Sulfate Zone Research Articles

The Enrichment Mechanism of REE at Sulfate and Methane Transition Zone (SMTZ) of the Northern Part of the South China Sea

Rare earth elements (REE) are important raw materials for electronic products and green-energy technology and deep-sea sediment as an important potential source of REE mineral. It is of great scientific significance to understand the influence of REE in deep-sea sediments. In this paper, thirty sediments samples and eleven sediments samples were collected at the site SH3 and SH1 of Shenhu area, respectively. The trace elements, major elements, and different Fe-Mn minerals were analyzed to investigate the role of anaerobic oxidation of methane (AOM) in the enrichment of rare earth elements in the marine sediments. The result showed that the content of ∑REE/Ti increased at the top of sulfate and methane transition zone (SMTZ) at site SH1 and SH3. Combined with the analysis of different forms of ferromanganese minerals and the REE patterns, it is inferred that there is little influence of terrigenous input to the REE content. In contrary, the REE-rich carbonate phase and REE-rich Fe-Mn oxides (hydroxides) phase have important contribution of REE enrichment at the top of SMTZ. Meanwhile, the calculations of the quantitative relationship between the REE-rich carbonate phase and REE-rich Fe-Mn oxides (hydroxides) phase also confirm this conclusion. And the AOM caused the decrease of the REE-rich Fe-Mn oxides (hydroxides) phase and increase of the REE-rich carbonate phase. This is the potential explanation of ∑REE/Ti enrichment at the top of SMTZ. This study is of great scientific significance for the study of REE enrichment mechanism in the methane seeps and provided a new sight of REE enrichment mechanism in deep-sea sediments.

Evaluation of rice production towards VietGAP standards in the Mekong delta

The study, conducted in threeecological sub-regions (flood, alluvial, and acid sulphate zones) in the Mekong delta region, aims to evaluate the efficiency of VietGAP practice to benefit, safe food and environment in paddy production. The research was demonstrated in three cooperatives, including Tan Cuong cooperative, Tam Nong district, Dong Thap province (flood zone);Khiet Tam cooperative, Vinh Thanh district, Can Tho city (alluvial zone); and Phuoc Trung cooperative, Chau Thanh A district, Hau Giang province (acid sulphate zone). At each cooperative, the rice VietGAP model (1 ha) was compared with the rice traditional model (1 ha) and collected the field diary record of 30 rice VietGAP model households and 30 rice traditional model households. Data were collected, analysed for evaluating technical, financial, and environmental effects. The results showed that applying VietGAP standards in paddy production obtained many benefits such as decreasing seed rate, fertiliser application, and pesticide use, and increasing rice yield by 2%. The profit of farmers applying VietGAP standards was raised by 28% compared to farmers not following the VietGAP practices. Thanks to reducing the number of times spraying pesticides, it reduced pesticide residues in rice grain, soil, and water at the end of the crop. Thus, rice production in the direction of VietGAP can increase profit, safe food and environment.

Propionate Converting Anaerobic Microbial Communities Enriched from Distinct Biogeochemical Zones of Aarhus Bay, Denmark under Sulfidogenic and Methanogenic Conditions.

The relationship between predominant physiological types of prokaryotes in marine sediments and propionate degradation through sulfate reduction, fermentation, and methanogenesis was studied in marine sediments. Propionate conversion was assessed in slurries containing sediment from three different biogeochemical zones of Aarhus Bay, Denmark. Sediment slurries were amended with 0, 3, or 20 mM sulfate and incubated at 25 °C and 10 °C for 514–571 days. Methanogenesis in the sulfate zone and sulfate reduction in the methane zone slurries was observed. Both processes occurred simultaneously in enrichments originating from samples along the whole sediment. Bacterial community analysis revealed the dominance of Desulfobacteraceae and Desulfobulbaceae members in sulfate-amended slurries incubated at 25°C and 10°C. Cryptanaerobacter belonging to the Peptococcaceae family dominated sulfate-free methanogenic slurries at 25°C, whereas bacteria related to Desulfobacteraceae were dominant at 10°C. Archaeal community analysis revealed the prevalence of different genera belonging to Methanomicrobiales in slurries incubated at different temperatures and amended with different sulfate concentrations. Methanosarcinaceae were only detected in the absence of sulfate. In summary, Aarhus Bay sediment zones contain sulfate reducers, syntrophs, and methanogens interacting with each other in the conversion of propionate. Our results indicate that in Aarhus Bay sediments, Cryptanaerobacter degraded propionate in syntrophic association with methanogens.

