Multiple Sulfur Isotopic Evidence for Sulfate Formation in Haze Pollution.

The mechanism of sulfate formation during winter haze events in North China remains largely elusive. In this study, the multiple sulfur isotopic composition of sulfate in different grain-size aerosol fractions collected seasonally from sampling sites in rural, suburban, urban, industrial, and coastal areas of North China are used to constrain the mechanism of SO2 oxidation at different levels of air pollution. The Δ33S values of sulfate in aerosols show an obvious seasonal variation, except for those samples collected in the rural area. The positive Δ33S signatures (0‰ < Δ33S < 0.439‰) observed on clean days are mainly influenced by tropospheric SO2 oxidation and stratospheric SO2 photolysis. The negative Δ33S signatures (-0.236‰ < Δ33S < ∼0‰) observed during winter haze events (PM2.5 > 200 µg/m3) are mainly attributed to SO2 oxidation by H2O2 and transition metal ion catalysis (TMI) in the troposphere. These results reveal that both the H2O2 and TMI pathways play critical roles in sulfate formation during haze events in North China. Additionally, these new data provide evidence that the tropospheric oxidation of SO2 can produce significant negative Δ33S values in sulfate aerosols.

Multi-isotope fingerprints of recent environmental samples from the Baltic coast and their implications for bioarchaeological studies.

Stable isotopes in coastal regions are influenced by the so-called sea spray effect which masks the actual terrestrial isotope fingerprint with a marine isotope signal. The sea spray impact on plants was investigated by analyzing different stable isotope systems (δ13Ccellulose, δ18Ocellulose, δ18Osulfate, δ34Ssulfate, δ34Stotal S, δ34Sorganic S, 87Sr/86Sr) in recent environmental samples (plants, soil, water) collected close to the Baltic Sea. All these isotopic systems are influenced by the sea spray, either by the uptake of ions (HCO3-, SO42-, Sr2+) of marine origin, thus exhibiting a marine isotopic signature, or by biochemical reactions associated with, e.g., salinity stress. A shift towards seawater values is observed for δ18Osulfate, δ34S, and 87Sr/86Sr. Cellulose becomes enriched in 13C and 18O due to sea spray, further enhanced (δ13Ccellulose) or mitigated (δ18Ocellulose) by salinity stress. The effect differs both regionally and seasonally, probably as a result of, e.g., differences in wind strength or prevailing wind direction, as well as between plants collected only few meters apart, in either the open field or at more wind-protected sites, reflecting samples more or less influenced by sea spray. The stable isotope data of recent environmental samples are compared to previously analyzed archaeological bone samples of animals from the Viking Haithabu and Early Medieval Schleswig sites located close to the Baltic Sea. Potential regions of origin can be predicted based on the magnitude of the (recent) local sea spray effect. This enables the identification of probably non-local individuals. The insights into sea spray mechanisms, biochemical reactions in plants, as well as seasonal, regional, and small-scale differences in stable isotope data will help to interpret multi-isotope fingerprints at coastal sites. Our study demonstrates the usefulness of environmental samples for bioarchaeological studies. Moreover, the detected seasonal and small-scale differences require adjusted sampling strategies for, e.g., isotopic baselines in coastal areas.

Identification and quantification of the sea spray effect on isotopic systems in α-cellulose (δ13C, δ18O), total sulfur (δ34S), and 87Sr/86Sr of European beach grass (Ammophila arenaria, L.) in a greenhouse experiment.

