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1.
Correlative fractionation relationships of sulphur isotope data for coexisting sulphate and sulphide pairs from hydrothermal ore deposits on δ38S versus Δ34S diagrams are deciphered theoretically. Taking into account dissolved H2S and SO42- in hydrothermal fluids during precipitation of both sulphate and sulphide minerals, a 4-species closed system is suggested for describing the conservation of mass among all sulphur-bearing species on the δ-Δ diagrams. The covariation in the δ34S values of both sulphate and sulphide is ascribed to isotopic exchange between oxidized and reduced sulphur species during mineral precipitation. The isotopic exchange could be a thermodynamic process due to simple cooling of high temperature fluids, which results in an equilibrium fractionation, or a kinetic process due to mixing of two sulphur reservoirs, which leads to a disequilibrium fractionation. The δ34S value of total sulphur in a hydrothermal system could change due to the precipitation of minerals, or due to the escape of H2S and/or SO42-. Sulphur isotope data for anhydrite and pyrite pairs from the Luohe porphyrite iron deposit in the Yangtze River Valley is used to illustrate the mixing responsible for the disequilibrium fractionation.  相似文献   

2.
岩浆去气作用碳硫同位素效应   总被引：6，自引：0，他引：6       下载免费PDF全文
 根据开放体系条件下的瑞利分馏原理,并考虑岩浆中可能溶解的合碳和含硫组分,从理论上定量模式了岩浆去气作用对火成岩碳、硫同位素组成的影响。结果表明,岩浆CO2去气作用能够导致岩石中碳酸盐显着亏损13C,其δ13C值能够从原始-5‰变化到-20‰(PDB);岩浆CH4去气作用则导致岩石中碳酸盐相对富集13C,其δ13C值能够从原始-5‰变化到+4‰。岩浆SO2去气作用可以导致岩石中硫化物显着亏损34S,其δ34S值能够从0‰变化到-8‰(CDT);岩浆H2S去气作用则导致岩石中的硫化物相对富集4S,其δ34S值能够从0‰变化到+6‰。因此,除源岩原始同位素不均一性和地壳物质混染能引起火成岩的碳、硫同位素组成发生较大变化外,岩浆去气作用也是重要原因之一。  相似文献   

3.
The effect of Rayleigh distillation by outgassing of SO2 and H2S on the isotopic composition of sulfur remaining in silicate melts is quantitatively modelled.A threshold mole fraction of sulfur in sulfide component of the melts is reckoned to be of critical importance in shifting the δ^34S of the melts mith respect to the original magmas.The partial equilibrium fractionation in a magmatic system is evaluated by assuming that a non-equilibrium flux of sulfur occurs between magmatic volatiles and the melts,while an equilibrium fractionation is approached between sulfate and sulfide within the melts.The results show that under high fo2 conditions,the sulfate/sulfide ratio in a melt entds to increase,and the δ^34S value of sulfur in a solidified rock might then be shifted in the positive direction.This may either be due to Rayleigh outgassing in case the mole fraction of sulfide is less than the threshold,or due to a unidirectional increase in δ^34S value of the sulfate with decreaing temperature,Conversely,at low fo2,the sulfate/sulfide ratio tends to decrease and the δ^34S value of total sulfur could be driven in the negative direction,either because of the Rayleigh outgassing in case the mole fraction of sulfide is greater than the threshold,or because of a unidirectional decrease inδ^34S value of the sulfide.To establish isotopic equilibrium between sulfate and sulfide,the HM,QFM or WM buffers in the magmatic system are suggested to provide the redox couple that could simultaneously reduce the sulfate and oxidize the sulfide.CaO present in the silicatte Melts is also called upon to participate in the chemical equilibrium between sulfate and sulfide,Consequently,the δ^34S value of an igneous rock could considerably deviate from that of its original magma due to the influence of oxygen fugacity and temperature at the time of magma solidification.  相似文献   

