Low Sulfide Concentrations Research Articles

Magmatic fluid input explaining the geochemical anomaly of very high arsenic in some southern Tibetan geothermal waters

Tibet is characterized by extremely high terrestrial heat flow and widely distributed hydrothermal systems, among which many are discharging geothermal waters with extremely high arsenic concentrations from over 10 mg/L to up to 126 mg/L. The distribution of these high arsenic waters is basically in accordance with the location of the Indian continental subduction zone. A detailed analysis indicates that host rock leaching alone cannot explain the observed arsenic anomaly. Instead, substantial contribution of arsenic from the underlying magma chambers is postulated, which are likely mantle-derived intrusions that have been severely contaminated by the very thick crustal material below southern Tibet, possibly including deep-seated arsenic-rich sedimentary rocks. Alternatively, the partial melts at crustal depths reflected by the detected low-velocity and/or high-conductivity anomalies in southern Tibet, serving as the magmatic heat source of the high‑arsenic hydrothermal systems, may also form indirectly under the high-temperature conditions generated by mantle upwelling or due to crustal thickening. Low sulfide concentrations further promote high dissolved arsenic concentrations with little formation of thioarsenates and no precipitation of limiting arsenic-sulfide phases. In contrast, mantle magmas less affected by crustal contamination, serving as the heat source of many hydrothermal systems in rift zones and hot spots worldwide where the crust is thinner, are releasing magmatic fluids lower in arsenic and higher in mantle sulfur species. Overall, the existence of a magmatic heat source alone does not ensure the formation of geothermal waters with very high arsenic concentrations, and geothermal waters from sedimentary rock-hosted systems are neither necessarily arsenic-rich. The most critical factor controlling the arsenic concentration of geothermal water discharging from a magmatic hydrothermal system is the geological genesis of the magma fluid and its chemical composition.

On the Nature of the Cathodic Reaction during Corrosion of Copper in Anoxic Sulfide Solutions

Sulfide-induced corrosion is expected to be the dominating long-term corrosion process for copper containers in technical concepts for deep geological disposal of spent nuclear fuel (SNF), adapted in several waste management programs around the world. The present study investigates the atomic-scale mechanism of the cathode side of the corrosion reaction using Density Functional Theory (DFT) calculations. Despite the central role of the reaction, neither the site of reaction nor the active species has been previously established. Here we compare the cathodic reaction leading to H2-evolution on pure copper and on chalcocite (Cu2S) surfaces. The considered H-donors are OH−/H2O and HS−/H2S which are all available at the neutral to alkaline conditions anticipated at the SNF disposal sites. Assuming Volmer-Tafel-Heyrovsky kinetics, we find that the cathodic reactions are many orders of magnitude faster on copper compared to copper sulfide. Although we find that HS−/H2S have lower reaction barriers than H2O, our kinetic analysis suggest that H2O is expected to be the main H-source for the cathodic reaction under SNF repository conditions as results of the low sulfide concentrations (≲ 10 μM) expected in SNF repositories in Sweden, Finland and Canada.

Corrosion of aluminium alloy AlSi7Mg0.3 in artificial sea water with added sodium sulphide

The corrosion behaviour of aluminium alloy AlSi7Mg0.3 in artificial sea water with added 0, 20, 50 and 100 ppm of Na2S was investigated over the course of immersion of 42 days. Samples were taken at various times and their electrochemical and microstructural properties characterized. The corrosion current densities in all immersion solutions was very low, in the range of 10−7–10−9 A cm−2. The structure, composition and protectiveness of the so formed oxide layers were dependent on the Na2S concentration and immersion time. The presence of low sulphide concentration (<50 ppm) is beneficial for the corrosion protection of AlSi7Mg0.3 alloy.