The sea spray effect can severely influence the isotopic signature of terrestrial individuals in coastal regions. To further specify this effect, beach grass was grown in a greenhouse under controlled environmental conditions and sprayed with mineral salt solution containing different mineral salts but only traces of NaCl (group 1). Another group of plants was sprayed with salty water from the Schlei inlet and the Baltic Sea, respectively (group 2). Control plants were only sprayed with tap water. Isotope analyses were conducted on the unwashed and washed plants (δ13Ccellulose, δ18Ocellulose, δ34Stotal S, 87Sr/86Sr), soil (δ18Osulfate, δ34Ssulfate, 87Sr/86Sr), and spray as well as irrigation water (δ18Osulfate, δ34Ssulfate, 87Sr/86Sr). Moreover, elemental analyses were performed on the water samples. The sea spray effect was visible in all isotopic systems under study. The uptake of SO42-, HCO3-, and Sr2+ directly affected plants of group 1, while plants of group 2, sprayed with salty water, additionally showed salinity stress in the case of α-cellulose and total sulfur due to biochemical reactions of the plants. Very high concentrations in HCO3- or SO42- also affected the plants' isotopic signatures. The impact of the sea spray and additional stress reactions were quantified. Our study is the first experiment creating an artificial sea spray effect in a greenhouse. This experiment for the first time enables the identification and quantification of the sea spray effect in environmental samples. The marine signature taken up by the plants and recorded by the investigated isotopic systems is apparently high and should have an impact on the isotopic fingerprints of animal consumers at the coast, as evidenced for archaeological animals from the Viking Haithabu and the early medieval Schleswig sites located close to the Baltic Sea. This result demonstrates the potential of greenhouse experiments as an isotopic predictor of the past local sea spray effect.

Seasonal phytoplankton and geochemical shifts in the subsurface chlorophyll maximum layer of a dimictic ferruginous lake.

Subsurface chlorophyll maxima layers (SCML) are ubiquitous features of stratified aquatic systems. Availability of the micronutrient iron is known to influence marine SCML, but iron has not been explored in detail as a factor in the development of freshwater SCML. This study investigates the relationship between dissolved iron and the SCML within the dimictic, ferruginous lake Grosses Heiliges Meer in northern Germany. The occurrence of the SCML under nonferruginous conditions in the spring and ferruginous conditions in the fall are context to explore temporal changes in the phytoplankton community and indicators of primary productivity. Results indicate that despite more abundant chlorophyll in the spring, the SCML sits below a likely primary productivity maximum within the epilimnion, inferred based on colocated dissolved oxygen, δ13 CDIC , and pH maxima. The peak amount of chlorophyll in the SCML is lower in the fall than in the spring, but in the fall the SCML is colocated with elevated dissolved iron concentrations and a local δ13 CDIC maximum. Cyanobacteria and Chlorophyta have elevated abundances within the SCML in the fall. Further investigation of the relationship of iron to primary productivity within ferruginous SCML may help to understand the environmental controls on primary productivity in past ferruginous oceans.

Simultaneous Compound-Specific Analysis of δ33S and δ34S in Organic Compounds by GC-MC-ICPMS Using Medium- and Low-Mass-Resolution Modes.

Compound-specific isotope analysis of sulfur (δ34S-CSIA) in organic compounds was established in the last decade employing gas chromatography connected to multiple-collector inductively coupled plasma mass spectrometry (GC-MC-ICPMS). However, δ33S-CSIA has not yet been reported so far. In this study, we present a method for the simultaneous determination of δ33S and δ34S in organic compounds by GC-MC-ICPMS applying medium- and also low-mass-resolution modes. The method was validated using the international isotope reference materials IAEA-S-1, IAEA-S-2, and IAEA-S-3. Overall analytical uncertainty including normalization and reproducibility for δ33S and δ34S was usually better than ±0.2 mUr (σ) for analytes containing at least 100 pmol of S. Further, it is demonstrated that, despite small isobaric interferences, results obtained at low mass resolution are indistinguishable from medium mass resolution offering the benefit of increased sensitivity and versatility of this method. Additionally, the method was applied for the δ33S and δ34S isotope analysis of industrially produced organic compounds to investigate potential mass-independent fractionation (MIF). The relation between δ34S and δ33S in these compounds followed a mass-dependent fractionation trend (MDF; Δ33S ≤ ±0.2 mUr). Degradation of dimethyl disulfide by direct photolysis caused a small but significant MIF (Δ33S = 0.55 ± 0.04 mUr, n = 3), demonstrating sufficient sensitivity of the method for these types of studies.

