Stable Sulfur Isotopic Compositions Research Articles

Origin of pyrite nodules at the top of the nantuo diamictites, Southern China

Pyrite nodules up to 20 cm in diameter are found at the top of the Marinoan (~ 635 Ma) Nantuo glacial diamictite as well as in the cap dolostones and shale/siltstones in the lower Doushantuo Formation in eastern Guizhou, southern China. Field occurrences, petrography, and stable sulfur isotopic compositions of pyrite nodules were studied from a section at Taoying, eastern Guizhou, China. Pyrite δ34S values from different nodules varied from 7.3 to 60.5‰ at different stratigraphic levels. No stratigraphic trend existed for the δ34S, supporting the scenario of pyrite formation in sediments before the precipitation of the cap dolostone. Pyrite δ34S values were also homogeneous within individual nodules at a 0.3 to 1 cm sampling scale, but were more heterogeneous at a 2 mm sampling scale. Homogeneity was not expected from the particular model for pyrite nodule formation in a largely closed or semi-closed environment. Thus, differential cementation and compaction of the pyrite-bearing sediments may have produced the nodular shape of the pyrite deposit.

Roles of Sulfur Oxidation Pathways in the Variability in Stable Sulfur Isotopic Composition of Sulfate Aerosols at an Urban Site in Beijing, China

Sulfate (SO42–) is an important chemical species in atmospheric aerosols, which strongly impacts atmospheric chemistry processes and climate change. Stable sulfur isotopes (δ34S) of sulfate aerosol...

Isotopic systematics point to wild origin of mummified birds in Ancient Egypt

Millions of mummified birds serving for religious purpose have been discovered from archeological sites along the Nile Valley of Egypt, in majority ibises. Whether these birds were industrially raised or massively hunted is a matter of heavy debate as it would have a significant impact on the economy related to their supply and cult, and if hunted it would have represented an ecological burden on the birds populations. Here we have measured and analysed the stable oxygen, carbon and radiogenic strontium isotope compositions as well as calcium and barium content of bones along with the stable carbon, nitrogen and sulfur isotope composition of feathers from 20 mummified ibises and birds of prey recovered from various archeological sites of Ancient Egypt. If these migratory birds were locally bred, their stable oxygen, radiogenic strontium and stable sulfur isotopic compositions would be similar to that of coexisting Egyptians, and their stable carbon, nitrogen and oxygen isotope variance would be close, or lower than that of Egyptians. On one hand, isotopic values show that ibises ingested food from the Nile valley but with a higher isotopic scattering than observed for the diet of ancient Egyptians. On the other hand, birds of prey have exotic isotopic values compatible with their migratory behaviour. We therefore propose that most mummified ibises and all the birds of prey analysed here were wild animals hunted for religious practice.

Contaminant sources and processes affecting spring water quality in a typical karst basin (Hongjiadu Basin, SW China): insights provided by hydrochemical and isotopic data.

Springs are an important source of drinking water supply in mountainous karst areas of SW China. However, the quality of many spring waters has deteriorated greatly in recent years, which leads to a significant problem of drinking water scarcity. In this study, hydrochemistry and stable sulfur and oxygen isotopic compositions of SO42- (δ34S and δ18OSO4) of 38 representative samples of waters (incl. spring water, surface water, rainwater, and sewage) from the Hongjiadu Basin, Guizhou province, SW China, were investigated in order to identify the sources of contaminates in spring waters and trace the processes affecting the karst groundwater quality. Approximately 28% of the total investigated springs has been suffered from serious contamination and the concentrations of NO3-, SO42-, and total iron (TFe) in many spring waters have exceeded the standards for drinking water. The springs that have NO3- concentrations of > 30 mg/L are concentrated in residential and agricultural areas, suggesting that NO3- in spring water are mainly derived from chemical fertilizers, manure, and sewage. δ34S and δ18OSO4 data indicate that SO42- in spring water mainly originates from sulfide oxidation, acid rain, and sewage. Furthermore, the high δ34S and δ18OSO4 values of SO42- in some spring waters may be related to the occurrence of bacterial sulfate reduction. Some springs that are discharged from abandoned coal mines have SO42- concentrations of > 250 mg/L, demonstrating that mining activities have accelerated the deterioration of spring water quality. Also, springs with TFe concentrations of > 0.3 mg/L are discharged from coal-bearing strata, revealing that iron in spring waters is mainly derived from the oxidation of pyrite. Our results show that the karst spring waters are highly vulnerable to anthropogenic contaminations and human activities, such as agricultural fertilizing and sewage and waste disposal as well as mining activities, which exert a great impact on the quality of groundwater in karst areas.