Variation of geochemical environments associated with whale-fall biomass mineralization processes in the sediment during the mobile scavenger, enrichment opportunist, and sulfophilic stages

The succession of faunal composition of a whale-fall community is believed to depend on the progress of decomposition of the whale carcass, which itself is dependent on microbial activity in the sediment around the carcass. This means that the faunal succession could be reflected in the variation of the geochemical environment. In this study, we examined sperm whale carcasses placed in two areas of Japanese waters. In Sagami Bay at a depth of ca. 500 m, dive surveys were performed 2 weeks, 2 months, and 9 months after implantation, when mobile scavengers and Osedax worms were observed. Off Cape Nomamisaki, 12 carcasses were implanted at a depth of 200–300 m, and dive surveys were performed there 17, 29, and 41 months after implantation, and abundant chemosynthesis-based mussels were observed at these times. The recovered sediment cores from beneath and around the carcasses in Sagami Bay showed increases in 15N-enriched ammonium and 34S-depleted sulfide and decreases in 34S-enriched sulfate during the 9 months following implantation, and their stoichiometric relationship suggested that proteinaceous matter from the carcass was decomposed preferentially followed by active bacterial sulfate reduction. In comparison, relatively low ammonium but high sulfide concentrations after 41 months off Cape Nomamisaki suggest that primarily lipids from the almost skeletonized carcasses were decomposed in the sediment during bacterial sulfate reduction. Such variation of decomposed organic substrates and geochemical environments result from interaction with the animals inhabiting in and on the sediments adjacent the whale carcasses. It is possible that evolution of the geochemical environment plays an important role in faunal succession, from the enrichment opportunist to sulfophilic stages.

Interactions of functional bacteria and their contributions to the performance in integrated autotrophic and heterotrophic denitrification

Compared to autotrophic and heterotrophic denitrification process, the Integrated autotrophic and heterotrophic denitrification (IAHD) has wider foreground of applications in the condition where the organic carbon, nitrate and inorganic sulfur compounds usually co-exist in the actual wastewaters. As the most well-known IAHD process, the denitrifying sulfide removal (DSR) could simultaneously convert sulfide, nitrate and organic carbon into sulfur, dinitrogen gas and carbon dioxide, respectively. Thus, systematical metabolic functions and contributions of autotrophic and heterotrophic denitrifiers to the IAHD-DSR performance became an problem demanding to be promptly studied. In this work, three upflow anaerobic sludge bioreactors (UASBs) were individually started up in autotrophic (a-DSR), heterotrophic (h-DSR) and mixotrophic conditions (m-DSR). Then, the operating conditions of each bioreactor were switched to different trophic conditions with low and high sulfide concentrations in the influent (200 and 400 mg/L). The removal efficiencies of sulfide, nitrate and acetate all reached 100% in all three bioreactors throughout the operational stages. However, the sulfur transformation ratio ranged from 34.5% to 39.9% at the low sulfide concentration and from 76.8% to 86.7% at the high sulfide concentration in the mixotrophic conditions. Microbial community structure analyzed by the Illumina sequencing indicated that Thiobacillus, which are autotrophic sulfide-oxidizing, nitrate-reducing bacteria (a-soNRB), was the dominant genus (81.3%) in the a-DSR bioreactor. With respect to the mixotrophic conditions, at low sulfide concentration in the m-DSR bioreactor, Thiobacillus (a-soNRB) and Thauera, which are heterotrophic nitrate-reducing bacteria (hNRB), were the dominant genera, with percentages of 48.8% and 14.9%, respectively. When the sulfide concentration in the influent was doubled, the percentage of Thiobacillus decreased by approximately 9-fold (from 48.8% to 5.4%), and the total percentage of Azoarcus and Pseudomonas, which are heterotrophic sulfide-oxidizing, nitrate-reducing bacteria (h-soNRB), increased by approximately 6-fold (from 10.1% to 59.4%). Therefore, the following interactions between functional groups and their functional mechanisms in the DSR process were proposed: (1) a-soNRB (Thiobacillus) and hNRB (Thauera) worked together to maintain the performance under the low sulfide concentration; (2) h-soNRB (Azoarcus and Pseudomonas) took the place of a-soNRB and worked together with hNRB (Thauera and Allidiomarina) under the high sulfide concentration; and (3) a-soNRB (such as Thiobacillus) were possibly the key bacteria and may have contributed to the low sulfur transformation, and h-soNRB may be responsible for the high sulfur transformation in the DSR process.

Decrypting the sulfur cycle in oceanic oxygen minimum zones.