Contamination patterns in river water from rural Beijing: A hydrochemical and multiple stable isotope study.

The pollution of urban river has reached a critical level. In the present study, the hydrochemical composition of local surface water collected during two seasons from the rural area around urban Beijing, China, was examined. Concentrations of selected cations and anions reveal the temporal and spatial distribution of anthropogenic and natural pollution. Multiple stable isotopes (δ15Nnitrate, δ18Onitrate, δ34Ssulfate, δ18Osulfate, Δ33Ssulfate) analyses were applied for detecting of specific hydrochemical processes and identifying the major sources of contamination. Twenty-eight percent of the river water samples from the wet season and 34% from the dry season exhibit a minor water quality of class IV (poor) and below due to high pH values as well as high nitrate, sulfate and fluoride concentrations. This water is hazardous for human health and the aquatic ecology. The seemingly better river water quality in the wet season is caused by higher precipitation and, hence, dilution of the water constituents. Multiple isotopes identify urban wastewater as the prime pollution source. The higher fraction of deteriorated river water in the southern rural area (42%) compared to the north (24%) points to a higher contribution of urban effluents to the downstream rivers in the rural south. It can, thus, be concluded that less discharge of wastewater to the local surface and subsurface environments by better controls of public and private sewage disposal combined with the renewal of leaking sewer pipes would reduce the risk of anthropogenic contamination of river water.

Contamination of heavy metals and isotopic tracing of Pb in surface and profile soils in a polluted farmland from a typical karst area in southern China.

Farmland top soils and soil profiles situated in the karst area of Guilin, Guangxi Zhuang Autonomous Region, southern China, reveal different degrees of heavy metal pollution, both in respect to the lateral as well as the vertical dimension. Pb isotope ratios clearly identify that heavy metal contributions to the soil represent the legacy of former Pb-Zn mining and smelting in the area. Depending upon soil properties, differences in the intensity of the vertical penetration of heavy metal pollution are discernible. Top soil coverage by local farmers provides little remediation. Consequently, hazardous conditions for the regional ecology, for agricultural usage and ultimately for human health remain in place. Based on chemical and isotopic results obtained, more effective remediation strategies need to be developed.

Preparation of Authigenic Pyrite from Methane-bearing Sediments for In Situ Sulfur Isotope Analysis Using SIMS.

Different sulfur isotope compositions of authigenic pyrite typically result from the sulfate-driven anaerobic oxidation of methane (SO4-AOM) and organiclastic sulfate reduction (OSR) in marine sediments. However, unravelling the complex pyritization sequence is a challenge because of the coexistence of different sequentially formed pyrite phases. This manuscript describes a sample preparation procedure that enables the use of secondary ion mass spectroscopy (SIMS) to obtain in situ δ34S values of various pyrite generations. This allows researchers to constrain how SO4-AOM affects pyritization in methane-bearing sediments. SIMS analysis revealed an extreme range in δ34S values, spanning from -41.6 to +114.8‰, which is much wider than the range of δ34S values obtained by the traditional bulk sulfur isotope analysis of the same samples. Pyrite in the shallow sediment mainly consists of 34S-depleted framboids, suggesting early diagenetic formation by OSR. Deeper in the sediment, more pyrite occurs as overgrowths and euhedral crystals, which display much higher SIMS δ34S values than the framboids. Such 34S-enriched pyrite is related to enhanced SO4-AOM at the sulfate-methane transition zone, postdating OSR. High-resolution in situ SIMS sulfur isotope analyses allow for the reconstruction of the pyritization processes, which cannot be resolved by bulk sulfur isotope analysis.

