compositions observed in the ash leachates.  相似文献   

4.
The concentrations and the isotopic compositions of S, N and C were studied in soils and in the dominant plant species of three forested watersheds (Québec, Canada) located along a latitudinal and atmospheric deposition gradient. Large increases in S, N and C isotope ratios (up to 3.9‰, 10‰, 2.6‰, respectively) were observed with increasing soil depth at the three watersheds. These increases were accompanied by a strong decrease in elemental concentrations resulting in a strong negative relationship between these two variables. Both S and N concentrations throughout the soil profile and δ34S and δ15N in the mineral soil appeared to increase with increasing S and N deposition rates and decreasing latitude. A strong positive linear relationship was found between δ34S and δ15N (R2 = 0.72) values and between organic S and N concentrations (R2 = 0.96) in soils. The slope of the linear relationship between δ34S and δ15N (δ34S = f(δ15N)) indicated that isotopic fractionation was almost 4 times higher for S than for N during transformations that occurred in soil. However, this difference might reflect a higher degree of openness of the S cycle compared to the N cycle rather than an isotope effect per se. Overall, the results suggest that N and S inputs significantly impact the isotope ratios and the concentrations of N and S in the soils, and that S and N were closely associated and subject to similar processes with the same isotopic effects throughout the soil profile. Contrary to most studies, δ34S-SO4 in stream water of the most northerly site with the lowest S deposition rate was significantly higher than δ34S-SO4 in atmospheric depositions but similar to the δ34S of the bulk mineral soil. It suggests that the mineral soil actually contributes a large portion of the stream S-SO4 for this site.  相似文献   

5.
Climate change in the SW USA is likely to involve drier conditions and higher surface temperatures. In order to better understand the evolution of water chemistry and the sources of aqueous SO4 in these semi-arid settings, chemical and S isotope compositions were determined of springs, groundwater, and bedrock associated with a Permian fractured carbonate aquifer located in the southern Sacramento Mountains, New Mexico, USA. The results suggest that the evolution of water chemistry in the semi-arid carbonate aquifer is mainly controlled by dedolomitization of bedrock, which was magnified by increasing temperature and increasing dissolution of gypsum/anhydrite along the groundwater flow path. The δ34S of dissolved SO4 in spring and groundwater samples varied from +9.0‰ to +12.8‰, reflecting the mixing of SO4 from the dissolution of Permian gypsum/anhydrite (+12.3‰ to +13.4‰) and oxidation of sulfide minerals (−24.5‰ to −4.2‰). According to S isotope mass balance constraints, the contribution of sulfide-derived SO4 was considerable in the High Mountain recharge areas, accounting for up to ∼10% of the total SO4 load. However, sulfide weathering decreased in importance in the lower reaches of the watershed. A smaller SO4 input of ∼2–4% was contributed by atmospheric wet deposition. This study implies that the δ34S variation of SO4 in semi-arid environments can be complex, but that S isotopes can be used to distinguish among the different sources of weathering. Here it was found that H2SO4 dissolution due to sulfide oxidation contributes up to 5% of the total carbonate weathering budget, while most of the SO4 is released from bedrock sources during dedolomitization.  相似文献   

6.
An anomalous enrichment in marine sulfate δ34SSO4 is preserved in globally-distributed latest Ediacaran-early Cambrian strata. The proximity of this anomaly to the Ediacaran-Cambrian boundary and the associated evolutionary radiation has invited speculation that the two are causally related. Here we present a high-resolution record of paired sulfate (δ34SSO4) and pyrite (δ34Spyr) from sediments spanning ca. 547-540 million years ago (Ma) from the Ara Group of the Huqf Supergroup, Sultanate of Oman. We observe an increase in δ34SSO4 from ∼20‰ to ∼42‰, beginning at ca. 550 Ma and continuing at least through ca. 540 Ma. There is a concomitant increase in δ34Spyr over this interval from ∼ −15‰ to 10‰. This globally correlative enrichment, here termed the Ara anomaly, constitutes a major perturbation to the sulfur cycle. The absolute values of δ34Spyr reported here and in equivalent sections around the world, require the isotopic composition of material entering the ocean (δ34Sin) to be significantly more enriched than modern (∼3‰) values, likely in excess of 12‰ during the late Ediacaran-early Cambrian. Against this background of elevated δ34Sin, the Ara anomaly is explained not by increased fractionation between sulfate and pyrite (Δδ34S), but by an increase in pyrite burial (fpyr), most likely driven by enhanced primary production and sequestration of organic carbon, consistent with earlier reports of elevated organic carbon burial and widespread phosphorite deposition.  相似文献   

