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1.
Sulfur isotope composition of carbonate-associated sulfate (δ34SCAS) and carbon isotope composition of carbonate (δ13Ccarb) were jointly investigated on the Late Permian rocks at Shangsi Section, Guanyuan, Northeast Sichuan, South China. Both δ34SCAS and δ13Ccarb show gradual decline trends in Late Permian strata, inferring the occurrence of the long-term variation of marine environmental
conditions. Associated with the long-term variation are the two coincident negative shifts in δ34SCAS and δ13Ccarb, with one occurring at the boundary between Middle Permian Maokou Formation and Late Permian Wujiaping Formation and another
at Middle Dalong Formation. Of significance is the second shift which clearly predates the regression and the biotic crisis
at the end of Permian at Shangsi Section, providing evidence that a catastrophic event occurred prior to the biotic crisis.
The frequent volcanisms indicated by the volcanic rocks or fragments, and the upwelling are proposed to cause the second negative
excursion. An abrupt extreme negative δ34SCAS (ca. −20‰) associated with a low relative concentration of CAS and total organic carbon without large change in δ13Ccarb is found at the end of the second shift, which might arise from the short-term oxygenation of bottom waters and sediments
that resulted from the abrupt sea level drop. 相似文献
2.
《Gondwana Research》2014,25(3-4):1276-1282
Concentrations of total organic matter (TOC), carbon isotopic compositions of carbonate and organic matter (δ13Ccarb, δ13Corg), and sulfur isotopic compositions of carbonate associated sulfate (δ34Ssulfate) across the Guadalupian–Lopingian (G–L) boundary were analyzed from identical samples of Tieqiao section, Laibin, Guangxi province, South China. The δ13Ccarb values show a positive excursion from − 0.45‰ to the peak of 3.80‰ in the Laibin limestone member of the Maokou Formation, followed by a drastic drop to − 2.60‰ in the lowest Heshan formation, then returned to about 1.58‰. Similar to the trends of the δ13Ccarb values, Δ13Ccarb–org values also show a positive excursion followed by a sharp negative shift. The onset of a major negative carbon isotope excursion postdates the end Guadalupian extinction that indicates subsequent severe disturbance of the ocean–atmosphere carbon cycle. The first biostratigraphic δ34Ssulfate values during the G–L transition exhibit a remarkable fluctuation: a dramatic negative shift followed by a rapid positive shift, ranging from 36.88‰ to − 37.41‰. These sulfate isotopic records suggest that the ocean during the G–L transition was strongly stratified, forming an unstable chemocline separating oxic shallow water from anoxic/euxinic deep water. Chemocline excursions, together with subsequent rapid transgression and oceanic anoxia, were likely responsible for the massive diversity decline of the G–L biotic crisis. 相似文献
3.
Pedro J. Marenco Frank A. Corsetti David J. Bottjer 《Geochimica et cosmochimica acta》2008,72(6):1570-1582
An integrated stable isotope, elemental and petrographic analysis of Early Triassic (Spathian) carbonates and evaporites along a proximal to deep environmental transect reveals significant variations in δ34S composition of carbonate associated sulfate (CAS). The variations in the δ34S of CAS are strongly correlated with the Ca/Mg composition of carbonates, suggesting that the variations are driven by the degree of dolomitization. The δ34S of dolostones and evaporites are similar to one another and exhibit lower δ34S values than limestones from all localities.Three hypotheses may explain the differences in δ34S between proximal dolostones/evaporites and inner/middle shelf limestones: (1) limestones experienced anaerobic sulfate reduction and subsequent incorporation of 34S-enriched sulfate into CAS during diagenesis, while dolostones did not—this is unlikely because of the lack of correlation between δ34SCAS and TOC, as well as other indicators of diagenesis, (2) dolomitization controlled the δ34SCAS in proximal paleoenvironments, where the source of the 34S depleted fluids was either continentally-derived or the result of Rayleigh distillation during evaporite formation, and (3) a δ34S depth gradient existed during the Early Triassic such that limestones formed in distal waters are more enriched in 34S versus evaporites and dolostones formed in proximal settings—we do not favor this hypothesis because the strong correlation between Ca/Mg and δ34SCAS implies that dolomitization controls the δ34SCAS in these samples. Results from subtidal, well-preserved (non-dolomitized) limestones suggest that the δ34S of Spathian seawater sulfate may have been heavier than previously suggested from analyses of evaporite deposits alone. 相似文献
4.