Stable sulfur isotope ratios and chemical compositions of fine aerosols (PM2.5) in Beijing, China

Pervasive particulate pollution has been observed over large areas of the North China Plain. The high level of sulfate, a major component in fine particles, is pronounced during heavy pollution periods. Being different from source apportionments by atmospheric chemistry-transport model and receptor modeling methods, here we utilize sulfur isotopes to discern the potential emission sources. Sixty-five daily PM2.5 samples were collected at an urban site in Beijing between September 2013 and July 2014. Inorganic ions, organic/elemental carbon and stable sulfur isotopes of sulfate were analyzed. The “fingerprint” characteristics of stable sulfur isotopic composition, together with trajectory clustering modeled by HYSPLIT-4 (HYbrid Single-Particle Lagrangian Integrated Trajectory) and FLEXPART (“FLEXible PARTicle dispersion model”), was employed to identify potential aerosol sources in Beijing. Results exhibited a distinctive seasonality with sulfate, nitrate, ammonium, organic matter, and element carbon being the dominant species of PM2.5. Elevated concentrations of chloride with high organic matter were found in autumn and winter as a result of enhanced fossil fuel (mainly coal) combustion. The δ34S values of the Beijing aerosols ranged from 2.8‰ to 9.9‰ with an average of 6.0 ± 1.8‰, further indicating that the major sulfur source was direct coal burning emission. Owing to the changing patterns between oxidation pathways of S(IV) in different seasons, δ34S values varied with a winter maximum (8.2 ± 1.1‰) and a summer minimum (4.9 ± 1.9‰). The results of trajectory clustering and FLEXPART demonstrated that higher concentrations of sulfate with lower sulfur isotope ratios (4.6 ± 0.8‰) were associated with air masses from the south or east, whereas lower sulfate concentrations with heavier sulfur isotope ratios (6.7 ± 1.6‰) were observed when the air masses were mainly from the north or northwest. These results suggested that the fine aerosol pollution in Beijing, especially sulfate pollution, was mainly due to coal combustion sources from regional and local regions.

Sulfur and carbon isotopic compositions of the Permian to Triassic TSR and non-TSR altered solid bitumen and its parent source rock in NE Sichuan Basin

Reservoir solid bitumens from the Permian to Triassic and potential source rocks in the northeastern Sichuan Basin were measured for elemental and stable carbon (δ13C) and sulfur (δ34S) isotopic compositions to determine the chemical and isotopic composition of non-TSR and TSR-altered solid bitumen and to develop proxies to reflect the extent of bitumen alteration by TSR. Non-TSR altered reservoir bitumen samples showed S/C atomic ratios ⩽0.03 and had δ13C values closer to Longtan Formation (P3l) kerogen than to the Lower Silurian and Cambrian kerogens, and δ34S values slightly more enriched than P3l kerogens. The TSR-altered solid bitumens have incorporated significant amounts of TSR-derived H2S resulting in S/C atomic ratios (0.047–0.074) and δ34S values (13.4–24.0‰) being significantly higher than those of the solid bitumen not altered by TSR (S/C: 0.013–0.030; δ34S: 5.8–9.6‰) and the potential source rock kerogen. The incorporation has produced a decrease in N/C ratio and negative shift of −2.7‰ in δ13C values that resulted from increasing TSR-H2S back reactions with 12C-rich n-alkanes from the gas phase, soluble solid bitumen or paleo-oil to generate organic sulfur compounds such as ethanethiol that were incorporated into the solid bitumens, which is followed by further aromatization and polymerization. The solid bitumens show positive relationships of S/C ratios and δ34S values to the associated gas H2S/(H2S+ΣC1–6) or TSR extents, and thus the S/C ratios and δ34S values can be used as proxies to reflect TSR extents.