7.
The acidophilic iron-oxidizing bacterium, Acidithiobacillus ferrooxidans, plays a part in the pyrite oxidation process and has been widely studied in order to determine the kinetics of the reactions and the isotopic composition of dissolved product sulphates, but the details of the oxidation processes at the surface of pyrite are still poorly known. In this study, oxygen and sulphur isotopic compositions (δ18O and δ34S) were analyzed for dissolved sulphates and water from experimental aerobic acidic (pH < 2) pyrite oxidation by A. ferrooxidans. The oxidation products attached to the pyrite surfaces were studied for their morphology (SEM), their chemistry (Raman spectroscopy) and for their δ18O (ion microprobe). They were compared to abiotically (Fe3+, H2O2, O2) oxidized pyrite surface compounds in order to constrain the oxidation pathways and to look for the existence of potential biosignatures for this system.The pyrite dissolution evolved from non-stoichiometric (during the first days) to stoichiometric (with increasing time) resulting in dissolved sulphates having distinct δ18O (e.g. +11.0‰ and −2.0‰, respectively) and δ34S (+4.5‰ and +2.8‰, respectively) values. The “oxidation layer” at the surface of pyrite is complex and made of iron oxides, sulphate, polysulphide, elemental sulphur and polythionates. Bio- and Fe3+-oxidation favour the development of monophased micrometric bumps made of hematite or sulphate while other abiotic oxidation processes result in more variable oxidation products. The δ18O of these oxidation products at the surface of oxidized pyrites are strongly variable (from ≈−40‰ to ≈+30‰) for all experiments.Isotopic fractionation between sulphates and pyrite, Δ34SSO4-pyrite, is equal to −1.3‰ and +0.4‰ for sulphates formed by stoichiometric and non-stoichiometric processes, respectively. These two values likely reflect either a S-S or a Fe-S bond breaking process. The Δ18OSO4-H2O and Δ18OSO4-O2 are estimated to be ≈+16‰ and ≈−25‰, respectively. These values are higher than previously published data and may reflect biological effects. The large δ18O heterogeneity measured at the surfaces of oxidized pyrites, whatever the oxidant, may be related (i) to the existence of local surface environments isolated from the solution in which the oxidation processes are different and (ii) to the stabilization at the pyrite surface of reaction intermediates that are not in isotopic equilibrium with the solution. Though the oxygen isotopic composition of surface oxidation products cannot be taken as a direct biosignature, the combined morphological, chemical and isotopic characterization of the surfaces of oxidized pyrites may furnish clues about a biological activity on a mineral surface.  相似文献   

8.
Copper isotope fractionation in acid mine drainage   总被引：4，自引：0，他引：4  
We measured the Cu isotopic composition of primary minerals and stream water affected by acid mine drainage in a mineralized watershed (Colorado, USA). The δ65Cu values (based on 65Cu/63Cu) of enargite (δ65Cu = −0.01 ± 0.10‰; 2σ) and chalcopyrite (δ65Cu = 0.16 ± 0.10‰) are within the range of reported values for terrestrial primary Cu sulfides (−1‰ < δ65Cu < 1‰). These mineral samples show lower δ65Cu values than stream waters (1.38‰ ? δ65Cu ? 1.69‰). The average isotopic fractionation (Δaq-min = δ65Cuaq − δ65Cumin, where the latter is measured on mineral samples from the field system), equals 1.43 ± 0.14‰ and 1.60 ± 0.14‰ for chalcopyrite and enargite, respectively. To interpret this field survey, we leached chalcopyrite and enargite in batch experiments and found that, as in the field, the leachate is enriched in 65Cu relative to chalcopyrite (1.37 ± 0.14‰) and enargite (0.98 ± 0.14‰) when microorganisms are absent. Leaching of minerals in the presence of Acidithiobacillus ferrooxidans results in smaller average fractionation in the opposite direction for chalcopyrite (Δaq-mino=-0.57±0.14‰, where mino refers to the starting mineral) and no apparent fractionation for enargite (Δaq-mino=0.14±0.14‰). Abiotic fractionation is attributed to preferential oxidation of 65Cu+ at the interface of the isotopically homogeneous mineral and the surface oxidized layer, followed by solubilization. When microorganisms are present, the abiotic fractionation is most likely not seen due to preferential association of 65Cuaq with A. ferrooxidans cells and related precipitates. In the biotic experiments, Cu was observed under TEM to occur in precipitates around bacteria and in intracellular polyphosphate granules. Thus, the values of δ65Cu in the field and laboratory systems are presumably determined by the balance of Cu released abiotically and Cu that interacts with cells and related precipitates. Such isotopic signatures resulting from Cu sulfide dissolution should be useful for acid mine drainage remediation and ore prospecting purposes.  相似文献   