In order to understand spatial variations of stable isotope geochemistry in the Quruqtagh basin (northwestern China) in the aftermath of an Ediacaran glaciation, we analyzed carbonate carbon isotopes (δ13Ccarb), carbonate oxygen isotopes (δ18Ocarb), carbonate associated sulfate sulfur (δ34SCAS) and oxygen isotopes (δ18OCAS), and pyrite sulfur isotopes (δ34Spy) of a cap dolostone atop the Ediacaran Hankalchough glacial diamictite at four sections. The four studied sections (YKG, MK, H and ZBS) represent an onshore-offshore transect in the Quruqtagh basin. Our data show a strong paleobathymetry-dependent isotopic gradient. From the onshore to offshore sections, δ13Ccarb values decrease from −2‰ to −16‰ (VPDB), whereas δ18Ocarb values increase from −4‰ to −1‰ (VPDB). Both δ34SCAS and δ34Spy show stratigraphic variations in the two onshore sections (MK and YKG), but are more stable in the two offshore sections (H and ZBS). δ18OCAS values of onshore samples are consistent with terrestrial oxidative weathering of pyrite. We propose that following the Hankalchough glaciation seawater in the Quruqtagh basin was characterized by a strong isotopic gradient. The isotopic data may be interpreted using a three-component mixing model that involves three reservoirs: deep-basin water, surface water, and terrestrial weathering input. In this model, the negative δ13Ccarb values in the offshore sections are related to the upwelling of deep-basin water (where anaerobic oxidation of dissolved organic carbon resulted in 13C-depleted DIC), whereas sulfur isotope variations are strongly controlled by surface water sulfate and terrestrial weathering input derived from oxidative weathering of pyrite. The new data provide evidence for the oceanic oxidation following the Hankalchough glaciation. 相似文献
5.
Stable carbon isotopic composition of organic matter (δ13Corg) and compound-specific δ13C values of biomarkers from 15 lacustrine source rocks were analyzed to identify the original paleoenvironment and source organisms. The δ13C values of hopanes (δ13Chop) ranged from −68.7‰ to −32‰ and exhibit strongly 13C-depleted values in the lower part of Member 1 of the Nenjiang Formation (K2n1, up to −68.7‰), suggesting an origin from predominantly methanotrophic bacteria. 13C-enriched δ13CGa values and significantly 13C-depleted δ13Chop in K2n1, which coincide with water stratification and an intermittent anoxic photic zone, represents a shallow chemocline. The presence of an intermittent anoxic photic zone, which means that the anoxia expanded into the euphotic zone, is beneficial for OM preservation and results in high values of TOC and HI in this section. However, the absence of gammacerane and 13C-enrichment of δ13Chop in Member 2 of Nenjiang Formation (K2n2) reflect a deeper chemocline, corresponding to relatively oxidizing conditions and low values of TOC and HI. Moreover, the negative correlation of TOC vs δ13Corg and HI vs δ13Corg reflects the control of OM formation by sedimentary environments rather than productivity in the water column. Thus, the depth of the chemocline not only controls the abundance of OM but also affects the development of the microbial community, such as chemoautotrophic bacteria in the deep chemocline and chemoautotrophic and methanotrophic bacteria in the shallow chemocline. Moreover, δ13CGa and δ13C values for 4-methyl steranes are related to water salinity, with a higher salinity accompanied by 13C-enrichment in gammacerane and 4-methyl steranes. 相似文献
6.
罗河铁矿(又称庐枞铁矿)是我国长江中下游火山岩地区大型铁矿床之一,是一种重要的矿床类型。十多年来,各研究单位和生产部门对该矿床进行了多方面、较系统的研究,取得可喜成果(张荣华等,1974;张荣华,1981;陈锦石等,1982)。然而,要进一步阐明这类矿床的成矿机理,还需要对该矿床的蚀变和成矿条件进行深入研究。本文着重讨论罗河铁矿的硫同位素分馏机制,并在此基础上结合地质和矿物包裹体的资料,近似定量地推算该矿床形成各阶段的物理化学条件范围及变化规律。 相似文献
7.