Effects of thermal maturation and thermochemical sulfate reduction on compound-specific sulfur isotopic compositions of organosulfur compounds in Phosphoria oils from the Bighorn Basin, USA

Compound-specific sulfur isotope analysis was applied to a suite of 18 crude oils generated from the Permian Phosphoria Formation in the Bighorn Basin, western USA. These oils were generated at various levels of thermal maturity and some experienced thermochemical sulfate reduction (TSR). This is the first study to examine the effects of thermal maturation on stable sulfur isotopic compositions of individual organosulfur compounds (OSCs) in crude oil. A general trend of 34S enrichment in all of the studied compounds with increasing thermal maturity was observed, with the δ34S values of alkyl-benzothiophenes (BTs) tending to be enriched in 34S relative to those of the alkyl-dibenzothiophenes (DBTs) in lower-maturity oils. As thermal maturity increases, δ34S values of both BTs and DBTs become progressively heavier, but the difference in the average δ34S value of the BTs and DBTs (Δ34S BT-DBT) decreases. Differences in the isotopic response to thermal stress exhibited by these two compound classes are considered to be the result of relative differences in their thermal stabilities. TSR-altered Bighorn Basin oils have OSCs that are generally enriched in 34S relative to non-TSR-altered oils, with the BTs being enriched in 34S relative to the DBTs, similar to the findings of previous studies. However, several oils that were previously interpreted to have been exposed to minor TSR have Δ34S BT-DBT values that do not support this interpretation. The δ34S values of the BTs and DBTs in some of these oils suggest that they did not experience TSR, but were derived from a more thermally mature source. The heaviest δ34S values observed in the OSCs are enriched in 34S by up to 10‰ relative to that of Permian anhydrite in the Bighorn Basin, suggesting that there may be an alternate or additional source of sulfate in some parts of the basin. These results indicate that the sulfur isotopic composition of OSCs in oil provides a sensitive indicator for the extent of TSR, which cannot be determined from other bulk geochemical parameters. Moreover, when combined with additional geochemical and geologic evidence, the sulfur isotopic composition of OSCs in oils can help to identify the source of sulfate for TSR alteration in petroleum reservoirs.

Determination of the sulfur isotope ratio in carbonyl sulfide using gas chromatography/isotope ratio mass spectrometry on fragment ions 32S+, 33S+, and 34S+.

Little is known about the sulfur isotopic composition of carbonyl sulfide (OCS), the most abundant atmospheric sulfur species. We present a promising new analytical method for measuring the stable sulfur isotopic compositions (δ(33)S, δ(34)S, and Δ(33)S) of OCS using nanomole level samples. The direct isotopic analytical technique consists of two parts: a concentration line and online gas chromatography-isotope ratio mass spectrometry (GC-IRMS) using fragmentation ions (32)S(+), (33)S(+), and (34)S(+). The current levels of measurement precision for OCS samples greater than 8 nmol are 0.42‰, 0.62‰, and 0.23‰ for δ(33)S, δ(34)S, and Δ(33)S, respectively. These δ and Δ values show a slight dependence on the amount of injected OCS for volumes smaller than 8 nmol. The isotope values obtained from the GC-IRMS method were calibrated against those measured by a conventional SF6 method. We report the first measurement of the sulfur isotopic composition of OCS in air collected at Kawasaki, Kanagawa, Japan. The δ(34)S value obtained for OCS (4.9 ± 0.3‰) was lower than the previous estimate of 11‰. When the δ(34)S value for OCS from the atmospheric sample is postulated as the global signal, this finding, coupled with isotopic fractionation for OCS sink reactions in the stratosphere, explains the reported δ(34)S for background stratospheric sulfate. This suggests that OCS is a potentially important source for background (nonepisodic or nonvolcanic) stratospheric sulfate aerosols.