9.
The main terminal processes of organic matter mineralization in anoxic Black Sea sediments underlying the sulfidic water column are sulfate reduction in the upper 2-4 m and methanogenesis below the sulfate zone. The modern marine deposits comprise a ca. 1-m-deep layer of coccolith ooze and underlying sapropel, below which sea water ions penetrate deep down into the limnic Pleistocene deposits from >9000 years BP. Sulfate reduction rates have a subsurface maximum at the SO42−-CH4 transition where H2S reaches maximum concentration. Because of an excess of reactive iron in the deep limnic deposits, most of the methane-derived H2S is drawn downward to a sulfidization front where it reacts with Fe(III) and with Fe2+ diffusing up from below. The H2S-Fe2+ transition is marked by a black band of amorphous iron sulfide above which distinct horizons of greigite and pyrite formation occur. The pore water gradients respond dynamically to environmental changes in the Black Sea with relatively short time constants of ca. 500 yr for SO42− and 10 yr for H2S, whereas the FeS in the black band has taken ca. 3000 yr to accumulate. The dual diffusion interfaces of SO42−-CH4 and H2S-Fe2+ cause the trapping of isotopically heavy iron sulfide with δ34S = +15 to +33‰ at the sulfidization front. A diffusion model for sulfur isotopes shows that the SO42− diffusing downward into the SO42−-CH4 transition has an isotopic composition of +19‰, close to the +23‰ of H2S diffusing upward. These isotopic compositions are, however, very different from the porewater SO42− (+43‰) and H2S (−15‰) at the same depth. The model explains how methane-driven sulfate reduction combined with a deep H2S sink leads to isotopically heavy pyrite in a sediment open to diffusion. These results have general implications for the marine sulfur cycle and for the interpretation of sulfur isotopic data in modern sediments and in sedimentary rocks throughout earth’s history.  相似文献   

10.
Understanding past climate change is critical to the interpretation of earth history. Even though relative temperature change has been readily assessed in the marine record, it has been more difficult in the terrestrial record due to restricted taxonomic distribution and isotopic fractionation. This problem could be overcome by the use of multiple paleoproxies. Therefore, the δ18O isotopic composition of five paleoproxies (rodent tooth enamel, δ18OPhosphate = +17.7 ± 2.0‰ n = 74 (VSMOW); fish scale ganoine δ18OPhosphate = +19.7 ± 0.7‰ n = 20 (VSMOW); gastropod shell δ18OCalcite = −1.7 ± 1.3‰ n = 50 (VPDB); charophyte gyrogonite δ18OCalcite = −2.4 ± 0.5‰ n = 20 (VPDB); fish otolith δ18OAragonite = δ18O = −3.6 ± 0.6‰ n = 20 (VPDB)) from the Late Eocene (Priabonian) Osborne Member (Headon Hill Formation, Solent Group, Hampshire Basin, UK) were determined. Because diagenetic alteration was shown to be minimal the phosphate oxygen component of rodent tooth enamel (as opposed to enamel carbonate oxygen) was used to calculate an initial δ18OLocal water value of 0.0 ± 3.4‰. However, a skewed distribution, most likely as a result of the ingestion of evaporating water, necessitated the calculation of a corrected δ18OLocal water value of −1.3 ± 1.7‰ (n = 62). This δ18OLocal water value corresponds to an approximate mean annual temperature of 18 ± 1°C. Four other mean paleotemperatures can also be calculated by combining the δ18OLocal water value with four independent freshwater paleoproxies. The calculated paleotemperature using the fish scale thermometry equations most likely represents the mean temperature (21 ± 2°C) of the entire length of the growing season. This should be concordant with the paleotemperature calculated using the Lymnaea shell thermometry equation (23 ± 2°C). The lack of concordance is interpreted to be the result of diagenetic alteration of the originally aragonitic Lymnaea shell to calcite. The mean paleotemperature calculated using the charophyte gyrogonite thermometry equation (21 ± 2°C), on the other hand, most likely represents the mean temperature of a single month toward the end of the growing season. The fish otolith mean paleotemperature (28 ± 2°C) most likely represents the mean temperature of the warmest months of the growing season. An approximate mean annual temperature of 18 ± 1°C, in addition to a mean growing season paleotemperature of 21 ± 2°C (using fish scale only) with a warmest month temperature of 28 ± 2°C, and high associated standard deviations suggest that a subtropical to warm temperate seasonal climate existed during the deposition of the Late Eocene Osborne Member.  相似文献   