Multiple Sulfur Isotope Constraints on Sources and Formation Processes of Sulfate in Beijing PM2.5 Aerosol.

Recently air pollution is seriously threatening the health of millions of people in China. The multiple sulfur isotopic composition of sulfate in PM2.5 samples collected in Beijing is used to better constrain potential sources and formation processes of sulfate aerosol. The Δ33S values of sulfate in PM2.5 show a pronounced seasonality with positive values in spring, summer and autumn and negative values in winter. Positive Δ33S anomalies are interpreted to result from SO2 photolysis with self-shielding, and may reflect air mass transport between the troposphere and the stratosphere. The negative Δ33S signature (-0.300‰ < Δ33S < 0‰) in winter is possibly related to incomplete combustion of coal in residential stoves during the heating season, implying that sulfur dioxide released from residential stoves in more rural areas is an important contributor to atmospheric sulfate. However, negative Δ33S anomalies (-0.664‰ < Δ33S ← 0.300‰) in winter and positive Δ33S anomalies (0.300‰ < Δ33S < 0.480‰) in spring, summer, and autumn suggest sulfur isotopic equilibrium on an annual time frame, which may provide an implication for the absence of mass-independent fractionation of sulfur isotopes (S-MIF) in younger sediments. Results obtained here reveal that reducing the usage of coal and improving the heating system in rural areas will be important for efficiently decreasing the emissions of sulfur in China and beyond.

Using stable isotopes to trace sources and formation processes of sulfate aerosols from Beijing, China.

Particulate pollution from anthropogenic and natural sources is a severe problem in China. Sulfur and oxygen isotopes of aerosol sulfate (δ(34)Ssulfate and δ(18)Osulfate) and water-soluble ions in aerosols collected from 2012 to 2014 in Beijing are being utilized to identify their sources and assess seasonal trends. The mean δ(34)S value of aerosol sulfate is similar to that of coal from North China, indicating that coal combustion is a significant contributor to atmospheric sulfate. The δ(34)Ssulfate and δ(18)Osulfate values are positively correlated and display an obvious seasonality (high in winter and low in summer). Although an influence of meteorological conditions to this seasonality in isotopic composition cannot be ruled out, the isotopic evidence suggests that the observed seasonality reflects temporal variations in the two main contributions to Beijing aerosol sulfate, notably biogenic sulfur emissions in the summer and the increasing coal consumption in winter. Our results clearly reveal that a reduction in the use of fossil fuels and the application of desulfurization technology will be important for effectively reducing sulfur emissions to the Beijing atmosphere.

Effect of the pollution control measures on PM2.5 during the 2015 China Victory Day Parade: Implication from water-soluble ions and sulfur isotope.

Air pollution by particulate matter is a serious problem in Beijing. Strict pollution control measures have been carried out in Beijing prior to and during the 2015 China Victory Day Parade in order to improve air quality. This distinct event provides an excellent opportunity for investigating the impact of such measures on the chemical properties of particulate matter with an aerodynamic diameter ≤2.5 µm (PM2.5). The water-soluble ions as well as sulfur and oxygen isotopes of sulfate in PM2.5 collected between August 19 and September 18, 2015 (n = 31) were analyzed in order to trace the sources and formation processes of PM2.5 in Beijing. The results exhibit a decrease in concentration of water-soluble ions in PM2.5 including aerosol sulfate. In contrast, the mean values of δ34Ssulfate (4.7 ± 0.8‰ vs. 5.0 ± 2.0‰) and δ18Osulfate (18.3 ± 2.3‰ vs. 17.2 ± 6.0) in PM2.5 during the air pollution control period and the non-source control period exhibit no significant differences, which suggests that despite a reduction in concentration, the sulfate source remains identical for the two periods. It is inferred that the decrease in concentration of sulfate in PM2.5 mainly results from variations in air mass transport. Notably, the air mass during the pollution control period originated mainly from north and northeast and changed to southerly directions thereafter. The sulfur and oxygen isotopes of the sulfate point to coal combustion as the major source of sulfate in PM2.5 from the Beijing area.