4.
《Sedimentary Geology》1999,123(3-4):255-273
This study investigates the sulphur source of gypsum sulphate and dissolved groundwater sulphate in the Central Namib Desert, home to one of Africa's most extensive gypsum (CaSO4·2H2O) accumulations. It investigates previously suggested sulphate precursors such as bedrock sulphides and decompositional marine biogenic H2S and studies the importance of other potential sources in order to determine the origin of gypsum and dissolved sulphate in the region. An attempt has been made to sample all possible sulphur sources, pathways and types of gypsum accumulations in the Central Namib Desert. We have subjected those samples to sulphur isotopic analyses and have compiled existing results. In addition, ionic ratios of Cl/SO4 are used to determine the presence of non-sea-salt (NSS) sulphur in groundwater and to investigate processes affecting groundwater sulphate. In contrast to previous work, this study proposes that the sulphur cycle, and the formation of gypsum, in the Namib Desert appears to be dominated by the deposition of atmospheric sulphates of phytoplanktonic origin, part of the primary marine production of the Benguela upwelling cells. The aerosol sulphates are subjected to terrestrial storage within the gypsum deposits on the hyper-arid gravel plain and are traceable in groundwater including coastal sabkhas. The hypothesis of decompositional marine biogenic H2S or bedrock sulphide sources, as considered previously for the Namib Desert, cannot account for the widespread accumulation of gypsum in the region. The study area in the Central Namib Desert, between the Kuiseb and Omaruru rivers, features extensive gypsum accumulations in a ca. 50–70 km wide band, parallel to the shore. They consist of surficial or shallow pedogenic gypsum crusts in the desert pavement, hydromorphic playa or sabkha gypsum, as thin isolated pockets on bedrock ridges and as discrete masses of gypsum selenite along some faults. The sulphur isotopic values (δ34S ‰CDT) of these occurrences are between δ34S +13.0 and +18.8‰, with lower values in proximity to sulphuric ore bodies (δ34S +3.1 and +3.4‰). Damaran bedrock sulphides have a wide range from δ34S −4.1 to +13.8‰ but seem to be significant sources on a local scale at the most. Dissolved sulphate at playas, sabkhas, springs, boreholes and ephemeral rivers have an overall range between δ34S +9.8 and +20.8‰. However, they do not show a systematic geographical trend. The Kalahari waters have lower values, between δ34S +5.9 and +12.3‰. Authigenic gypsum from submarine sediments in the upwelling zone of the Benguela Current between Oranjemund and Walvis Bay ranges between δ34S −34.6 to −4.6‰. A single dry atmospheric deposition sample produced a value of δ34S +15.9‰. These sulphur isotopic results, complemented by meteorological, hydrological and geological information, suggest that sulphate in the Namib Desert is mainly derived from NSS sulphur, in particular oxidation products of marine dimethyl sulphide CH3SCH3 (DMS). The hyper-arid conditions prevailing along the Namibian coast since Miocene times favour the overall preservation of the sulphate minerals. However, sporadic and relatively wetter periods have promoted gypsum formation: the segregation of sulphates from the more soluble halite, and the gradual seaward redistribution of sulphate. This study suggests that the extreme productivity of the Benguela Current contributes towards the sulphur budget in the adjacent Namib Desert.  相似文献   

5.
Sulphur cycling in organic-rich marine sediments from a Scottish fjord   总被引：1，自引：0，他引：1  
In this study, the biogeochemical transformations of sulphur in organic‐rich marine sediments in a Scottish fjord are investigated by a combination of pore water and sediment geochemistry with sulphide diffusive gradient thin‐film probes and sulphate isotopic data (δ34S and δ18O). Particular attention is paid to sulphur cycling in the upper sediment profile where sulphate reduction occurs but free sulphide is below the detection limits of conventional pore water geochemical analysis but quantifiable by sulphide diffusive gradient thin film. In the uppermost part of the sediment core, δ18O sulphate decreased from near‐sea water values to +7‰, indicating that anoxic sulphide oxidation dominated during this interval. Sulphate δ34S remained unchanged as there was no net sulphate reduction (i.e. reduction was balanced by re‐oxidation). Below 4 cm depth, there was a slight increase in sulphate δ34S from 20‰ to 23‰ associated with minor accumulation of iron sulphide. The δ18O of the sulphate also increased, to around +10‰ at 10 cm depth, as a result of the isotopic exchange of sulphate–oxygen with pore water and/or sulphur disproportionation reactions mediated during sulphur cycling. These processes continued to increase the δ18O of the sulphate to 14‰ at 20 cm depth with no further change in the δ34S of the sulphate. Below 20 cm depth, free sulphide is detectable in pore waters and both the δ34S of the sulphate and sulphide increase with depth with an offset controlled by kinetic fractionation during bacterial sulphate reduction. The δ34S of the sedimentary organic fraction shifted towards lower, more bacteriogenic, values with depth in the profile, without any increase in the size of this sulphur pool. Thus, the organic sulphur fraction was open to interaction with bacteriogenic sulphide without the occurrence of net addition. Therefore, caution should be exercised when using sulphur isotopic compositions to infer simple net addition of bacteriogenic sulphide to the organic sulphur fraction.  相似文献   