11.
We present high-precision measurements of Mg and Fe isotopic compositions of olivine, orthopyroxene (opx), and clinopyroxene (cpx) for 18 lherzolite xenoliths from east central China and provide the first combined Fe and Mg isotopic study of the upper mantle. δ56Fe in olivines varies from 0.18‰ to −0.22‰ with an average of −0.01 ± 0.18‰ (2SD, n = 18), opx from 0.24‰ to −0.22‰ with an average of 0.04 ± 0.20‰, and cpx from 0.24‰ to −0.16‰ with an average of 0.10 ± 0.19‰. δ26Mg of olivines varies from −0.25‰ to −0.42‰ with an average of −0.34 ± 0.10‰ (2SD, n = 18), opx from −0.19‰ to −0.34‰ with an average of −0.25 ± 0.10‰, and cpx from −0.09‰ to −0.43‰ with an average of −0.24 ± 0.18‰. Although current precision (∼±0.06‰ for δ56Fe; ±0.10‰ for δ26Mg, 2SD) limits the ability to analytically distinguish inter-mineral isotopic fractionations, systematic behavior of inter-mineral fractionation for both Fe and Mg is statistically observed: Δ56Feol-cpx = −0.10 ± 0.12‰ (2SD, n = 18); Δ56Feol-opx = −0.05 ± 0.11‰; Δ26Mgol-opx = −0.09 ± 0.12‰; Δ26Mgol-cpx = −0.10 ± 0.15‰. Fe and Mg isotopic composition of bulk rocks were calculated based on the modes of olivine, opx, and cpx. The average δ56Fe of peridotites in this study is 0.01 ± 0.17‰ (2SD, n = 18), similar to the values of chondrites but slightly lower than mid-ocean ridge basalts (MORB) and oceanic island basalts (OIB). The average δ26Mg is −0.30 ± 0.09‰, indistinguishable from chondrites, MORB, and OIB. Our data support the conclusion that the bulk silicate Earth (BSE) has chondritic δ56Fe and δ26Mg.The origin of inter-mineral fractionations of Fe and Mg isotopic ratios remains debated. δ56Fe between the main peridotite minerals shows positive linear correlations with slopes within error of unity, strongly suggesting intra-sample mineral-mineral Fe and Mg isotopic equilibrium. Because inter-mineral isotopic equilibrium should be reached earlier than major element equilibrium via chemical diffusion at mantle temperatures, Fe and Mg isotope ratios of coexisting minerals could be useful tools for justifying mineral thermometry and barometry on the basis of chemical equilibrium between minerals. Although most peridotites in this study exhibit a narrow range in δ56Fe, the larger deviations from average δ56Fe for three samples likely indicate changes due to metasomatic processes. Two samples show heavy δ56Fe relative to the average and they also have high La/Yb and total Fe content, consistent with metasomatic reaction between peridotite and Fe-rich and isotopically heavy melt. The other sample has light δ56Fe and slightly heavy δ26Mg, which may reflect Fe-Mg inter-diffusion between peridotite and percolating melt.  相似文献   