Eutrophication, microbial-sulfate reduction and mass extinctions.

In post-Cambrian time, life on Earth experienced 5 major extinction events, likely instigated by adverse environmental conditions. Biodiversity loss among marine taxa, for at least 3 of these mass extinction events (Late Devonian, end-Permian and end-Triassic), has been connected with widespread oxygen-depleted and sulfide-bearing marine water. Furthermore, geochemical and sedimentary evidence suggest that these events correlate with rather abrupt climate warming and possibly increased terrestrial weathering. This suggests that biodiversity loss may be triggered by mechanisms intrinsic to the Earth system, notably, the biogeochemical sulfur and carbon cycle. This climate warming feedback produces large-scale eutrophication on the continental shelf, which, in turn, expands oxygen minimum zones by increased respiration, which can turn to a sulfidic state by increased microbial-sulfate reduction due to increased availability of organic matter. A plankton community turnover from a high-diversity eukaryote to high-biomass bacterial dominated food web is the catalyst proposed in this anoxia-extinction scenario and stands in stark contrast to the postulated productivity collapse suggested for the end-Cretaceous mass extinction. This cascade of events is relevant for the future ocean under predicted greenhouse driven climate change. The exacerbation of anoxic "dead" zones is already progressing in modern oceanic environments, and this is likely to increase due to climate induced continental weathering and resulting eutrophication of the oceans.

Tales of mystery and imagination in stable isotope geochemistry: celebrating the 75th birthday of Jochen Hoefs.

We celebrate the contribution of Jochen Hoefs to the development of stable isotope (bio)geochemistry on the occasion of his 75th birthday.

A Rare Glimpse of Paleoarchean Life: Geobiology of an Exceptionally Preserved Microbial Mat Facies from the 3.4 Ga Strelley Pool Formation, Western Australia.

Paleoarchean rocks from the Pilbara Craton of Western Australia provide a variety of clues to the existence of early life on Earth, such as stromatolites, putative microfossils and geochemical signatures of microbial activity. However, some of these features have also been explained by non-biological processes. Further lines of evidence are therefore required to convincingly argue for the presence of microbial life. Here we describe a new type of microbial mat facies from the 3.4 Ga Strelley Pool Formation, which directly overlies well known stromatolitic carbonates from the same formation. This microbial mat facies consists of laminated, very fine-grained black cherts with discontinuous white quartz layers and lenses, and contains small domical stromatolites and wind-blown crescentic ripples. Light- and cathodoluminescence microscopy, Raman spectroscopy, and time of flight-secondary ion mass spectrometry (ToF-SIMS) reveal a spatial association of carbonates, organic material, and highly abundant framboidal pyrite within the black cherts. Nano secondary ion mass spectrometry (NanoSIMS) confirmed the presence of distinct spheroidal carbonate bodies up to several tens of µm that are surrounded by organic material and pyrite. These aggregates are interpreted as biogenic. Comparison with Phanerozoic analogues indicates that the facies represents microbial mats formed in a shallow marine environment. Carbonate precipitation and silicification by hydrothermal fluids occurred during sedimentation and earliest diagenesis. The deciphered environment, as well as the δ13C signature of bulk organic matter (-35.3‰), are in accord with the presence of photoautotrophs. At the same time, highly abundant framboidal pyrite exhibits a sulfur isotopic signature (δ34S = +3.05‰; Δ33S = 0.268‰; and Δ36S = -0.282‰) that is consistent with microbial sulfate reduction. Taken together, our results strongly support a microbial mat origin of the black chert facies, thus providing another line of evidence for life in the 3.4 Ga Strelley Pool Formation.

Multiple sulphur and oxygen isotopes reveal microbial sulphur cycling in spring waters in the Lower Engadin, Switzerland.