Here we present ecophysiological studies of the anaerobic sulfide oxidizers considered critical to cryptic sulfur cycling in oceanic oxygen minimum zones (OMZs). We find that HS- oxidation rates by microorganisms in the Chilean OMZ offshore from Dichato are sufficiently rapid (18 nM h-1), even at HS- concentrations well below 100 nM, to oxidize all sulfide produced during sulfate reduction in OMZs. Even at 100 nM, HS- is well below published half-saturation concentrations and we conclude that the sulfide-oxidizing bacteria in OMZs (likely the SUP05/ARTIC96BD lineage of the gammaproteobacteria) have high-affinity (>105 g-1 wet cells h-1) sulfur uptake systems. These specific affinities for sulfide are higher than those recorded for any other organism on any other substrate. Such high affinities likely allow anaerobic sulfide oxidizers to maintain vanishingly low sulfide concentrations in OMZs driving marine cryptic sulfur cycling. If more broadly distributed, such high-affinity sulfur biochemistry could facilitate sulfide-based metabolisms and prominent S-cycles in many other ostensibly sulfide-free environments.

Transdermal Detection of Low Concentrations of Hydrogen Sulfide

Transdermal Detection of Low Concentrations of Hydrogen Sulfide

Robust Mercury Methylation across Diverse Methanogenic Archaea.

ABSTRACTMethylmercury (MeHg) production was compared among nine cultured methanogenic archaea that contain hgcAB, a gene pair that codes for mercury (Hg) methylation. The methanogens tested produced MeHg at inherently different rates, even when normalized to growth rate and Hg availability. Eight of the nine tested were capable of MeHg production greater than that of spent- and uninoculated-medium controls during batch culture growth. Methanococcoides methylutens, an hgcAB+ strain with a fused gene pair, was unable to produce more MeHg than controls. Maximal conversion of Hg to MeHg through a full batch culture growth cycle for each species (except M. methylutens) ranged from 2 to >50% of the added Hg(II) or between 0.2 and 17 pmol of MeHg/mg of protein. Three of the species produced >10% MeHg. The ability to produce MeHg was confirmed in several hgcAB+ methanogens that had not previously been tested (Methanocella paludicola SANAE, Methanocorpusculum bavaricum, Methanofollis liminatans GKZPZ, and Methanosphaerula palustris E1-9c). Maximal methylation was observed at low sulfide concentrations (<100 μM) and in the presence of 0.5 to 5 mM cysteine. For M. hollandica, the addition of up to 5 mM cysteine enhanced MeHg production and cell growth in a concentration-dependent manner. As observed for bacterial Hg methylators, sulfide inhibited MeHg production. An initial evaluation of sulfide and thiol impacts on bioavailability showed methanogens responding to Hg complexation in the same way as do Deltaproteobacteria. The mercury methylation rates of several methanogens rival those of the better-studied Hg-methylating sulfate- and iron-reducing Deltaproteobacteria.

NanoSIMS and tissue autoradiography reveal symbiont carbon fixation and organic carbon transfer to giant ciliate host

The giant colonial ciliate Zoothamnium niveum harbors a monolayer of the gammaproteobacteria Cand. Thiobios zoothamnicoli on its outer surface. Cultivation experiments revealed maximal growth and survival under steady flow of high oxygen and low sulfide concentrations. We aimed at directly demonstrating the sulfur-oxidizing, chemoautotrophic nature of the symbionts and at investigating putative carbon transfer from the symbiont to the ciliate host. We performed pulse-chase incubations with 14C- and 13C-labeled bicarbonate under varying environmental conditions. A combination of tissue autoradiography and nanoscale secondary ion mass spectrometry coupled with transmission electron microscopy was used to follow the fate of the radioactive and stable isotopes of carbon, respectively. We show that symbiont cells fix substantial amounts of inorganic carbon in the presence of sulfide, but also (to a lesser degree) in the absence of sulfide by utilizing internally stored sulfur. Isotope labeling patterns point to translocation of organic carbon to the host through both release of these compounds and digestion of symbiont cells. The latter mechanism is also supported by ultracytochemical detection of acid phosphatase in lysosomes and in food vacuoles of ciliate cells. Fluorescence in situ hybridization of freshly collected ciliates revealed that the vast majority of ingested microbial cells were ectosymbionts.