Speciation and stable isotopic compositions of humic sulfur in mud sediment of the East China Sea: Constraints on origins and pathways of organic sulfur formation

Humic sulfur is commonly the most important pool of organic sulfur (OS) in marine sediments and also important for the budget of total sedimentary sulfur. In this study, contents and stable sulfur isotopic compositions of hydrolyzable organic sulfur (HYOS), humic acid sulfur (HA-S) and fulvic acid sulfur (FA-S) in one core collected from the East China Sea (ECS) inner shelf were determined to investigate the sources and pathways of OS formation and to compare diagenetic geochemistry of HA-S and FA-S. HYOS in the core is essentially biological in origin and diagenetically refractory, with a fairly low fraction of labile sulfur bearing biomolecules. HA-S in the core is largely terrigenous residual bio-OS, while FA-S is a mixture of marine bio- and diagenetic OS (diag-OS), with the diag-OS fractions between 44% and 71%. Both HA-S and FA-S contents in the core are at the lower ends of the corresponding values reported in the literature. The HA in the sediments is diagenetically inert, subject to neither significant diagenetic sulfurization nor bio-OS mineralization loss, while the FA is reactive, prone to both sulfurization and decomposition loss of diagenetically bound OS. Low contents of humic S [i.e., ∑(HA-S+FA-S)] in the core may suggest that OS burial has only minor contribution to the burial of total sulfur in the sediments due to generally low OM sulfurization.

Formation and burial of pyrite and organic sulfur in mud sediments of the East China Sea inner shelf: Constraints from solid-phase sulfur speciation and stable sulfur isotope

Solid-phase sulfur speciation and stable sulfur isotopic compositions are used to elucidate the formation and burial of pyrite-sulfur (Spy) and organic sulfur (OS) at three selected sites in mud sediments of the East China Sea (ECS) inner shelf, and to infer potential factors influencing the preservation of Spy and OS in the sediments. Our results in combination with previous studies show that the overall reactivity of sedimentary organic matter (OM) is low, while OM at the site impacted by frequent algal-bloom events displays somewhat enhanced reactivity. We observed characteristically low contents of acid volatile sulfide (AVS) and Spy in the sediments, which can be attributed to low sulfate reduction rate due to high redox potential together with limited availability of labile OM. Several geochemical features, for example, persistent occurrence of S0, good coupling among the profiles of AVS, S0 and Spy, and large 34Spy depletion, all suggest that the polysulfide pathway and disproportionation are likely involved in the pyrite formation. Organic sulfur amounts in the sediments are at the lower end of OS contents reported in many other marine sediments around the world. The sources of OS are both biosynthetic and diagenetic, with the biosynthetic OS being the major share (59–73%). In one site studied (C702), enhanced accumulation of OS within the upper layers (14cm) is believed to be associated with frequent algal-bloom events. Net burial fluxes of Spy and OS in the three sites studied range from 0.27 to 0.82mmol/m2/d and from 0.22 to 0.74mmol/m2/d, respectively. Sedimentation rate and algal-bloom events are two important factors influencing the spatial variability of Spy and OS burial fluxes in the whole shelf.