12.
Previous geochemical and microbiological studies in the Cariaco Basin indicate intense elemental cycling and a dynamic microbial loop near the oxic-anoxic interface. We obtained detailed distributions of sulfur isotopes of total dissolved sulfide and sulfate as part of the on-going CARIACO time series project to explore the critical pathways at the level of individual sulfur species. Isotopic patterns of sulfate (δ34SSO4) and sulfide (δ34SH2S) were similar to trends observed in the Black Sea water column: δ34SH2S and δ34SSO4 were constant in the deep anoxic water (varying within 0.6‰ for sulfide and 0.3‰ for sulfate), with sulfide roughly 54‰ depleted in 34S relative to sulfate. Near the oxic-anoxic interface, however, the δ34SH2S value was ∼3‰ heavier than that in the deep water, which may reflect sulfide oxidation and/or a change in fractionation during in situ sulfide production through sulfate reduction (SR). δ34SH2S and Δ33SH2S data near the oxic-anoxic interface did not provide unequivocal evidence to support the important role of sulfur-intermediate disproportionation suggested by previous studies. Repeated observation of minimum δ34SSO4 values near the interface suggests ‘readdition’ of 34S-depleted sulfate during sulfide oxidation. A slight increase in δ34SSO4 values with depth extended over the water column may indicate a reservoir effect associated with removal of 34S-depleted sulfur during sulfide production through SR. Our δ34SH2S and Δ33SH2S data also do not show a clear role for sulfur-intermediate disproportionation in the deep anoxic water column. We interpret the large difference in δ34S between sulfate and sulfide as reflecting fractionations during SR in the Cariaco deep waters that are larger than those generally observed in culturing studies.  相似文献   

13.
Groundwater from karst subterranean streams is among the world’s most important sources of drinking water supplies, and the hydrochemical characteristics of karst water are affected by both natural environment and people. Therefore, the study of karst groundwater hydrochemistry and its solutes’ sources is very important to ensure the normal function of life support systems. This paper focused on the major ion chemistry and sulfate isotope of karst groundwater in Chongqing for tracing the sulfate sources and related hydrochemical processes. Hydrochemical types of karst groundwater in Chongqing were mainly of the Ca-HCO3 type or Ca(Mg)-HCO3 type. However, some hydrochemical types were the K + Na + Ca-SO4 type (G25 site) or Ca-HCO3 + SO4 type (G26 and G14 sites), indicating that the hydrochemistry of these sites may be strongly influenced by anthropogenic activities or unique geological characteristics. The δ34S-SO4 2? of collected karst groundwater sample fell into a range of ?6.8 to 21.5 ‰, with a mean value of 5.6 ‰. In dolomite aquifer, the δ34S-SO4 2? value ranges from ?4.3 to 11.0 ‰, and in limestone aquifer, it ranged from ?6.8 to 21.5 ‰. The groundwater samples from different land use types showed distinctive δ34S-SO4 2? value. The δ34S-SO4 2? value of groundwater samples had range of ?6.8 to 16.7 ‰ (mean 4.0 ‰, n = 11) in cultivated land areas, 1.5–21.5 ‰ (mean 7.2 ‰, n = 20) in forested land areas, and ?4.3 to 0.8 ‰ (mean ?1.7 ‰, n = 2) in coalmine areas. The δ34S-SO4 2? values of groundwater samples collected from factory area and town area were 2.2 and 9.9 ‰, respectively. According to the δ34S information of potential sulfate sources, this paper discussed the possible sulfate sources of collected karst groundwater samples in Chongqing. The variations of both δ34S and 1/SO4 2? values of the groundwater samples indicated that the atmospheric acid deposition (AAD), dissolution of gypsum (GD), oxidation of sulfide mineral (OS) or anthropogenic inputs (SF: sewage or fertilizer) contributed to sulfate in karst groundwater. The influence of oxidation of sulfide mineral, atmospheric acid deposit and anthropogenic inputs to groundwater in Chongqing karst areas was much widespread. For protecting, sustaining, and utilizing the groundwater resources, the sewage possibly originating from urban, mine or industrial area must be controlled and treated, and the use of fertilizer should be limited.  相似文献   