Highly mineralized springs in the Scuol-Tarasp area of the Lower Engadin and in the Albula Valley near Alvaneu, Switzerland, display distinct differences with respect to the source and fate of their dissolved sulphur species. High sulphate concentrations and positive sulphur (δ(34)S) and oxygen (δ(18)O) isotopic compositions argue for the subsurface dissolution of Mesozoic evaporitic sulphate. In contrast, low sulphate concentrations and less positive or even negative δ(34)S and δ(18)O values indicate a substantial contribution of sulphate sulphur from the oxidation of sulphides in the crystalline basement rocks or the Jurassic sedimentary cover rocks. Furthermore, multiple sulphur (δ(34)S, Δ(33)S) isotopes support the identification of microbial sulphate reduction and sulphide oxidation in the subsurface, the latter is also evident through the presence of thick aggregates of sulphide-oxidizing Thiothrix bacteria.

Flourishing ocean drives the end-Permian marine mass extinction.

The end-Permian mass extinction, the most severe biotic crisis in the Phanerozoic, was accompanied by climate change and expansion of oceanic anoxic zones. The partitioning of sulfur among different exogenic reservoirs by biological and physical processes was of importance for this biodiversity crisis, but the exact role of bioessential sulfur in the mass extinction is still unclear. Here we show that globally increased production of organic matter affected the seawater sulfate sulfur and oxygen isotope signature that has been recorded in carbonate rock spanning the Permian-Triassic boundary. A bifurcating temporal trend is observed for the strata spanning the marine mass extinction with carbonate-associated sulfate sulfur and oxygen isotope excursions toward decreased and increased values, respectively. By coupling these results to a box model, we show that increased marine productivity and successive enhanced microbial sulfate reduction is the most likely scenario to explain these temporal trends. The new data demonstrate that worldwide expansion of euxinic and anoxic zones are symptoms of increased biological carbon recycling in the marine realm initiated by global warming. The spatial distribution of sulfidic water column conditions in shallow seafloor environments is dictated by the severity and geographic patterns of nutrient fluxes and serves as an adequate model to explain the scale of the marine biodiversity crisis. Our results provide evidence that the major biodiversity crises in Earth's history do not necessarily implicate an ocean stripped of (most) life but rather the demise of certain eukaryotic organisms, leading to a decline in species richness.

Biosignatures in chimney structures and sediment from the Loki's Castle low-temperature hydrothermal vent field at the Arctic Mid-Ocean Ridge.

We investigated microbial life preserved in a hydrothermally inactive silica­barite chimney in comparison with an active barite chimney and sediment from the Loki's Castle low-temperature venting area at the Arctic Mid-Ocean Ridge (AMOR) using lipid biomarkers. Carbon and sulfur isotopes were used to constrain possible metabolic pathways. Multiple sulfur (dδ34S, Δ33S) isotopes on barite over a cross section of the extinct chimney range between 21.1 and 22.5 % in δ34S, and between 0.020 and 0.034 % in Δ33S, indicating direct precipitation from seawater. Biomarker distributions within two discrete zones of this silica­barite chimney indicate a considerable difference in abundance and diversity of microorganisms from the chimney exterior to the interior. Lipids in the active and inactive chimney barite and sediment were dominated by a range of 13C-depleted unsaturated and branched fatty acids with δ13C values between -39.7 and -26.7 %, indicating the presence of sulfur-oxidizing and sulfate-reducing bacteria. The majority of lipids (99.5 %) in the extinct chimney interior that experienced high temperatures were of archaeal origin. Unusual glycerol monoalkyl glycerol tetraethers (GMGT) with 0­4 rings were the dominant compounds suggesting the presence of mainly (hyper-) thermophilic archaea. Isoprenoid hydrocarbons with δ13C values as low as -46 % also indicated the presence of methanogens and possibly methanotrophs.