Hydrous pyrolysis experiments at 200 to 365°C were carried out on a thermally immature organic-rich limestone containing Type-IIS kerogen from the Ghareb Limestone in North Negev, Israel. This work focuses on the thermal behavior of both organic and inorganic sulfur species and the partitioning of their stable sulfur isotopes among organic and inorganic phases generated during hydrous pyrolyses. Most of the sulfur in the rock (85%) is organic sulfur. The most dominant sulfur transformation is cleavage of organic-bound sulfur to form H2S(gas). Up to 70% of this organic sulfur is released as H2S(gas) that is isotopically lighter than the sulfur in the kerogen. Organic sulfur is enriched by up to 2‰ in 34S during thermal maturation compared with the initial δ34S values. The δ34S values of the three main organic fractions (kerogen, bitumen and expelled oil) are within 1‰ of one another. No thermochemical sulfate reduction or sulfate formation was observed during the experiments. The early released sulfur reacted with available iron to form secondary pyrite and is the most 34S depleted phase, which is 21‰ lighter than the bulk organic sulfur. The large isotopic fractionation for the early formed H2S is a result of the system not being in equilibrium. As partial pressure of H2S(gas) increases, retro reactions with the organic sulfur in the closed system may cause isotope exchange and isotopic homogenization. Part of the δ34S-enriched secondary pyrite decomposes above 300°C resulting in a corresponding decrease in the δ34S of the remaining pyrite. These results are relevant to interpreting thermal maturation processes and their effect on kerogen-oil-H2S-pyrite correlations. In particular, the use of pyrite-kerogen δ34S relations in reconstructing diagenetic conditions of thermally mature rocks is questionable because formation of secondary pyrite during thermal maturation can mask the isotopic signature and quantity of the original diagenetic pyrite. The main transformations of kerogen to bitumen and bitumen to oil can be recorded by using both sulfur content and δ34S of each phase including the H2S(gas). H2S generated in association with oil should be isotopically lighter or similar to oil. It is concluded that small isotopic differentiation obtained between organic and inorganic sulfur species suggests closed-system conditions. Conversely, open-system conditions may cause significant isotopic discrimination between the oil and its source kerogen. The magnitude of this discrimination is suggested to be highly dependent on the availability of iron in a source rock resulting in secondary formation of pyrite. 相似文献
8.
9.
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
10.
J. Maarten de Moor Tobias P. Fischer Erik H. Hauri Viorel Atudorei 《Geochimica et cosmochimica acta》2010,74(18):5382-5397
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
11.
Sulfur cycling in a stratified euxinic lake with moderately high sulfate: Constraints from quadruple S isotopes 总被引：1，自引：0，他引：1
Aubrey L. Zerkle Alexey Kamyshny Jr. Lee R. Kump James Farquhar Harry Oduro Michael A. Arthur 《Geochimica et cosmochimica acta》2010,74(17):4953-154
We present a 3-year study of concentrations and sulfur isotope values (δ34S, Δ33S, and Δ36S) of sulfur compounds in the water column of Fayetteville Green Lake (NY, USA), a stratified (meromictic) euxinic lake with moderately high sulfate concentrations (12-16 mM). We utilize our results along with numerical models (including transport within the lake) to identify and quantify the major biological and abiotic processes contributing to sulfur cycling in the system. The isotope values of sulfide and zero-valent sulfur across the redox-interface (chemocline) change seasonally in response to changes in sulfide oxidation processes. In the fall, sulfide oxidation occurs primarily via abiotic reaction with oxygen, as reflected by an increase in sulfide δ34S at the redox interface. Interestingly, S isotope values for zero-valent sulfur sampled at this time still reflect production and recycling by phototrophic S-oxidation. In the spring, sulfide S isotope values suggest an increased input from phototrophic oxidation, consistent with a more pronounced phototroph population at the chemocline. This trend is associated with smaller fractionations between sulfide and zero-valent sulfur, suggesting a metabolic rate control on fractionation similar to that for sulfate reduction. Comparison of our data with previous studies indicates that the S isotope values of sulfate and sulfide in the deep waters are remarkably stable over long periods of time, with consistently large fractionations of up to 58‰ in δ34S. Models of the δ34S and Δ33S trends in the deep waters (considering mass transport via diffusion and advection along with biological processes) require that these fractionations are a consequence of sulfur compound disproportionation at and below the redox interface in addition to large fractionations during sulfate reduction. The large fractionations during sulfate reduction appear to be a consequence of the high sulfate concentrations and the distribution of organic matter in the water column. The occurrence of disproportionation in the lake is supported by profiles of intermediate sulfur compounds and by lake microbiology, but is not evident from the δ34S trends alone. These results illustrate the utility of including minor S isotopes in sulfur isotope studies to unravel complex sulfur cycling in natural systems. 相似文献
12.