6.
The Navia gold belt is located in the West Asturian-Leonese Zone of the Iberian Variscan Orogen. The host rocks of the mineralization are quartzites, sandstones and black shales of Cambro-Ordovician age. The gold belt extends along 35 km and has five major veins: Penedela, Encarnita, Fornaza, Carmina and S. Jose. The ores belong to at least four associations having contrasting mineralogies and textures. The δ34S values for individual mineral phases reflect the polyphase metallogenic history. The older association (Stage 1) is Fe-Mn-rich and is made up of spessartine, grunerite-dannemorite and quartz, with magnetite, pyrrhotite and chalcopyrite as metallic phases. The mineralization of Stage 1 is followed by the As-rich Stage 2 with quartz, arsenopyrite and pyrite. The δ34S values for pyrite range from 14.9 to 19.9 per mil (n = 16), and for arsenopyrite from 13.2 to 17.3 per mil (n = 7). The observed isotopic homogeneity likely implies isotopic equilibrium at the scale of the gold vein. Stage 3 contains a coarse-grained base metal sulphide-rich association. The δ4S values for sphalerite range from 16.4 to 20.6 per mil (n= 16), and for galena from 17.0 to 18.7 per mil (n = 11). δ34Ssp > δ34Sgl suggests that the sulphur isotopic fractionation of the ore-forming system had reached equilibrium. The youngest crosscutting mineral association (Stage 4) consists of Pb-Sb sulphosalts, bornite, electrum and quartz. The δ34S values for sulphosalts range from 9.7 to 15.8 per mil, showing the lightest results of the Navia sulphides.The relatively tight clustering of δ34S values of the Au-related sulphides, and the results of fluid inclusions and paragenetic studies, can be interpreted to indicate that the hydrothermal fluids of the last three stages were dominated by H2S. In the H2S predominant field, sulphide minerals precipitating from solutions would exhibit δ34S values similar to the δ34SΣS value of the ore fluid. The heavy δ34SΣS of the Navia fluids is consistent with leaching of sulphur from the host rocks. The main sulphur source could be diagenetic pyrite from the siliciclastic rocks of the Cabos and Luarca Formations, which exhibit δ34S values from 8.3 to 21.2 per mil. An additional sulphur-source in Stage 3 would be the leaching of disseminated sphalerite and galena present in Cambrian carbonates.  相似文献   

7.
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   

8.
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   

9.
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   

10.
The sulphide deposits of the Iberian Pyrite Belt (IPB) represent an ore province of global importance. Our study presents 113 new sulphur isotope analyses from deposits selected to represent the textural spectrum of ores. Measured 34S values range from −26 to +10‰ mostly for massive and stockwork ores, in agreement with data previously published. In situ laser 34S analyses reveals a close correlation of 34S with texture. Primary diagenetic textures are dominated by relatively low 34S (−8‰ to −2‰), whereas stockwork feeder textures are dominated by higher 34S (∼+3‰ to +5‰). Intermediate textures (mainly coarse textures in stratiform zones) have intermediate 34S, although they are mostly dominated by the high 34S component. Rare barite has a homogeneous 34S around +18‰, which is consistent with direct derivation from Lower Carboniferous seawater sulphate. A dual source of sulphide sulphur in the IPB deposits has been considered. A hydrothermal source, derived from reduction of coeval seawater sulphate in the convective systems, is represented by sulphide in the feeder zones. Here variations in 34S are caused by variations in the extent of the sulphate reduction, which governs the SO4:H2S ratio. The second end-member was derived from the bacterial reduction of coeval seawater sulphate at or near the surface, as reflected in the primary textures. A distinct geographical variation in 34S and texture from SW (more bacteriogenic and primary textures) to NE (more hydrothermal textures and 34S) which reflects a variation in the relative input of each source was likely controlled by local geological environments. Given that the sulphur isotope characteristics of the IPB deposits are unlike most VMS and Kuroko deposits, and noting the dominance of a mixed reduced sedimentary and volcanic environment, we suggest that the IPB could represent an ore style which is intermediate between volcanic and sedimentary hosted massive sulphide types. Received: 8 October 1997 / Accepted: 14 May 1998  相似文献   