Tracing the source of Beijing soil organic carbon: a carbon isotope approach.

Bulk soil organic carbon concentration and isotopic composition characterize its sources and fate, identify the anthropogenic input of organic carbon into the soil, and trace soil carbon turnover. Coal and/or coal combustion products represent the prime anthropogenic input of organic carbon into three soil profiles located in the vicinity of a steel company. Three profiles positioned away from any direct industrial contribution display vertical pattern in soil organic carbon concentration and isotopic composition that resemble more commonly observed downward gradients in soil carbon chemistry and indicate microbial soil carbon turnover. Two additional profiles located outside of the immediate industrial area display vertical carbon isotope profiles between typical of those from industrial and non-industrial areas. Eight soil profiles and their vertical distribution of bulk organic carbon isotopic composition and concentration collected in the Beijing area reveal and distinguish both anthropogenic and natural contributions of carbon to these soils.

Widespread occurrence of two carbon fixation pathways in tubeworm endosymbionts: lessons from hydrothermal vent associated tubeworms from the mediterranean sea.

Vestimentiferan tubeworms (siboglinid polychetes) of the genus Lamellibrachia are common members of cold seep faunal communities and have also been found at sedimented hydrothermal vent sites in the Pacific. As they lack a digestive system, they are nourished by chemoautotrophic bacterial endosymbionts growing in a specialized tissue called the trophosome. Here we present the results of investigations of tubeworms and endosymbionts from a shallow hydrothermal vent field in the Western Mediterranean Sea. The tubeworms, which are the first reported vent-associated tubeworms outside the Pacific, are identified as Lamellibrachia anaximandri using mitochondrial ribosomal and cytochrome oxidase I (COI) gene sequences. They harbor a single gammaproteobacterial endosymbiont. Carbon isotopic data, as well as the analysis of genes involved in carbon and sulfur metabolism indicate a sulfide-oxidizing chemoautotrophic endosymbiont. The detection of a hydrogenase gene fragment suggests the potential for hydrogen oxidation as alternative energy source. Surprisingly, the endosymbiont harbors genes for two different carbon fixation pathways, the Calvin-Benson-Bassham (CBB) cycle as well as the reductive tricarboxylic acid (rTCA) cycle, as has been reported for the endosymbiont of the vent tubeworm Riftia pachyptila. In addition to RubisCO genes we detected ATP citrate lyase (ACL - the key enzyme of the rTCA cycle) type II gene sequences using newly designed primer sets. Comparative investigations with additional tubeworm species (Lamellibrachia luymesi, Lamellibrachia sp. 1, Lamellibrachia sp. 2, Escarpia laminata, Seepiophila jonesi) from multiple cold seep sites in the Gulf of Mexico revealed the presence of acl genes in these species as well. Thus, our study suggests that the presence of two different carbon fixation pathways, the CBB cycle and the rTCA cycle, is not restricted to the Riftia endosymbiont, but rather might be common in vestimentiferan tubeworm endosymbionts, regardless of the habitat.

Sulphur diagenesis in the sediments of the Kiel Bight, SW Baltic Sea, as reflected by multiple stable sulphur isotopes.

In this work, the biogeochemistry of marine sediments from the Kiel Bight, coastal SW Baltic Sea, is studied based on the abundance and isotopic composition of organic carbon and different forms of sedimentary sulphur. Active bacterial sulphate reduction, partly under sulphate-limiting conditions, is evident from paired δ(34)S and δ(18)O values of pore water sulphate. The resulting pore water sulphide is partly precipitated as acid-volatile iron sulphide and subsequently forms sedimentary pyrite, partly serves in later diagenetic sulphurisation of organic matter, or remains dissolved in the pore water, all evident from the respective δ(34)S values. Microbial sulphate turnover is associated with an apparent isotopic fractionation between dissolved sulphate and dissolved sulphide (Δ(34)S) that varies between 46 and 66‰.