Hydrogeochemical evolution of Ordovician limestone groundwater in Yanzhou, North China

AbstractMajor‐ion compositions of groundwater are employed in this study of the water–rock interactions and hydrogeochemical evolution within a carbonate aquifer system. The groundwater samples were collected from boreholes or underground tunnels in the Ordovician limestone of Yanzhou Coalfield where catastrophic groundwater inflows can be hazardous to mining and impact use of the groundwater as a water supply. The concentration of total dissolved solid (TDS) ranged from 961 to 3555 mg/l and indicates moderately to highly mineralized water. The main water‐type of the middle Ordovician limestone groundwater is Ca‐Mg‐SO4, with SO42‐ ranging from 537 to 2297 mg/l, and average values of Ca2+ and Mg2+ of 455.7 and 116.6 mg/l, respectively. The water samples were supersaturated with respect to calcite and dolomite and undersaturated or saturated with respect to gypsum. Along the general flow direction, deduced from increases of TDS and Cl‐, the main water–rock interactions that caused hydrogeochemical evolution of the groundwater within the aquifer were the dissolution of gypsum, the precipitation of calcite, the dissolution or precipitation of dolomite, and ion exchange. Ion exchange is the major cause for the lower mole concentration of Ca2+ than that of SO42‐. The groundwater level of Ordovician aquifer is much higher than that of C‐P coal‐bearing aquifers, so the potential flow direction is upward, and the pyrite in coal is not a possible source of sulfate; additional data on the stable sulfur and oxygen isotopic composition of the sulfate may be helpful to identify its origin. Although ion exchange probably accounts for the higher mole concentration of Na+ than that of Cl‐, the dissolution of aluminosilicate cannot be ruled out. The data evaluation methods and results of this study could be useful in other areas to understand flow paths in aquifers and to provide information needed to identify the origin of groundwater. Copyright © 2012 John Wiley & Sons, Ltd.

Sulfur isotopic composition and source identification of atmospheric environment in central Zhejiang, China

Sulfur dioxide and sulfate aerosols in the atmosphere are significant factors leading to acidification of the atmospheric environment and worsening the pollution of acid deposition. Because of the “fingerprint” characteristics of the stable sulfur isotopic composition, sulfur isotope has been widely adopted in environmental researches concerning sulfur cycle and source identification. In this study, the atmospheric environment of Jinhua City, central Zhejiang Province, was continuously monitored, and the sulfur isotopic composition of SO2 and sulfate aerosols in the atmosphere was analyzed. The results indicate that the variation of δ34S values for SO2 ranges from 1.0‰ to 7.5‰, and annual average is 4.7‰±2.3‰, whereas that of sulfate aerosols ranges from 6.4‰ to 9.8‰, and annual average is 8.1‰±1.0‰. The δ34S values for SO2 have significant seasonal variations, which are 7.0‰ in winter and 3.3‰ in summer. These variations cannot be attributed to a single factor, and we suggest a temperature-dependent isotope equilibrium fractionation and elevated biogenic sulfur emissions of isotopically light S in summer may be the main controlling mechanisms. Furthermore, we also discuss the δ34S model of atmospheric SO2 oxidation to form sulfate, and suggest that heterogeneous oxidation dominates in the oxidation reactions of atmospheric SO2 in the central Zhejiang Province. We further suggest that the relative humidity in the atmosphere plays an important role in the oxidation mechanism of atmospheric SO2.

Regional variation in eelgrass ( Zostera marina) morphology, production and stable sulfur isotopic composition along the Baltic Sea and Skagerrak coasts

Morphology, total sulfur content and stable sulfur isotopic composition of Zostera marina were examined in the Baltic Sea–Skagerrak transition zone through surveys. The seagrass meadows were denser and less productive at the low salinities in the Baltic Sea (salinity 6–7 psu), and total sulfur accumulations in plants were lower and δ 34 S values were higher compared to the west coast of Sweden (salinity 21–29 psu). The δ 34 S values of the three plant compartments (leaves, rhizomes, roots) indicated lower sulfide invasion at low salinities, which was mainly due to environmental conditions (e.g. low epiphytic biomass, low sediment organic matter and low sulfate concentration) and plant characteristics (productivity, shoot morphology). Between 13% and 63% of the sulfur in the plants was derived from sediment sulfides with highest percentages in the roots (27–63%) and lower in rhizomes (13–50%) and leaves (14–51%). The high sulfide invasion on the west coast of Sweden was coincident with high sediment organic matter, probably increasing sulfide pressure on the plants, and high epiphytic biomass, probably constraining the oxygen dynamics in the plants and enhancing sulfide invasion. Regional and spatial variability in the δ 34 S were extensive, emphasizing the need for detailed analysis of local sources when applying stable sulfur isotopes in food web analyses. The observed invasion of sulfides suggests sulfide as a contributing factor to reported declines of Z. marina in the Skagerrak region.