11.
《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   

12.
Reaction between dissolved water and sulphide was experimentally investigated in soda-lime-silicate (NCS) and sodium trisilicate (NS3) melts at temperatures from 1000 to 1200 °C and pressures of 100 or 200 MPa in internally heated gas pressure vessels. Diffusion couple experiments were conducted at water-undersaturated conditions with one half of the couple being doped with sulphide (added as FeS or Na2S; 1500-2000 ppm S by weight) and the other with H2O (∼3.0 wt.%). Additionally, two experiments were performed using a dry NCS glass cylinder and a free H2O fluid. Here, the melt was water-saturated at least at the melt/fluid interface. Profiling by electron microprobe (sulphur) and infrared microscopy (H2O) demonstrate that H2O diffusion in the melts is faster by 1.5-2.3 orders of magnitude than sulphur diffusion and, hence, H2O can be considered as a rapidly diffusing oxidant while sulphur is quasi immobile in these experiments.In Raman spectra a band at 2576 cm−1 appears in the sulphide - H2O transition zone which is attributed to fundamental S-H stretching vibrations. Formation of new IR absorption bands at 5025 cm−1 (on expense of the combination band of molecular H2O at 5225 cm−1) and at 3400 cm−1 was observed at the front of the in-diffusing water in the sulphide bearing melt. The appearance and intensity of these two IR bands is correlated with systematic changes in S K-edge XANES spectra. A pre-edge excitation at 2466.5 eV grows with increasing H2O concentration while the sulphide peak at 2474.0 eV decreases in intensity relative to the peak at 2477.0 eV and the feature at 2472.3 eV becomes more pronounced (all energies are relative to the sulphate excitation, calibrated to 2482.5 eV). The observations by Raman, IR and XANES spectroscopy indicate a well coordinated S2− - H2O complex which was probably formed in the glasses during cooling at the glass transition. No oxidation of sulphide was observed in any of the diffusion couple experiments. On the contrary, XANES spectra from experiments conducted with a free H2O fluid show complete transformation of sulphide to sulphate near the melt surface and coexistence of sulphate and sulphide in the center of the melt. This can be explained by a lower H2O activity in the diffusion couple experiments or by the need of a sink for hydrogen (e.g., a fluid which can dissolve high concentration of hydrogen) to promote oxidation of sulphide by H2O via the reaction S2− + 4H2O = SO42− + 4H2. Sulphite could not be detected in any of the XANES spectra implying that this species, if it exists in the melt, it is a subordinate or transient species only.  相似文献   

13.
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   

14.
The Tyndrum Pb+Zn veins, hosted by late Proterozoic quartzites, were probably generated in the Tournaisian (360 Ma). By determination of sulphur isotopic ratios of vein minerals three aspects of the Tyndrum mineralization were addressed, (i) sulphate sulphur sources; (ii) reduced sulphur source; (iii) isotopic equilibrium in the vein system including geothermometry. Twelve galenas have δ34S values ranging from +3.55 ‰ to +6.38 ‰ (this excludes one value of +11.21 ‰ from a large but nearly barren quartz vein). Other sulphides are enriched or depleted in 34S in the sense expected for isotopic equilibrium although there is no evidence for isotopic equilibrium between the vein minerals. The sulphide sulphur source was probably in the Dalradian metasediments where disseminated pyrite averages +6 ‰. Baryte had δ34S values averaging 14 ‰ and was therefore not in isotopic equilibrium with sulphides: a continental groundwater source is most likely.  相似文献   