Assessment of the eruptive activity and identification of the mud breccia's source in the Olimpi mud volcano field, Eastern Mediterranean

Even though the intensity and frequency of the eruptive episodes of deep-sea mud volcanoes (MVs) substantially regulate the methane fluxes into the hydrosphere and the development of the near-seafloor sulfate zone that affects the position of the gas hydrate stability zone, these factors are not yet adequately investigated. Moreover, the evaluation of the eruptive sediment's thermal maturity may provide solid documentation of the petroleum generation potential in high depths below seafloor (bsf). Hence, the present study, through the integration of sedimentary facies analysis with hydrocarbon biomarker analysis (based on the concentrations of long-chain (C25–C35) n-alkanes, hopanes and steranes), supported by swath bathymetry data, examined five sediment cores recovered from the Gelendzhik, Moscow, Milano, Leipzig and Heraklion MVs of the Olimpi mud volcano field (OMVF) on the central Mediterranean Ridge. The main objective of this investigation was to assess the ‘modern’ eruptive activity in the OMVF and identify the mud breccia's origin and mobilization depth (based on its maturity level), and the ages of the source beds. Among the studied MVs, Milano, Leipzig and Heraklion appear ‘recently’ active, while Moscow perhaps remains in dormancy for at least one century. The eruptive activity in the OMVF seems to be, generally, vigorous and persistent, while it is linked with several source beds of variable stratigraphy or environmental condition. The multiple eruptive episodes, occurring as uninterrupted events or via pulses, create conditions that perhaps favour high releases of methane into the water column as well as the growth of the gas hydrate phase near the seafloor. The identified ‘modern’ mudflows appear thermally immature for oil generation, while they most probably originate from terrestrial source beds located not deeper than 2 km bsf. A Messinian age could be suggested for the principal sources of the very soft to soft mud breccias of the OMVF, while stratigraphic horizons of Early-Middle Miocene might be proposed as the likely major sources for the firm to very stiff mud breccias of the area.

The acid sulfate zone and the mineral alteration styles of the Roman Puteoli (Neapolitan area, Italy): clues on fluid fracturing progression at the Campi Flegrei volcano

Abstract. Active fumarolic solfataric zones represent important structures of dormant volcanoes, but unlike emitted fluids, their mineralizations are omitted in the usual monitoring activity. This is the case of the Campi Flegrei caldera in Italy, among the most hazardous and best-monitored explosive volcanoes in the world, where the landscape of Puteoli is characterized by an acid sulfate alteration that has been active at least since Roman time. This paper provides temperature, mineralogical, textural, compositional and stable isotope data for those solfataric terrains sampled at the crater and Pisciarelli slope of the Solfatara volcano between 2013 and 2019. Temperatures vary between 40 and 95 ∘C. Minerals include alunite with grain sizes generally larger than 20 µm, alunogen, native sulfur, well-ordered kaolinite, and, common at Pisciarelli, pyrite, illite and NH4 sulfates. Sulfate terrains have higher contents of Ti, Ba, Au, As, Hg and Tl relative to their parent substrate. The Pisciarelli slope is anomalous in terms of the presence of NH4. δ34S values for sulfides and native S range between −3.00 ‰ and 0.49 ‰ and from −4.42 ‰ to 0.80 ‰, respectively. Sulfates show δ34S and δ18O values in the range of −2.78 ‰ to 2.09 ‰ and between 4.60 ‰ and 31.33 ‰, respectively. The style of mineralization and the stable isotope geochemistry do produce complex and not completely consistent classifications and genetic constraints. We merge our data with volcanological information, data from exploration drillings and geophysical results. With the conceptual model, we suggest a series of shallow and deep aquifers interconnected like “communicating vessels” through a main fault system that downthrows Solfatara with respect to Pisciarelli. Fluid outflow from the different discrete aquifers hosted in sediments – and possibly bearing organic imprints – is the main dataset that allows determination of the steam-heated environment with a supergene setting superimposed. Supergene conditions and high-sulfidation relicts, together with the narrow sulfate alteration zone buried under the youngest volcanic deposits, point to the existence of an evolving paleo-conduit. The data will contribute to monitoring and evaluating the volcanic hazards.