Significance of euxinic condition in the middle Eocene paleo-Arctic basin: A geochemical study on the IODP Arctic Coring Expedition 302 sediments

Integrated Ocean Drilling Program (IODP) Expedition 302 Arctic Coring Expedition (ACEX) obtained the first relatively continuous long sediment cores from the Lomonosov Ridge in the central Arctic Ocean in 2004. Preceding microfossil studies indicated the dominance of low salinity surface waters in the early to middle Eocene Arctic basin. The main purpose of this study is to reconstruct paleoceanographic conditions including the extent of saline (seawater) mass presence. To attain this goal we performed geochemical analyses of total sulfur (%TS), total organic carbon (%TOC) and stable sulfur isotopic composition (δ 34S) on the early to middle Eocene section of the ACEX cores. The %TS were high in all the examined intervals and the sedimentary sulfur occurred mainly as framboidal pyrite, indicating that sufficient sulfate, indicative of seawater, was present in the deep layer of the paleo-Arctic basin and that the pyrite was formed in the sediments under sufficient iron input. The high %TS values with low δ 34S values also indicate the continuous existence and supply of seawater. The high accumulation of sulfide in Unit 1/6 was due to a significant increase of TOC supply which increased sulfate reduction rates by bacteria. The %TOC–%TS diagram shows excess sulfur content relative to the TOC, suggesting euxinic condition of the bottom water during the studied period. Such an oxygen depleted environment was brought about by salinity stratification and restricted water circulation. The patterns observed in the ACEX data can be comparable with the Mediterranean sapropels. The global δ 34S of seawater sulfate abruptly increased from + 17 to + 22‰ in the early to middle Eocene. Previous studies suggested that enhanced pyrite burial caused the isotopic shift during this period. The large pyrite burial in the anoxic Arctic basin could have contributed to the remarkable isotopic event accounting for about 3‰ of the global increase during this period.

Bacterial formation of phosphatic laminites off Peru

Authigenic phosphatic laminites enclosed in phosphorite crusts from the shelf off Peru (10 degrees 01' S and 10 degrees 24' S) consist of carbonate fluorapatite layers, which contain abundant sulfide minerals including pyrite (FeS(2)) and sphalerite (ZnS). Low delta(34)S(pyrite) values (average -28.8 per thousand) agree with bacterial sulfate reduction and subsequent pyrite formation. Stable sulfur isotopic compositions of sulfate bound in carbonate fluorapatite are lower than that of sulfate from ambient sea water, suggesting bacterial reoxidation of sulfide by sulfide-oxidizing bacteria. The release of phosphorus and subsequent formation of the autochthonous phosphatic laminites are apparently caused by the activity of sulfate-reducing bacteria and associated sulfide-oxidizing bacteria. Following an extraction-phosphorite dissolution-extraction procedure, molecular fossils of sulfate-reducing bacteria (mono-O-alkyl glycerol ethers, di-O-alkyl glycerol ethers, as well as the short-chain branched fatty acids i/ai-C(15:0), i/ai-C(17:0) and 10MeC(16:0)) are found to be among the most abundant compounds. The fact that these molecular fossils of sulfate-reducing bacteria are distinctly more abundant after dissolution of the phosphatic laminite reveals that the lipids are tightly bound to the mineral lattice of carbonate fluorapatite. Moreover, compared with the autochthonous laminite, molecular fossils of sulfate-reducing bacteria are: (1) significantly less abundant and (2) not as tightly bound to the mineral lattice in the other, allochthonous facies of the Peruvian crusts consisting of phosphatic coated grains. These observations confirm the importance of sulfate-reducing bacteria in the formation of the phosphatic laminite. Model calculations highlight that organic matter degradation by sulfate-reducing bacteria has the potential to liberate sufficient phosphorus for phosphogenesis.