15.
《Applied Geochemistry》1987,2(2):205-211
Carbon and sulphur isotope investigations of human urinary stones have been expanded to relate such data to various body components and to diet. Techniques include isotopic determinations for various body components, for example, hair and urine, as well as trace sulphate and sulphide in apatite-struvite stones.Hair from individuals in Calgary was found to be, on average, about 3‰ depleted in13C in comparison to samples from Hawaii. Uric acid stones from both locations were found to be 1 to 3‰ enriched in13C, compared to hair. Oxalate stones from Calgary had δ13C values very close to those of hair. In contrast, oxalate stones from 31 patients from Honolulu fit the regression lineδ13Coxalate= 0.8 δ13Chair− 4.4‰, with a correlation coefficient of 0.77. It remains debatable as to whether the isotopic differences between the stones and hair reflects preferential incorporation of dietary components or kinetic isotope effects during biochemical conversions. There was no evidence in the data from Honolulu that ethnic background significantly influenced the carbon isotope composition of hair or kidney stones. There was a suggestion that recent arrivals had hair and stones slightly depleted in13C as compared to longer residents.The δ34S values of cystine stones from Calgary were markedly consistent, near 0‰, and isotopic variations among different body components of individuals were of the order of 1‰.The trace sulphate content of a bladder stone from Papua New Guinea, was 300ppm S, whereas the sulphide content was negligible (determined by in vacuo Kiba extraction). The total S content of three samples from Calgary averaged 250 ppm, whereas 150 ppm was found for two stones each from Quito, Ecuador and Honolulu, Hawaii. For stones other than the speciment from Papua New Guinea, the sulphate-to-sulphide ratio varied from 1 to 4. The source of sulphide is uncertain but degradation of organic S could contribute to this fraction during Kiba extraction. The small range of δ34S values (+3.5 to +7.4‰) for trace total S in the phosphate-containing urinary stones is believed to reflect only a fraction of the global variation of these materials. Trace sulphate was variably enriched in34S (0 to 9‰) as compared to sulphide. Neither these enrichments, nor the sulphate-to-sulphide ratio, could be related to the struvite-to-apatite ratio.There were no significant differences in the carbon and sulphur isotope compositions of hair from patients and non-stone formers. Both the carbon and sulphur isotope variations can be attributed to the isotopic compositions of diets and the superposition of small kinetic isotope effects during biochemical conversions.  相似文献   

16.
<正>The Ordos Cretaceous Groundwater Basin,located in an arid-semiarid area in northwestern China,is a large-style groundwater basin.SO_4~(2-) is one of the major harmful components in groundwater.Dissolved SO_4~(2-) concentrations,andδ~(34)S-SO_4~(2-) andδ~(18)O-SO_4~(2-) in groundwater from 14 boreholes and in gypsum from aquifer were analyzed.Results show that SO_4~(2-) in shallow groundwaters originates from precipitation,sulfide oxidation,and dissolution of stratum sulphate,with a big range ofδ~(34)S values,from-10.7‰to 9.2‰,and addition of SO_4~(2-) in deep groundwater results from dissolution of stratum sulphate,with biggerδ~(34)S values,from 7.8‰to 18.5‰,compared with those in shallow groundwater.This research also indicates that three types of sulphate are present in the strata,and characterized by highδ~(34)S values and highδ~(18)O values-style,highδ~(34)S values and middleδ~(18)O valuesstyle, middleδ~(34)S values and lowδ~(18)O values-style,respectively.Theδ~(34)S-SO_4~(2-) andδ~(18)O-SO_4~(2-) in groundwater have a good perspective for application in distinguishing different groundwater systems and determining groundwater circulation and evolution in this area.  相似文献   

17.
The sulphur isotopic composition of ocean water sulphate   总被引：3，自引：0，他引：3  
The sulphur isotopic composition of ocean water sulphate was determined, using the SF6 method, for samples from various depths of the Geosecs Stations II and 3 and for a single Pacific Ocean surface sample. The total spread in values obtained is less than that found in previous studies and is consistent with the experimental precision except for one Geosecs II sample which has an unusually low δ34S value. The mean value, + 20.99%., is markedly different from the hitherto accepted value of +20.0%.. The difference is attributed to the greater accuracy obtained when SF6 rather than SO2 is used as the sample gas for sulphur isotope analysis.  相似文献   

18.
This contribution describes the setup and operating procedures of the first operational laser ablation microprobe for stable (sulphur) isotope analysis in Australia as well as some brief geological applications. A significant feature on this laser ablation microprobe is automated gas purification and analysis; operator control is only required to locate and ablate sample targets. As with other laboratories, samples were ablated in an oxygen atmosphere, producing a SO2/O2 gas mixture. SO2 was separated from this mixture by either of two techniques. In the first technique, SO2 was condensed into a liquid N2 trap by cryogenic pumping, and O2 was pumped away. This resulted in the collection of 60–70% of the produced SO2. In the second technique, SO2 was condensed into a liquid N2 trap as the SO2/O2 mixture was slowly bled away. This technique collected 90–95% of the SO2, with a small fractionation of 0.16%. Laser ablation and SO2 collection via the second technique required a mineral dependent, additive correction of 2.85–5.75% to convert raw δ34S values to δ34SCDT. These correction factors are mineral and laboratory dependent, and from our data, seem to be dependent on the quality of polish of the ablated sample. Precision (1σ) of laser ablation sulphur isotope analysis is 0.4–0.5%o for 150 μm ablation craters.