English

Anaerobic co-digestion improves the pig faeces digestion process. This work presents anaerobic digestion of pig faeces (C) as compared to 2 co-substrates: Sludge (L) from waste waters and bovine ruminal gastric content (R). Pig faeces used were generated in a local farm at the Juarez Autonomous University of Tabasco (UJAT), with a total population of 148 animals. Analytical determinations were made on the substrate and co-substrates. Each treatment was performed in triplicate (9 experimental units), for 18 weeks. C+R co-digestion had the highest removal of chemical oxygen demand (COD) with 90%. Biogas production (0.012 L day-1) was quantified for C and C+R, with concentrations of 70.87±8.65 and 71.89 ± 7.60% of methane (CH4), respectively. For C+L, it was 0.009 L day-1, with 77.89±6.74% of CH4. Results obtained showed that co-digestion of C+L was better with regards to the quality of biogas from low hydrogen sulfide (H2S) concentrations (70.33±6.36 ppm). The use of anaerobic co-digestion systems represents an alternative treatment for faeces generated in pig farms and other kinds of wastes to reduce the potential source of infection produced by these types of waste. Key words: Biogas, digester, manure, pig faeces, rumen.

Pre- and posttreatment with hydrogen sulfide prevents ventilator-induced lung injury by limiting inflammation and oxidation.

Although essential in critical care medicine, mechanical ventilation often results in ventilator-induced lung injury. Low concentrations of hydrogen sulfide have been proven to have anti-inflammatory and anti-oxidative effects in the lung. The aim of this study was to analyze the kinetic effects of pre- and posttreatment with hydrogen sulfide in order to prevent lung injury as well as inflammatory and oxidative stress upon mechanical ventilation. Mice were either non-ventilated or mechanically ventilated with a tidal volume of 12 ml/kg for 6 h. Pretreated mice inhaled hydrogen sulfide in low dose for 1, 3, or 5 h prior to mechanical ventilation. Posttreated mice were ventilated with air followed by ventilation with hydrogen sulfide in various combinations. In addition, mice were ventilated with air for 10 h, or with air for 5 h and subsequently with hydrogen sulfide for 5 h. Histology, interleukin-1β, neutrophil counts, and reactive oxygen species formation were examined in the lungs. Both pre-and posttreatment with hydrogen sulfide time-dependently reduced or even prevented edema formation, gross histological damage, neutrophil influx and reactive oxygen species production in the lung. These results were also observed in posttreatment, when the experimental time was extended and hydrogen sulfide administration started as late as after 5 h air ventilation. In conclusion, hydrogen sulfide exerts lung protection even when its application is limited to a short or delayed period. The observed lung protection is mediated by inhibition of inflammatory and oxidative signaling.

Molybdenum isotope fractionation and speciation in a euxinic lake—Testing ways to discern isotope fractionation processes in a sulfidic setting

The molybdenum (Mo) isotope composition in euxinic shales has been used as a proxy for the global distribution of anoxic conditions in ancient oceans, and since more recently also as a proxy for sulfide concentrations in depositional environments. However, there is currently no way to distinguish isotope fractionation at low bottom water sulfide concentrations in ‘local’ basins from ‘global’ secular isotope variations associated with changing seawater composition. This uncertainty is challenging the use of Mo isotopes for paleoceanographic reconstructions.To explore this further, we present new data from sediments deposited over the past ~9800years in one of the best studied euxinic localities in the world: Lake Cadagno in Switzerland. The sample set allows us to test ways to discern isotope fractionation processes at play in a highly restricted euxinic basin.Most of our drill core samples (n=18) show high δ98Mo values similar to previously studied shallow sediments, indicative of quantitative Mo removal from the water column (Dahl et al. 2010a). However, a few samples (n=3) deposited between about 1200 and 3400years ago carry low δ98Mo values and have been isotopically fractionated in the lake. Sedimentological and geochemical characterizations show that these δ98Mo-fractionated sediments formed during times of frequent injection of O2- and sediment-rich river water into the deep sulfidic water column. A positive correlation between δ98Mo and sedimentary Mo contents suggests that isotope fractionation occurred during times of non-quantitative Mo removal, although Mn-oxide cycling at the chemocline might also contribute a subordinate proportion of (98Mo-depleted) molybdenum into the sulfidic zone. Sedimentary Mo/U enrichments relative to oxic lake water further supports the hypothesis that a particulate Mo shuttle was most efficient during times of quantitative Mo removal. Therefore, periods with inefficient Mo capture are ascribed to incomplete conversion of molybdate to particle reactive Mo species when bottom water H2S levels were low or less stable than today.Using XAFS spectroscopy, we found that the two distinct Mo compounds predominating in the sediments (MoIV-S and MoVI-OS) are not diagnostic for isotope fractionation that has occurred in Lake Cadagno. Instead, we infer that δ98Mo-fractionated products (forming via a low-sulfide Mo pathway) can be subsequently altered with little or no isotopic imprint during remobilization and re-precipitation (e.g., at higher sulfide levels in the sediments) as well as during post-depositional oxidation.Future work could investigate local δ98Mo-fractionation processes expressed in other euxinic settings and explore other sedimentary metrics to constrain the steps involved in the euxinic burial pathway(s). One tantalizing prospect of this is to distinguish between local bottomwater sulfide levels and variations in the fraction of global seafloor anoxia from the Mo isotope composition in ancient euxinic mudrocks.