Controls on volatile fatty acid concentrations in marine sediments (Baltic Sea)

Abstract Volatile fatty acids (VFA) are key intermediates in the degradation pathway of organic matter (OM) in marine sediments. They are products of fermentation and are utilized as substrates in the terminal steps of microbial OM mineralization, such as sulfate reduction and methanogenesis. We studied the distribution of formate, acetate, propionate and butyrate concentrations in the pore water throughout 100-m deep sedimentary sequences in the Baltic Sea. The sediments included both sulfate and methane zones and were retrieved during the Integrated Ocean Drilling Program Expedition 347. VFA concentrations were consistently low throughout the sulfate and methane zones, ranging from few hundred nanomolar to about hundred micromolar, thus pointing to efficient microbial utilization in the terminal OM mineralization steps in both zones. Concentrations of formate followed a different depth trend than the other three VFAs suggesting a different mechanistical control of the formate turnover. Calculations of the Gibbs energy reveal that acetoclastic methanogenesis is exergonic (up to −30 kJ (mol CH4)−1) throughout the sulfate zone and suggest that methanogens can potentially coexist with sulfate reducers in the sulfate zone while sharing acetate as a substrate. In the deeper methane-rich sediments, the energy yield of acetoclastic methanogenesis is generally very low (less negative than −10 kJ (mol CH4)−1). The uniformly low acetate concentrations in the methane zone suggest its active microbial turnover but the pathway from acetate to methane still remains unclear. Interestingly, acetoclastic sulfate reduction still yields at least −20 kJ (mol sulfate)−1 in the methane zone and, thus, sulfate reducers may utilize acetate as electron donor in the methane zone, which is in agreement with the earlier findings of sulfate reducers in methanogenic sediments.

Hydrothermal alteration environments and recent dynamics of the Ischia volcanic island (southern Italy): Insights from repeated field, mineralogical and geochemical surveys before and after the 2017 Casamicciola earthquake

This study presents the results of repeated surveys conducted in hydrothermally altered areas on the active volcanic island of Ischia (in the Gulf of Naples, southern Italy). Data were obtained from field work, in situ temperature measurements, X-ray diffraction, optical and scanning electron microscopy, EDS-SEM micro-analysis, infrared spectroscopy and whole-rock geochemistry analyses on samples collected in October 2016, September 2017, March 2018 and November 2018, both prior to and following the damaging seismic event that occurred in August 2017 at Casamicciola. Mineralogical results point to the evolution of acid sulfate zones along the northern and western flanks of a resurgent block located in the central part of the island, in strict relation with endogenous fluid outgassing indicated in the literature. Mineralogy and whole-rock geochemistry of these acid sulfate zones reveal magmatic-hydrothermal environments in association with major structures that enable fluid circulation. It is interpreted that rare coarser alunites within dominant steam-heated and supergene alteration mineral assemblages are associated with environments that are no longer active, but which are supplied by magmatic vapours. In addition, collected data indicate slow endogenous degassing from hydrothermal reservoirs. Data from September 2017 show variations in the sulfate assemblage within the acidic sulfate zone located near the earthquake's epicentre, and acidification and the transitory appearance of alum-(K) is apparent under a nearly unchanged endogenous supply. Meteorological conditions of late summer could, in principle, justify the appearance of alum-(K), but its coexistence with alunogen and soil temperatures refute this possibility. Alum-(K) is interpreted to be the product of alunite decomposition at a local temperature of ca. 100 °C. Assuming a correct space-time relationship between the appearance of alum-(K) and the earthquake, it is thus inferred that mechanical activation by tectonic stress is the possible cause of alunite decomposition.

Organoclastic sulfate reduction in the sulfate-methane transition of marine sediments

Abstract Sulfate and methane diffuse vertically along opposed concentration gradients into the sulfate-methane transition in subsurface marine sediments where anaerobic oxidation of methane with sulfate takes place. The stoichiometry of this process is 1:1, yet the calculated sulfate flux often exceeds the calculated methane flux. Our aim was to determine whether organoclastic sulfate reduction, fueled by the oxidation of buried organic matter, explains this excess sulfate flux into the sulfate-methane transition. We analyzed data for sulfate, methane and sulfate reduction from eight sites in Danish coastal waters. Fluxes of sulfate and methane were determined by diffusion-reaction modeling whereas sulfate reduction rates were determined by 35S radiotracer experiments at high depth resolution. The sulfate reduction data showed that the organic carbon mineralization rates followed a log-log linear depth trend throughout the sulfate zone. Extrapolation of this power law trend down into the sulfate-methane transition showed organic carbon oxidation corresponded to 14–59% of the total sulfate flux into the zone and in average explained 82% of the excess sulfate consumption above the 1:1 stoichiometry. A part of the excess sulfate was consumed directly by organoclastic sulfate reduction while a part drove a cryptic methane cycle by which the organic matter was degraded to methane and the methane concurrently oxidized to CO2 with sulfate. We extrapolated the same power law trend down through the methanogenic zone and found that this provided a good estimate of total methanogenesis in the sediment column when compared to the upward flux of methane.