E. M. Ripley 《Mineralium Deposita》1983,18(1):3-15
The Deer Lake Complex, located in north-central Minnesota, consists of a series of layered peridotite-pyroxenite-gabbro sills. Sulfide minerals occur as fine disseminations throughout pyroxenite and gabbro units, and occur more sporadically in peridotite and basal chilled margin units. Sulfide volume percentage rarely exceeds 0.5. A distinct zonation in sulfide mineralogy and sulfur isotopic composition characterizes the sills. Cobaltian pentlandite is the dominant sulfide mineral in peridotite (pd) units, with Ni-enrichment most likely linked to the serpentinization process. δ34Spd values are variable, ranging from ?3.5 to +2.8‰. Sulfide assemblages in pyroxenite (px) and lower gabbro units consist of chalcopyrite, pyrrhotite, and minor pentlandite. δ34Spx values range from ?1 to +1 ‰. Pyrite is the principal sulfide mineral in upper gabbro (μg) units. Its origin may be related to increased f02 conditions of the remaining melt and to reaction between a S-bearing volatile phase and mafic silicates. δ34Sug values range from 1 to 3.5 ‰. Sulfur isotopic values of chilled margin (2–9 ‰) and peridotite units, together with the erratic spatial distribution of sulfide minerals in these zones, suggests that the parent magma was not initially saturated with sulfur, and that local sulfide concentrations are the result of incorporation of sulfur derived from metasedimentary country rocks. Sulfide saturation was more uniformly reached during pyroxenite formation, with contained sulfur being of magmatic origin. Enrichment in 34S of pyrite from upper gabbro may be explained by buildup of isotopically heavy sulfur following a Rayleigh process, coupled with possible involvement of a SO2-rich fluid phase during hydrothermal alteration. 相似文献
13.
Acid sulfate-chloride thermal water samples collected together with fumarolic gases from various volcanic areas in northeastern Japan were studied chemically and isotogdically. δ34S (COT) values of sulfate and hydrogen sulfide from these volcanic hot springs range from +4.0 to +31 and from ?15.0 to ?2.0% respectively, with δ34Sys value of +2.5 to +31. The δ34S of the sulfate in the more saline waters tends to become smaller with increasing ratio of SO4 to Cl, although the chemical and isotopic composition of acid thermal water within some areas may be altered by secondary processes during the discharge of the thermal waters. This trend can be explained by the reaction of the volcanic gases, having S/Cl of 4 ~ 7 and total sulfur of ~0% in δ34S, with ground water at 200°C, and/or the removal of sulfide phase depleted in 34S from the acid thermal water formed by the disproportionation of volcanic sulfur. The sulfur species in acid sulfate-chloride thermal water are shown to be volcanic exhalations. 相似文献
14.
Heinrich D Holland 《Geochimica et cosmochimica acta》1973,37(12):2605-2616
Past treatments of the variation of δS34 in marine evaporites have either assumed a steady-state ocean or have invoked rather simplified ocean input-output models. This paper derives more completely the relationships between the parameters that influence the time variation of δS34 in ocean water and the relationship between δS34 in ocean water and net gains and losses of atmospheric oxygen due to the operation of the sulfur cycle. The lower and mid-Paleozoic are shown to have been periods of net gain of atmospheric oxygen by the operation of the sulfur cycle; the upper Paleozoic, particularly the Permian, a period of oxygen loss. It is difficult to relate these oxygen gains and losses to variations in the oxygen content of the atmosphere, because the oxygen flux due to the operation of the carbon cycle is approximately twice as large as the flux due to the operation of the sulfur cycle. Data for the organic carbon and sulfide content of sedimentary rocks of the Russian Platform suggest that a decrease in sulfide from the Paleozoic to the Mesozoic and Cenozoic Era was roughly balanced by an increase in the proportion of organic carbon; however, such data are insufficient to define the abundance of atmospheric oxygen during the Phanerozoic. Biologic data and a better understanding of controls on atmospheric Po2 are more likely to produce convincing evidence regarding variations of atmospheric oxygen in the past. 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.