14.
Organic carbon (OC) and total nitrogen (TN) concentrations and stable isotope ratios (δ13C, δ15N) of fine (<50 μm) size fractions of deep-sea sediments from the central North Atlantic were employed to identify changes in sources of organic matter over the past 50 ka BP. Ambient glacial sediments are characterised by values that reflect mixtures of marine and terrestrial inputs (averages ± 1σ: OC/TN = 7.6 ± 0.8; δ13C = −22.8 ± 1.0‰; δ15N = 5.5 ± 0.6‰). δ13C, OC, and TN concentrations shift to higher values during the Holocene, indicating a gradual decrease of fine terrigenous supply to the North Atlantic. The unchanged δ15N record between last glacial and Holocene stages indicates that the central North Atlantic region remained oligotrophic at least during the past 50 ka BP, but additional studies are required to support this result in terms of nitrogen oceanic budget. During the phases of enhanced ice-rafted detrital supply corresponding to prominent Heinrich events (HL1, HL2, HL4, and HL5), fine-sized sedimentary organic matter has lower OC and TN concentrations, contrasting sharply with those of ambient glacial sediments. Lower δ13C (down to −28‰) and δ15N (down to 1.6‰) values and high OC:TN ratios (up to 14.7 ± 1.1) are found for HL1, HL2, and with lesser extent for HL4. These values reflect enhanced detrital supply originating from poorly differentiated soil horizons that characterise periglacial climate conditions and from organic matter-bearing rock sources of the underlying geological basement. During HL5, only the δ13C offset records the input of fine size ice-rafted organic matter. Gradually changing soil development conditions during the time interval covering HL5 to HL1 (marine isotope stages 5 to 2), as well as varying erosion levels, have been hypothesized on the basis of constant δ13C, increasing OC/TN and decreasing δ15N values.  相似文献   

15.
Multiple sulfur isotope system is a powerful new tracer for atmospheric, volcanic, and biological influences on sulfur cycles in the anoxic early Earth. Here, we report high-precision quadruple sulfur isotope analyses (32S/33S/34S/36S) of barite, pyrite in barite, and sulfides in related hydrothermal and igneous rocks occurring in the ca. 3.5 Ga Dresser Formation, Western Australia. Our results indicate that observed isotopic variations are mainly controlled by mixing of mass-dependently (MD) and non-mass-dependently fractionated (non-MD) sulfur reservoirs. Based on the quadruple sulfur isotope systematics (δ34S-Δ33S-Δ36S) for these minerals, four end-member sulfur reservoirs have been recognized: (1) non-MD sulfate (δ34S = −5 ± 2‰; Δ33S = −3 ± 1‰); (2) MD sulfate (δ34S = +10 ± 3‰); (3) non-MD sulfur (δ34S > +6‰; Δ33S > +4‰); and (4) igneous MD sulfur (δ34S = Δ33S = 0‰). The first and third components show a clear non-MD signatures, thus probably represent sulfate and sulfur aerosol inputs. The MD sulfate component (2) is enriched in 34S (+10 ± 3‰) and may have originated from microbial and/or abiotic disproportionation of volcanic S or SO2. Our results reconfirm that the Dresser barites contain small amounts of pyrite depleted in 34S by 15-22‰ relative to the host barite. These barite-pyrite pairs exhibit a mass-dependent relationship of δ33S/δ34S with slope less than 0.512, which is consistent with that expected for microbial sulfate reduction and is significantly different from that of equilibrium fractionation (0.515). The barite-pyrite pairs also show up to 1‰ difference in Δ36S values and steep Δ36S/Δ33S slopes, which deviate from the main Archean array (Δ36S/Δ33S = −0.9) and are comparable to isotope effects exhibited by sulfate reducing microbes (Δ36S/Δ33S = −5 to −11). These new lines of evidence support the existence of sulfate reducers at ca. 3.5 Ga, whereas microbial sulfur disproportionation may have been more limited than recently suggested.  相似文献   