Paleoceanography of the middle Eocene Arctic Ocean based on geochemical measurements of biogenic matter

Geochemical analyses of biogenic opal, total organic carbon (TOC), total sulfur (TS), and stable sulfur isotopic composition were conducted on the middle Eocene section of the ACEX cores obtained by IODP Expedition 302. The analyzed %TS contents were high in all the examined intervals, indicating sufficient sea water was present in the deep layer of the paleo Arctic basin in contrast with the low salinity surface waters determined by freshwater siliceous microfossils. From the high %TS in Lithological Unit 1/6, the extent of sea water supply from outside of the Arctic basin appeared to have increased after 45 Ma. The euxinic condition of the bottom water is suggested by the TOC-TS diagram. The anoxic environment was brought about by the estuarine type circulation pattern and salinity stratification. The light sulfur isotope composition ($ delta^{34} $S) indicates the microbial sulfate reduction in an open system. The trend of $ delta^{34} $S shift toward lower values with time is an indication of the history that the water exchange between the Arctic Ocean and the outside basin became progressively extensive. The high %TS, the plotted pattern of TOC vs TS, and the extremely low sulfur isotopic values are unique and not comparable with the modern analogous such as the Black Sea. These results illustrate that the middle Eocene Arctic Ocean retained characteristically unique environments on the geochemical aspect.

Changes in biomarker abundances and sulfur isotopes of pyrite across the Permian–Triassic (P/Tr) Schuchert Dal section (East Greenland)

In this study, we report on biomarker abundances through parts of the Permian/Triassic boundary (PTB) of Schuchert Dal (East Greenland) that contains rich marine faunal records and excellent terrestrial palynological records. Biomarker abundances and sulfur isotopes are used to correlate the series of events (including changes in element cycling and associated redox conditions of the ocean) surrounding the collapse of the marine and terrestrial ecosystems through this record of a major crisis of life on Earth during a mass extinction episode. The Upper Schuchert Dal Formation contains a low diversity palynological assemblage, ascribed to arborescent cordiaite–conifer–pteridosperm vegetation. Samples from this pre-collapse interval are characterised by high abundances of dibenzofuran (DBF), dibenzothiophene (DBT) and biphenyl. Since these compounds have similar base structures, and show comparable abundance curves, it is plausible that they probably derive from a common source. We propose that phenolic compounds of lignin of the woody plants present during this period could be the source for DBF, DBT and biphenyl. The redox conditions during this period of time also support the formation of DBF and DBT. Just above the extinction interval, there is a dramatic decrease in the abundances of DBF and DBT which occurs at the same time as a sudden change in the stable sulfur isotopic composition ( δ 34S) of pyrite, indicating a change in redox conditions from oxic to anoxic/euxinic conditions. δ 34S values leading up to the extinction are highly depleted in the heavy sulfur isotope (about − 40‰ vs. VCDT), whilst shortly after the extinction interval much more positive isotope values are observed (about − 25‰). An inferred change in the biogeochemical sulfur cycle is supported by facies evidence from similar neighbouring sections. It is suggested that two processes are operating closely here; 1) Changes in redox conditions and 2) extinction and/or transgression accounting for the absence of woody material.