Preliminary results of studies on samples from the Broken Hill, Hellyer and active sea floor Pacmanus deposits indicate that laser ablation microprobe analysis can show subtle variations in δ34S not apparent using either conventional or SHRIMP analysis. Laser ablation analysis indicates a larger range, but similar mean values, to conventional analysis on the same samples.  相似文献   

19.
The δ34S-values of total sulfur in the Jurassic tholeiite flows on Mt. Falla in Antarctica range from ?1.45 to +11.73‰. The concentrations of sulfur range from 80 to 480 ppm, which is typical of subaerial lava flows that lose varying proportions of sulfur by out-gassing of SO2. The concentrations of magnetite range from less than 1% to more than 4% and appear to correlate inversely with the total Fe content of the flows. However, the five flows which are anomalously enriched in 34S also have elevated magnetite concentrations. We suggest that the elevated magnetite concentrations and the 34S enrichment were both caused by high oxygen fugacities (fO2) in the melt. The magnetite concentrations are affected by the fugacity of oxygen through equilibrium in the FMQ buffer whereas the enrichment of the flows in 34S resulted from outgassing of SO2 at fO2 greater than ～ 10?8 atm. The dependence of δ34S and the magnetite concentrations of the flows on fO2 is supported by the stratigraphic variation of these parameters and by their direct linear correlation.  相似文献   

20.
Evaluation of the extent of volatile element recycling in convergent margin volcanism requires delineating likely source(s) of magmatic volatiles through stable isotopic characterization of sulfur, hydrogen and oxygen in erupted tephra with appropriate assessment of modification by degassing. The climactic eruption of Mt. Mazama ejected approximately 50 km3 of rhyodacitic magma into the atmosphere and resulted in formation of a 10-km diameter caldera now occupied by Crater Lake, Oregon (lat. 43°N, long. 122°W). Isotopic compositions of whole-rocks, matrix glasses and minerals from Mt. Mazama climactic, pre-climactic and postcaldera tephra were determined to identify the likely source(s) of H2O and S. Integration of stable isotopic data with petrologic data from melt inclusions has allowed for estimation of pre-eruptive dissolved volatile concentrations and placed constraints on the extent, conditions and style of degassing.Sulfur isotope analyses of climactic rhyodacitic whole rocks yield δ34S values of 2.8-14.8‰ with corresponding matrix glass values of 2.4-13.2‰. δ34S tends to increase with stratigraphic height through climactic eruptive units, consistent with open-system degassing. Dissolved sulfur concentrations in melt inclusions (MIs) from pre-climactic and climactic rhyodacitic pumices varies from 80 to 330 ppm, with highest concentrations in inclusions with 4.8-5.2 wt% H2O (by FTIR). Up to 50% of the initial S may have been lost through pre-eruptive degassing at depths of 4-5 km. Ion microprobe analyses of pyrrhotite in climactic rhyodacitic tephra and andesitic scoria indicate a range in δ34S from −0.4‰ to 5.8‰ and from −0.1‰ to 3.5‰, respectively. Initial δ34S values of rhyodacitic and andesitic magmas were likely near the mantle value of 0‰. Hydrogen isotope (δD) and total H2O analyses of rhyodacitic obsidian (and vitrophyre) from the climactic fall deposit yielded values οf −103 to −53‰ and 0.23-1.74 wt%, respectively. Values of δD and wt% H2O of obsidian decrease towards the top of the fall deposit. Samples with depleted δD, and mantle δ18O values, have elevated δ34S values consistent with open-system degassing. These results imply that more mantle-derived sulfur is degassed to the Earth’s atmosphere/hydrosphere through convergent margin volcanism than previously attributed. Magmatic degassing can modify initial isotopic compositions of sulfur by >14‰ (to δ34S values of 14‰ or more here) and hydrogen isotopic compositions by 90‰ (to δD values of −127‰ in this case).  相似文献   

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