Methane emission from rice cultivation in different agro-ecological zones of the Mekong river delta: seasonal patterns and emission factors for baseline water management

ABSTRACTThis study comprises a set of methane emission measurements in rice fields located in the four agro-ecological zones of the Mekong River Delta (MRD), namely the zones with (i) alluvial soils, (ii) salinity intrusion, (iii) deep flood, and (iv) acid sulfate soils. These zones have very distinct bio-physical conditions and cropping cycles that will affect methane emissions in various forms. Our study includes comprehensive mapping of these zones as well as an overview of rice statistics (activity data) at provincial level for each cropping season. Emission data were obtained by the closed chamber method. The available data set comprises 7 sites with 15 cropping seasons. Mean emission rates showed large variations ranging from 0.31 to 9.14 kg CH4 ha−1 d−1. Statistical analysis resulted in weighted means for all zones that we use as zone-specific CH4 emission factors (EFz) in the context of the IPCC Tier 2 approach. The lowest EFz was computed for the saline accounting for 1.14 kg CH4 ha−1 d−1 (confidence interval: 0.60–2.14). The EFz values of the alluvial and acid sulfate zones were 2.39 kg CH4 ha−1 d−1 (2.19–4.13) and 2.78 kg CH4 ha−1 d−1 (2.65–3.76), respectively, which indicated that they were not different from each other derived from their confidence intervals. The deep flood zone, however, required a season-specific, assessment of EFz because emission in the autumn–winter cropping season, corresponding to the wet period, was significantly higher (9.14 kg CH4 ha−1 d−1 (7.08–11.2)) than the other seasons (2.24 kg CH4 ha−1 d−1 (1.59–3.47)). Although these emission factors correspond to baseline water management and do not capture the diversity of farmers’ practices, we see the availability of zone-specific data as an important step for a more detailed assessment of Business as Usual emissions as well as possible mitigation potentials in one of the most important rice growing regions of the world.

Bioturbation as a key driver behind the dominance of Bacteria over Archaea in near-surface sediment

The factors controlling the relative abundances of Archaea and Bacteria in marine sediments are poorly understood. We determined depth distributions of archaeal and bacterial 16S rRNA genes by quantitative PCR at eight stations in Aarhus Bay, Denmark. Bacterial outnumber archaeal genes 10–60-fold in uppermost sediments that are irrigated and mixed by macrofauna. This bioturbation is indicated by visual observations of sediment color and faunal tracks, by porewater profiles of dissolved inorganic carbon and sulfate, and by distributions of unsupported 210Pb and 137Cs. Below the depth of bioturbation, the relative abundances of archaeal genes increase, accounting for one third of 16S rRNA genes in the sulfate zone, and half of 16S rRNA genes in the sulfate-methane transition zone and methane zone. Phylogenetic analyses reveal a strong shift in bacterial and archaeal community structure from bioturbated sediments to underlying layers. Stable isotopic analyses on organic matter and porewater geochemical gradients suggest that macrofauna mediate bacterial dominance and affect microbial community structure in bioturbated sediment by introducing fresh organic matter and high-energy electron acceptors from overlying seawater. Below the zone of bioturbation, organic matter content and the presence of sulfate exert key influences on bacterial and archaeal abundances and overall microbial community structure.

Controls on subsurface methane fluxes and shallow gas formation in Baltic Sea sediment (Aarhus Bay, Denmark)

Shallow gas accumulates in coastal marine sediments when the burial rate of reactive organic matter beneath the sulfate zone is sufficiently high and the methanogenic zone is sufficiently deep. We investigated the controls on methane production and free methane gas accumulation along a 400m seismo-acoustic transect across a sharp transition from gas-free into gas-bearing sediment in Aarhus Bay (Denmark). Twelve gravity cores were taken, in which the pore water was analyzed for inorganic solutes while rates of organic carbon mineralization were measured experimentally by 35SO42− radiotracer method. The thickness of organic-rich Holocene mud increased from 5 to 10m along the transect concomitant with a shallowing of the depth of the sulfate-methane transition from >4m to 2.5m. In spite of drastic differences in the distribution of methane and sulfate in the sediment along the transect, there were only small differences in total mineralization, and methanogenesis was only equivalent to about 1% of sulfate reduction. Shallow gas appeared where the mud thickness exceeded 8–9m. Rates of methanogenesis increased along the transect as did the upward diffusive flux of methane. Interestingly, the increase in the sedimentation rate and Holocene mud thickness had only a modest direct effect on methanogenesis rates in deep sediments. This increase in methane flux, however, triggered a shallowing of the sulfate-methane transition which resulted in a large increase in methanogenesis at the top of the methanogenic zone. Thus, our results demonstrate a positive feedback mechanism that causes a strong enhancement of methanogenesis and explains the apparently abrupt appearance of gas when a threshold thickness of organic-rich mud is exceeded.