Microbial sulfate reduction in deep sediments of the Southwest Pacific (ODP Leg 181, Sites 1119–1125): evidence from stable sulfur isotope fractionation and pore water modeling

Interstitial water samples from seven ODP sites (Leg 181, Sites 1119–1125) of the southwestern Pacific Ocean have been analyzed for the stable sulfur isotopic composition of dissolved sulfate along with major and minor ions. Sulfate from the interstitial fluids (δ 34S values between +20.7 and +60‰ vs. the SO 2-based Vienna–Canyon Diablo troilite standard) was enriched in 34S with respect to modern sea water (δ 34S≈+20.6‰) indicating that microbial sulfate reduction takes place to different extents at all investigated sites. Microbial sulfate reduction (MSR) was found at all sites, the intensity depending on the availability of organic matter which is controlled by paleo-sedimentation conditions (sedimentation rate, presence of turbidites) and productivity. Microbial net sulfate reduction was additionally confirmed by modeling interstitial water sulfate profiles. Areal net sulfate reduction rates up to 14 mmol m −2 yr −1 have been calculated which were positively related to sedimentation rates. Total reduced inorganic sulfur (TRIS; essentially pyrite) as a product of microbial sulfate reduction was isotopically characterized in squeeze cake samples and gave δ 34S values between −51 and +9‰ indicating pyrite formation both close to the sediment–water interface and later diagenetic contributions.

Stable Isotope Evidence for a Putative Endosymbiont-Based Lithotrophic Bathymodiolus sp. Mussel Community Atop a Serpentine Seamount

A putative endosymbiont-based benthic animal community composed of at least two kinds of bivalves has been found atop the South Chamorro serpentine seamount in the Mariana fore-arc, western Pacific. Multiple stable isotopic analyses (hydrogen, carbon, nitrogen, and sulfur) were carried out on the soft tissues of an undescribed mussel species belonging to the genus Bathymodiolus . Markedly higher stable carbon ( i 13 C: m 21.4 to m 18.9 vs. PDB) and lower sulfur ( i 34 S: +10.2 to +10.6 vs. CDT) isotopic compositions of the mussel tissues suggested that they utilized both methane and sulfide as nutrient sources of carbon and sulfur. Analyses of in situ shimmering water and clayey sediment under the mussel bed supported these findings. These results strongly suggest that the mussels harbored both methanotrophic and thioautotrophic bacterial symbionts in their gills. This is the first stable isotopic evidence of a dual symbiotic Bathymodiolus sp. in the western Pacific. It is proposed that the major substrates for energy acquisition--methane and hydrogen sulfide--may be responsible for results from serpentinization in the lower crust. This abiotic process would be followed by abiotic or archaeal methane production and bacterial sulfate-reduction as evidenced by high i 13 C value ( m 14.6) of methane in the shimmering water and low i 34 S value ( m 32.3) of sulfides in the immediate sediments, respectively. Due to the very low organic matter content (0.5 mg C/g dry sediment) of the immediate sediment, it is further proposed that sulfate-reduction occurred using hydrogen (or possibly methane) as an electron donor. Thus, the mussel community living independently of magmatism and sedimentary organic matter is a lithotrophic animal community.

Application of stable sulfur isotopes to differentiate sources of size‐resolved Particulate sulfate in polluted marine air at Bermuda during spring

Stable sulfur isotopic compositions of size‐segregated aerosols were measured at Bermuda during spring 1998 to differentiate contributions of marine biogenic and pollution sources of non‐sea‐salt SO42− (NSS). Marine biogenic sources contributed an average 0.41±0.33 nmol m−3 (15±7%) of supermicron NSS and 2.55±0.45 nmol m−3 (11±2%) of submicron NSS. Calculated concentrations of submicron NSS from marine biogenic sources are within the range of reported values for the remote southeastern Pacific. The average molar ratio of marine biogenic NSS/CH3SO3− for aerosol with geometric mean radius (GMR) of 0.6 µm (10.1±1.9) was significantly greater than that for aerosols with GMR 0.34 µm (3.9±1.4), suggesting differential atmospheric processing. Supermicron radius aerosol accounted for 75% of the NSS dry‐deposition flux.