David A. Fike Niko Finke Jessica Zha Tori M. Hoehler 《Geochimica et cosmochimica acta》2009,73(20):6187-6204
Substantial isotopic fractionations are associated with many microbial sulfur metabolisms and measurements of the bulk δ34S isotopic composition of sulfur species (predominantly sulfates and/or sulfides) have been a key component in developing our understanding of both modern and ancient biogeochemical cycling. However, the interpretations of bulk δ34S measurements are often non-unique, making reconstructions of paleoenvironmental conditions or microbial ecology challenging. In particular, the link between the μm-scale microbial activity that generates isotopic signatures and their eventual preservation as a bulk rock value in the geologic record has remained elusive, in large part because of the difficulty of extracting sufficient material at small scales. Here we investigate the potential for small-scale (∼100 μm-1 cm) δ34S variability to provide additional constraints for environmental and/or ecological reconstructions. We have investigated the impact of sulfate concentrations (0.2, 1, and 80 mM SO4) on the δ34S composition of hydrogen sulfide produced over the diurnal (day/night) cycle in cyanobacterial mats from Guerrero Negro, Baja California Sur, Mexico. Sulfide was captured as silver sulfide on the surface of a 2.5 cm metallic silver disk partially submerged beneath the mat surface. Subsequent analyses were conducted on a Cameca 7f-GEO secondary ion mass spectrometer (SIMS) to record spatial δ34S variability within the mats under different environmental conditions. Isotope measurements were made in a 2-dimensional grid for each incubation, documenting both lateral and vertical isotopic variation within the mats. Typical grids consisted of ∼400-800 individual measurements covering a lateral distance of ∼1 mm and a vertical depth of ∼5-15 mm. There is a large isotopic enrichment (∼10-20‰) in the uppermost mm of sulfide in those mats where [SO4] was non-limiting (field and lab incubations at 80 mM). This is attributed to rapid recycling of sulfur (elevated sulfate reduction rates and extensive sulfide oxidation) at and above the chemocline. This isotopic gradient is observed in both day and night enrichments and suggests that, despite the close physical association between cyanobacteria and select sulfate-reducing bacteria, photosynthetic forcing has no substantive impact on δ34S in these cyanobacterial mats. Perhaps equally surprising, large, spatially-coherent δ34S oscillations (∼20-30‰ over 1 mm) occurred at depths up to ∼1.5 cm below the mat surface. These gradients must arise in situ from differential microbial metabolic activity and fractionation during sulfide production at depth. Sulfate concentrations were the dominant control on the spatial variability of sulfide δ34S. Decreased sulfate concentrations diminished both vertical and lateral δ34S variability, suggesting that small-scale variations of δ34S can be diagnostic for reconstructing past sulfate concentrations, even when original sulfate δ34S is unknown. 相似文献
17.
V. I. Vinogradov 《Lithology and Mineral Resources》2007,42(1):1-14
Based on evaporite sequences of the Irkutsk amphitheater, it is shown that sulfur in the Vendian-Lower Cambrian sedimentary sulfates displays a very wide scatter of sulfur isotope ratios and enrichment in heavy sulfur up to average values of δ34S ≈ +(27–30)‰. These features are related to sulfate reduction, which is distinctly expressed like other secondary alterations in the studied sections. Average δ34S values reflect the dynamics of isotopic effects rather than the initial sulfur composition of the oceanic water. The Irkutsk amphitheater can be considered natural model of sulfur isotopic variations in ancient evaporites. Existing concepts of the sulfur isotopic composition of Cambrian oceans need to be revised. 相似文献
18.
The sulfur and strontium isotopic compositions of Permian evaporites from the Zechstein basin, northern Germany 总被引：1，自引：0，他引：1
The sulfur isotopic composition of stratigraphically well constrained samples from five evaporitic cycles of the German Zechstein (upper Permian) displays no systematic lateral variation and no significant temporal trend. With an average δ34S value close to 11‰, results confirm the previously determined sulfur isotope minimum for Phanerozoic seawater. Least radiogenic 87Sr/86Sr ratios for these sulfates define a clear temporal variation with a minimum value at 0.707008. A conclusive assessment of this temporal trend in comparison with other data sets for upper Permian seawater is not possible due to substantial differences in (bio)stratigraphic assignments. 相似文献
19.
The sulfur cycle of Mariager Fjord was studied by following the pool of sulfide in the anoxic water and its isotopic composition during a period of 3 yr. Though most of the sulfide accumulating in the fjord was formed in the sediment, the isotopic composition of sulfide in the water was different from the isotopic composition of sulfide diffusing into the water from the sediment. The mean isotopic composition of the water column sulfide (δ34S) varied during the year between −13‰ and −21‰ with the most negative values reached during winter/early spring, while the sulfide diffusing into the water from the sediment had a mean isotope composition of −11.3‰. This annual pattern suggested that processes in the oxidative part of the sulfur cycle were responsible for the excess fractionation, and mass-balance considerations indicated that the excess fractionation of the sulfur isotopes could be accounted for by disproportionation of S0 or S2O32− in the water column, but not by water column sulfate reduction or sulfide oxidation alone. MPN counts demonstrated that a population of more than 3 × 104 cells mL−1 capable of growing by disproportionation of these two substrates was present in all depths of the fjord. The results presented in this communication demonstrate that the isotopic depletion of sulfide in anoxic systems may vary between periods of net sulfate reduction versus periods of net sulfide oxidation and indicate that disproportionation of sulfur compounds may be an important step in the sulfur cycle of euxinic basins. 相似文献
20.
Xiaona Li William P. Gilhooly III Timothy W. Lyons Josef P. Werne Ramon Varela 《Geochimica et cosmochimica acta》2010,74(23):6764-6778
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