Formate, acetate, and propionate as substrates for sulfate reduction in sub-arctic sediments of Southwest Greenland.

Volatile fatty acids (VFAs) are key intermediates in the anaerobic mineralization of organic matter in marine sediments. We studied the role of VFAs in the carbon and energy turnover in the sulfate reduction zone of sediments from the sub-arctic Godthåbsfjord (SW Greenland) and the adjacent continental shelf in the NE Labrador Sea. VFA porewater concentrations were measured by a new two-dimensional ion chromatography-mass spectrometry method that enabled the direct analysis of VFAs without sample pretreatment. VFA concentrations were low and surprisingly constant (4–6 μmol L−1 for formate and acetate, and 0.5 μmol L−1 for propionate) throughout the sulfate reduction zone. Hence, VFAs are turned over while maintaining a stable concentration that is suggested to be under a strong microbial control. Estimated mean diffusion times of acetate between neighboring cells were <1 s, whereas VFA turnover times increased from several hours at the sediment surface to several years at the bottom of the sulfate reduction zone. Thus, diffusion was not limiting the VFA turnover. Despite constant VFA concentrations, the Gibbs energies (ΔGr) of VFA-dependent sulfate reduction decreased downcore, from −28 to −16 kJ (mol formate)−1, −68 to −31 kJ (mol acetate)−1, and −124 to −65 kJ (mol propionate)−1. Thus, ΔGr is apparently not determining the in-situ VFA concentrations directly. However, at the bottom of the sulfate zone of the shelf station, acetoclastic sulfate reduction might operate at its energetic limit at ~ −30 kJ (mol acetate)−1. It is not clear what controls VFA concentrations in the porewater but cell physiological constraints such as energetic costs of VFA activation or uptake could be important. We suggest that such constraints control the substrate turnover and result in a minimum ΔGr that depends on cell physiology and is different for individual substrates.

Mineralogical characterization related to physico-chemical conditions in the pyrite-rich tailings in Guryong Mine, Korea

The detailed characterization of mineralogical changes with depth in pyrite-rich tailings from an abandoned mine provides insight into the future geochemical progression of the tailings. Based on the pH and mineralogical characterization, the Guryong mine tailings can be divided into four zones: jarosite zone, iron (Fe)-sulfate zone, Fe-oxyhydroxide and gypsum-bearing pyrite zone, and calcite-bearing pyrite zone. The jarosite zone was approximately 50 cm deep from the surface and had secondary gypsum (CaSO4·2H2O) and jarosite [KFe3(SO4)2(OH)6]. The pH of the jarosite zone ranged from 2.3 to 4.0, and the ratio of total Fe to total sulfur (S) ranged from 0.7 to 4.3. These results show that the solid phase, schwertmannite or jarosite, is associated with the total sulfate (SO4) content. The Fe-sulfate zone had low pH values caused by strong pyrite oxidation and greatest amounts of the secondary minerals and acid-leachable heavy metals. The Fe-oxyhydroxide and gypsum-bearing pyrite zone reflects partial alteration of pyrite resulting in the coexistence of secondary gypsum and primary pyrite. The calcite-bearing pyrite zone had pH values exceeding 7.0 at greater depths and contained primary calcite (CaCO3). However, the GS6 and GS10 profiles, which contained coarse particles near the water table, were the most acidic and their calcite contents were not dectected. The oxidation of pyrite is the most important factor in the mineral cycling of Guryong mine tailings, controlling the changes in pH, the precipitation of secondary mineral phases, and the behavior of heavy metals through the profile.