16.
An investigation of the thermal waters in the Ústí nad Labem area in the northeastern part of the Eger Rift has been carried out, with the principal objective of determining their origin. Waters from geothermal reservoirs in the aquifers of the Bohemian Cretaceous Basin (BCB) from depths of 240 to 616 m are exploited here. For comparison, thermal waters of the adjacent Teplice Spa area were also incorporated into the study. Results based on water chemistry and isotopes indicate mixing of groundwater from aquifers of the BCB with groundwater derived from underlying crystalline rocks of the Erzgebirge Mts. Unlike thermal waters in Dě?ín, which are of Ca–HCO3 type, there are two types of thermal waters in Ústí nad Labem, Na–HCO3–Cl–SO4 type with high TDS values and Na–Ca–HCO3–SO4 type with low TDS values. Carbon isotope data, speciation calculations, and inverse geochemical modeling suggest a significant input of endogenous CO2 at Ústí nad Labem in the case of high TDS groundwaters. Besides CO2 input, both silicate dissolution and cation exchange coupled with dissolution of carbonates may explain the origin of high TDS thermal waters equally well. This is a consequence of similar δ13C and 14C values in endogenous CO2 and carbonates (both sources have 14C of 0 pmc, endogenous CO2 δ13C around −3‰, carbonates in the range from −5‰ to +3‰ V-PDB). The source of Cl− seems to be relict brine formed in Tertiary lakes, which infiltrated into the deep rift zone and is being flushed out. The difference between high and low TDS groundwaters in Ústí nad Labem is caused by location of the high mineralization groundwater wells in CO2 emanation centers linked to channel-like conduits. This results in high dissolution rates of minerals and in different δ13C(DIC) and 14C(DIC) fingerprints. A combined δ34S and δ18O study of dissolved SO4 indicates multiple SO4 sources, involving SO4 from relict brines and oxidation of H2S. The study clearly demonstrates potential problems encountered at sites with multiple sources of C, where several evolutionary groundwater scenarios are possible.  相似文献   

17.
The quality of water in the Upper Floridan aquifer near Valdosta, Georgia is affected locally by discharge of Withlacoochee River water through sinkholes in the river bed. Data on transient tracers and other dissolved substances, including Cl−, 3H, tritiogenic helium-3 (3He), chlorofluorocarbons (CFC-11, CFC-12, CFC-113), organic C (DOC), O2 (DO), H2S, CH4, δ18O, δD, and 14C were investigated as tracers of Withlacoochee River water in the Upper Floridan aquifer. The concentrations of all tracers were affected by dilution and mixing. Dissolved Cl−, δ18O, δD, CFC-12, and the quantity (3H+3He) are stable in water from the Upper Floridan aquifer, whereas DOC, DO, H2S, CH4, 14C, CFC-11, and CFC-113 are affected by microbial degradation and other geochemical processes occurring within the aquifer. Groundwater mixing fractions were determined by using dissolved Cl− and δ18O data, recognizing 3 end-member water types in the groundwater mixtures: (1) Withlacoochee River water (δ18O=−2.5±0.3‰, Cl−=12.2±2 mg/l), (2) regional infiltration water (δ18O=−4.2±0.1‰, Cl−=2.3±0.1 mg/l), and (3) regional paleowater resident in the Upper Floridan aquifer (δ18O=−3.4±0.1‰, Cl−=2.6±0.1 mg/l) (uncertainties are ±1σ). Error simulation procedures were used to define uncertainties in mixing fractions. Fractions of river water in groundwater range from 0 to 72% and average 10%. The influence of river-water discharge on the quality of water in the Upper Floridan aquifer was traced from the sinkhole area on the Withlacoochee River 25 km SE in the direction of regional groundwater flow. Infiltration of water is most significant to the N and NW of Valdosta, but becomes negligible to the S and SE in the direction of general thickening of post-Eocene confining beds overlying the Upper Floridan aquifer.  相似文献   