Anaerobic oxidation of methane in an iron‐rich Danish freshwater lake sediment

Freshwater systems are identified as one of the main natural methane sources, but little is known about the importance of anaerobic oxidation of methane (AOM) in these systems. We investigated AOM in a lake sediment characterized by a high reactive iron content, normal sulfate concentrations in the bottom water (∼ 250 µmol L−1), and a relatively deep sulfate penetration of ∼ 14 cm, which facilitated the spatial resolution of the zones of methane production and consumption. Methane concentrations, δ13C methane profiles, and directly measured and modeled AOM rates all consistently demonstrated methane consumption throughout the anoxic, nitrate‐free, Fe(III)‐ and sulfate‐containing zone, oxidizing ∼ 90% of the diffusive methane flux. Thus, the concentration gradient of methane was steepest at the base of the Fe(III) and sulfate zone and decreased strongly toward the sediment surface; while δ13CH4 increased from &lt; −80‰ in the methanogenic zone to −48‰ in the surface sediment. Direct measurements demonstrated AOM activity throughout the Fe(III) and sulfate zone. AOM rates peaked at sulfate concentrations below 3 µmol L−1, which suggests a possible coupling of AOM to the reduction of more crystalline Fe(III) oxides. Alternatively, AOM could be coupled to sulfate reduction, which was in turn supported by a cryptic sulfur cycle coupled to Fe(III) reduction. Our results show that AOM can substantially reduce methane emission from freshwater sediments, and the finding of AOM at sulfate concentrations &lt; 3 µmol L−1 suggests that AOM could be of greater importance in freshwater systems, and in ancient low‐sulfate oceans, than was previously appreciated.

Anaerobic methane oxidation in low-organic content methane seep sediments

Sulfate-dependent anaerobic oxidation of methane (AOM) is the key sedimentary microbial process limiting methane emissions from marine sediments and methane seeps. In this study, we investigate how the presence of low-organic content sediment influences the capacity and efficiency of AOM at Bullseye vent, a gas hydrate-bearing cold seep offshore of Vancouver Island, Canada. The upper 8m of sediment contains <0.4wt.% total organic carbon (OC) and primarily consists of glacially-derived material that was deposited 14,900–15,900yrs BP during the retreat of the late Quaternary Cordilleran Ice Sheet. We hypothesize this aged and exceptionally low-OC content sedimentary OM is biologically refractory, thereby limiting degradation of non-methane OM by sulfate reduction and maximizing methane consumption by sulfate-dependent AOM. A radiocarbon-based dissolved inorganic carbon (DIC) isotope mass balance model demonstrates that respired DIC in sediment pore fluids is derived from a fossil carbon source that is devoid of 14C. A fossil origin for the DIC precludes remineralization of non-fossil OM present within the sulfate zone as a significant contributor to pore water DIC, suggesting that nearly all sulfate is available for anaerobic oxidation of fossil seep methane. Methane flux from the SMT to the sediment water interface in a diffusion-dominated flux region of Bullseye vent was, on average, 96% less than at an OM-rich seep in the Gulf of Mexico with a similar methane flux regime. Evidence for enhanced methane oxidation capacity within OM-poor sediments has implications for assessing how climate-sensitive reservoirs of sedimentary methane (e.g., gas hydrate) will respond to ocean warming, particularly along glacially-influenced mid and high latitude continental margins.

Interaction between hydrocarbon seepage, chemosynthetic communities, and bottom water redox at cold seeps of the Makran accretionary prism: insights from habitat-specific pore water sampling and modeling

Abstract. The interaction between fluid seepage, bottom water redox, and chemosynthetic communities was studied at cold seeps across one of the world's largest oxygen minimum zones (OMZ) located at the Makran convergent continental margin. Push cores were obtained from seeps within and below the core-OMZ with a remotely operated vehicle. Extracted sediment pore water was analyzed for sulfide and sulfate concentrations. Depending on oxygen availability in the bottom water, seeps were either colonized by microbial mats or by mats and macrofauna. The latter, including ampharetid polychaetes and vesicomyid clams, occurred in distinct benthic habitats, which were arranged in a concentric fashion around gas orifices. At most sites colonized by microbial mats, hydrogen sulfide was exported into the bottom water. Where macrofauna was widely abundant, hydrogen sulfide was retained within the sediment. Numerical modeling of pore water profiles was performed in order to assess rates of fluid advection and bioirrigation. While the magnitude of upward fluid flow decreased from 11 cm yr−1 to &lt;1 cm yr−1 and the sulfate/methane transition (SMT) deepened with increasing distance from the central gas orifice, the fluxes of sulfate into the SMT did not significantly differ (6.6–9.3 mol m−2 yr−1). Depth-integrated rates of bioirrigation increased from 120 cm yr−1 in the central habitat, characterized by microbial mats and sparse macrofauna, to 297 cm yr−1 in the habitat of large and few small vesicomyid clams. These results reveal that chemosynthetic macrofauna inhabiting the outer seep habitats below the core-OMZ efficiently bioirrigate and thus transport sulfate down into the upper 10 to 15 cm of the sediment. In this way the animals deal with the lower upward flux of methane in outer habitats by stimulating rates of anaerobic oxidation of methane (AOM) with sulfate high enough to provide hydrogen sulfide for chemosynthesis. Through bioirrigation, macrofauna engineer their geochemical environment and fuel upward sulfide flux via AOM. Furthermore, due to the introduction of oxygenated bottom water into the sediment via bioirrigation, the depth of the sulfide sink gradually deepens towards outer habitats. We therefore suggest that – in addition to the oxygen levels in the water column, which determine whether macrofaunal communities can develop or not – it is the depth of the SMT and thus of sulfide production that determines which chemosynthetic communities are able to exploit the sulfide at depth. We hypothesize that large vesicomyid clams, by efficiently expanding the sulfate zone down into the sediment, could cut off smaller or less mobile organisms, as e.g. small clams and sulfur bacteria, from the sulfide source.

A cryptic sulfur cycle driven by iron in the methane zone of marine sediment (Aarhus Bay, Denmark)

Sulfate reduction and sulfur–iron geochemistry were studied in 5–6 m deep gravity cores of Holocene mud from Aarhus Bay (Denmark). A goal was to understand whether sulfate is generated by re-oxidation of sulfide throughout the sulfate and methane zones, which might explain the abundance of active sulfate reducers deep below the main sulfate zone. Sulfate penetrated down to 130 cm where methane started to build up and where the concentration of free sulfide peaked at 5.5 mM. Below this sulfate–methane transition, sulfide diffused downwards to a sulfidization front at 520 cm depth, below which dissolved iron, Fe 2+, accumulated in the pore water. Sulfate reduction rates measured by 35S-tracer incubations in the sulfate zone were high due to high concentrations of reactive organic matter. Within the sulfate–methane transition, sulfate reduction was distinctly stimulated by the anaerobic oxidation of methane. In the methane zone below, sulfate remained at positive “background” concentrations of <0.5 mM down to the sulfidization front. Sulfate reduction decreased steeply to rates which at 300–500 cm depth were 0.2–1 pmol SO 4 2− cm −3 d −1, i.e., 4–5 orders of magnitude lower than rates measured near the sediment surface. The turn-over time of sulfate increased from 3 years at 12 cm depth to 100–1000 years down in the methane zone. Sulfate reduction in the methane zone accounted for only 0.1% of sulfate reduction in the entire sediment column and was apparently limited by the low pore water concentration of sulfate and the low availability of organic substrates. Amendment of the sediment with both sulfate and organic substrates immediately caused a 10- to 40-fold higher, “potential sulfate reduction” which showed that a physiologically intact community of sulfate reducing bacteria was present. The “background” sulfate concentration appears to be generated from the reaction of downwards diffusing sulfide with deeply buried Fe(III) species, such as poorly-reactive iron oxides or iron bound in reactive silicates. The oxidation of sulfide to sulfate in the sulfidic sediment may involve the formation of elemental sulfur and thiosulfate and their further disproportionation to sulfide and sulfate. The net reaction of sulfide and Fe(III) to form pyrite requires an additional oxidant, irrespective of the formation of sulfate. This could be CO 2 which is reduced with H 2 to methane. The methane subsequently diffuses upwards to become re-oxidized at the sulfate–methane transition and thereby removes excess reducing power and enables the formation of excess sulfate. We show here how the combination of these well-established sulfur–iron–carbon reactions may lead to the deep formation of sulfate and drive a cryptic sulfur cycle. The iron-rich post-glacial sediments underlying Holocene marine mud stimulate the strong sub-surface sulfide reoxidation observed in Aarhus Bay and are a result of the glacial to interglacial history of the Baltic Sea area. Yet, processes similar to the ones described here probably occur widespread in marine sediments, in particular along the ocean margins.

Role of sulfate reduction and methane production by organic carbon degradation in eutrophic fjord sediments (Limfjorden, Denmark)

The anaerobic mineralization of buried organic matter through sulfate reduction and methanogenesis was studied in 2‐m‐long piston cores of organic‐rich, silty‐clay sediment from two sites in Limfjorden, Denmark. An extended sulfate‐methane transition (SMT) zone was found at 1–1.5‐m sediment depth, accompanied by peaks in sulfide (4–6 mmol L−1) and high dissolved inorganic carbon (30–50 mmol L−1). Pore‐water acetate concentrations were 2‐10 µmol L‐1. 14C‐acetate was oxidized to 14CO2 in the sulfate zone and reduced to 14CH4 at and below the SMT. CO2 reduction was the predominant pathway of methanogenesis below the sulfate zone. Sulfate reduction rates (SRRs) determined by 35S tracer experiments decreased with depth throughout the sulfate zone from &gt; 100 nmol cm−3 d−1 near the sediment surface to &lt; 1 nmol cm−3 d−1 at depth. The depth trend of rates was equally well described by a power law function and a reactive continuum model. Only a small percentage of the total 35S‐SRR was due to anaerobic oxidation of methane. In contrast, diffusion‐reaction modeling of pore‐water sulfate indicated that sulfate reduction was insignificant throughout the sulfate zone and that most of the activity occurred at the SMT. A comparison of the burial flux of organic carbon below the sulfate zone and the returning flux of methane indicated that the diffusion modeling of pore‐water sulfate strongly underestimated in situ SRRs, whereas the 35S data may have overestimated the rates at depth. Modeled and measured SRR could be reconciled provided that bioirrigation reached to at least 20–40‐cm sediment depth, which appears realistic given the predominant burrowing polychaete fauna.