18.
This study investigates the application of sulphur isotope ratios (δ34S) in combination with carbon (δ13C) and nitrogen (δ15N) ratios to understand the influence of environmental sulphur on the isotopic composition of archaeological human and faunal remains from Roman era sites in Oxfordshire, UK. Humans (n = 83), terrestrial animals (n = 11), and freshwater fish (n = 5) were analysed for their isotope values from four locations in the Thames River Valley, and a broad range of δ34S values were found. The δ34S values from the terrestrial animals were highly variable (−13.6‰ to +0.5‰), but the δ34S values of the fish were clustered and 34S-depleted (−20.9‰ to −17.3‰). The results of the faunal remains suggest that riverine sulphur influenced the terrestrial sulphur isotopic signatures. Terrestrial animals were possibly raised on the floodplains of the River Thames, where highly 34S-depleted sulphur influenced the soil. The humans show the largest range of δ34S values (−18.8‰ to +9.6‰) from any archaeological context to date. No differences in δ34S values were found between the males (−7.8 ± 6.0‰) and females (−5.3 ± 6.8‰), but the females had a linear correlation (R2 = 0.71; p < 0.0001) between their δ15N and δ34S compositions. These δ34S results suggest a greater dietary variability for the inhabitants of Roman Oxfordshire than previously thought, with some individuals eating solely terrestrial protein resources and others showing a diet almost exclusively based on freshwater protein such as fish. Such large dietary variability was not visible by analysing only the carbon and nitrogen isotope ratios, and this research represents the largest and most detailed application of δ34S analysis to examine dietary practices (including breastfeeding and weaning patterns) during the Romano-British Period.  相似文献   

19.
Many waters sampled in Yellowstone National Park, both high-temperature (30–94 °C) and low-temperature (0–30 °C), are acid–sulfate type with pH values of 1–5. Sulfuric acid is the dominant component, especially as pH values decrease below 3, and it forms from the oxidation of elemental S whose origin is H2S in hot gases derived from boiling of hydrothermal waters at depth. Four determinations of pH were obtained: (1) field pH at field temperature, (2) laboratory pH at laboratory temperature, (3) pH based on acidity titration, and (4) pH based on charge imbalance (at both laboratory and field temperatures). Laboratory pH, charge imbalance pH (at laboratory temperature), and acidity pH were in close agreement for pH < 2.7. Field pH measurements were predominantly used because the charge imbalance was <±10%. When the charge imbalance was generally >±10%, a selection process was used to compare acidity, laboratory, and charge balance pH to arrive at the best estimate. Differences between laboratory and field pH can be explained based on Fe oxidation, H2S or S2O3 oxidation, CO2 degassing, and the temperature-dependence of pK2 for H2SO4. Charge imbalances are shown to be dependent on a speciation model for pH values <3. The highest SO4 concentrations, in the thousands of mg/L, result from evaporative concentration at elevated temperatures as shown by the consistently high δ18O values (−10‰ to −3‰) and a δD vs. δ18O slope of 3, reflecting kinetic fractionation. Low SO4 concentrations (<100 mg/L) for thermal waters (>350 mg/L Cl) decrease as the Cl− concentration increases from boiling which appears inconsistent with the hypothesis of H2S oxidation as a source of hydrothermal SO4. This trend is consistent with the alternate hypothesis of anhydrite solubility equilibrium. Acid–sulfate water analyses are occasionally high in As, Hg, and NH3 concentrations but in contrast to acid mine waters they are low to below detection in Cu, Zn, Cd, and Pb concentrations. Even concentrations of SO4, Fe, and Al are much lower in thermal waters than acid mine waters of the same pH. This difference in water chemistry may explain why certain species of fly larvae live comfortably in Yellowstone’s acid waters but have not been observed in acid rock drainage of the same pH.  相似文献   

20.
This paper presents the results of an isotopic study of spring waters in ?wi?tokrzyski (Holy Cross Mountain) National Park (?NP), south-central Poland. The δ34SV-CDT and δ18OV-SMOW of soluble sulfates (n = 40) varied from 0.5‰ to 18.1‰ and from 3.5‰ to 12.2‰, respectively. The average δ34S values are closely similar to those of rainwater, soils and rocks (comprising scattered pyrite). This suggests that soluble sulfates in the springs originated from mixing of recent and historic deposition, sulfates derived from pyrite oxidation, and CS-mineralization in soils and debris. An additional anthropogenic sulfur input (inorganic fertilizer) occurs in the water of spring S-61 located in the ?wi?tokrzyski National Park buffer zone. The δ18OV-SMOW of spring waters (n = 4) were in the range of −10.6‰ to −10.2‰ indicating that they are derived from vadose groundwater in ?NP. This was the first isotope study of spring waters in the national parks of Poland. It enabled the determination of sulfur pathways and discrimination between natural and anthropogenic sources of this element in a relatively pristine area.  相似文献   

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