Gas hydrates in shallow deposits of the Amsterdam mud volcano, Anaximander Mountains, Northeastern Mediterranean Sea

We investigated gas hydrate in situ inventories as well as the composition and principal transport mechanisms of fluids expelled at the Amsterdam mud volcano (AMV; 2,025 m water depth) in the Eastern Mediterranean Sea. Pressure coring (the only technique preventing hydrates from decomposition during recovery) was used for the quantification of light hydrocarbons in near-surface deposits. The cores (up to 2.5 m in length) were retrieved with an autoclave piston corer, and served for analyses of gas quantities and compositions, and pore-water chemistry. For comparison, gravity cores from sites at the summit and beyond the AMV were analyzed. A prevalence of thermogenic light hydrocarbons was inferred from average C1/C2+ ratios <35 and δ13C-CH4 values of −50.6‰. Gas venting from the seafloor indicated methane oversaturation, and volumetric gas–sediment ratios of up to 17.0 in pressure cores taken from the center demonstrated hydrate presence at the time of sampling. Relative enrichments in ethane, propane, and iso-butane in gas released from pressure cores, and from an intact hydrate piece compared to venting gas suggest incipient crystallization of hydrate structure II (sII). Nonetheless, the co-existence of sI hydrate can not be excluded from our dataset. Hydrates fill up to 16.7% of pore volume within the sediment interval between the base of the sulfate zone and the maximum sampling depth at the summit. The concave-down shapes of pore-water concentration profiles recorded in the center indicate the influence of upward-directed advection of low-salinity fluids/fluidized mud. Furthermore, the SO42− and Ba2+ pore-water profiles in the central part of the AMV demonstrate that sulfate reduction driven by the anaerobic oxidation of methane is complete at depths between 30 cm and 70 cm below seafloor. Our results indicate that methane oversaturation, high hydrostatic pressure, and elevated pore-water activity caused by low salinity promote fixing of considerable proportions of light hydrocarbons in shallow hydrates even at the summit of the AMV, and possibly also of other MVs in the region. Depending on their crystallographic structure, however, hydrates will already decompose and release hydrocarbon masses if sediment temperatures exceed ca. 19.3°C and 21.0°C, respectively. Based on observations from other mud volcanoes, the common occurrence of such temperatures induced by heat flux from below into the immediate subsurface appears likely for the AMV.

Sulfate‐reducing bacteria in marine sediment (Aarhus Bay, Denmark): abundance and diversity related to geochemical zonation

In order to better understand the main factors that influence the distribution of sulfate-reducing bacteria (SRB), their population size and their metabolic activity in high- and low-sulfate zones, we studied the SRB diversity in 3- to 5-m-deep sediment cores, which comprised the entire sulfate reduction zone and the upper methanogenic zone. By combining EMA (ethidium monoazide that can only enter damaged/dead cells and may also bind to free DNA) treatment with real-time PCR, we determined the distributions of total intact bacteria (16S rDNA genes) and intact SRB (dsrAB gene), their relative population sizes, and the proportion of dead cells or free DNA with depth. The abundance of SRB corresponded in average to 13% of the total bacterial community in the sulfate zone, 22% in the sulfate-methane transition zone and 8% in the methane zone. Compared with the total bacterial community, there were relatively less dead/damaged cells and free DNA present than among the SRB and this fraction did not change systematically with depth. By DGGE analysis, based on the amplification of the dsrA gene (400 bp), we found that the richness of SRB did not change with depth through the geochemical zones; but the clustering was related to the chemical zonation. A full-length clone library of the dsrAB gene (1900 bp) was constructed from four different depths (20, 110, 280 and 500 cm), and showed that the dsrAB genes in the near-surface sediment (20 cm) was mainly composed of sequences close to the Desulfobacteraceae, including marine complete and incomplete oxidizers such as Desulfosarcina, Desulfobacterium and Desulfococcus. The three other libraries were predominantly composed of Gram-positive SRB.