Measurement of Low Hydrogen Sulfide Concentrations in the Coastal Area Near the Ulsan Industrial Complex

Measurement of Low Hydrogen Sulfide Concentrations in the Coastal Area Near the Ulsan Industrial Complex

Abundance and Diversity of Denitrifying and Anammox Bacteria in Seasonally Hypoxic and Sulfidic Sediments of the Saline Lake Grevelingen.

Denitrifying and anammox bacteria are involved in the nitrogen cycling in marine sediments but the environmental factors that regulate the relative importance of these processes are not well constrained. Here, we evaluated the abundance, diversity, and potential activity of denitrifying, anammox, and sulfide-dependent denitrifying bacteria in the sediments of the seasonally hypoxic saline Lake Grevelingen, known to harbor an active microbial community involved in sulfur oxidation pathways. Depth distributions of 16S rRNA gene, nirS gene of denitrifying and anammox bacteria, aprA gene of sulfur-oxidizing and sulfate-reducing bacteria, and ladderane lipids of anammox bacteria were studied in sediments impacted by seasonally hypoxic bottom waters. Samples were collected down to 5 cm depth (1 cm resolution) at three different locations before (March) and during summer hypoxia (August). The abundance of denitrifying bacteria did not vary despite of differences in oxygen and sulfide availability in the sediments, whereas anammox bacteria were more abundant in the summer hypoxia but in those sediments with lower sulfide concentrations. The potential activity of denitrifying and anammox bacteria as well as of sulfur-oxidizing, including sulfide-dependent denitrifiers and sulfate-reducing bacteria, was potentially inhibited by the competition for nitrate and nitrite with cable and/or Beggiatoa-like bacteria in March and by the accumulation of sulfide in the summer hypoxia. The simultaneous presence and activity of organoheterotrophic denitrifying bacteria, sulfide-dependent denitrifiers, and anammox bacteria suggests a tight network of bacteria coupling carbon-, nitrogen-, and sulfur cycling in Lake Grevelingen sediments.

Transdermal Detection of Low Concentrations of Hydrogen Sulfide

We report here a novel approach to measure circulating hydrogen sulfide (H2S) non‐invasively as a potential way to diagnose and monitor endothelial dysfunction and peripheral artery disease (PAD). PAD is a life‐threatening condition caused by arterial constriction and obstruction of blood flow leading to limb ischemia. Current methods to diagnose and monitor PAD lack sensitivity, result in frequent false‐negatives, and require specialized technicians. Recent studies indicate that decreased H2S production is an underlying cause of PAD. In addition, reduced plasma H2S correlates with endothelial dysfunction in untreated hypertension, diabetes, sleep apnea and other cardiovascular diseases. Conversely, excess H2S is cytotoxic causing irreversible damage to mitochondrial function. Therefore, careful monitoring of plasma H2S levels is essential to diagnose and treat vascular disease and to prevent H2S toxicity. This device was designed to measure H2S at the surface of the skin to test the hypothesis that the diffusion rate (and therefore gas phase concentration) of H2S is directly proportional to the concentration of H2S in the blood. Our results demonstrate that the device is sensitive enough to detect H2S at 10 part per billion (ppb) or lower in gas standards and in the headspace of a 3 nM solution of Na2S (H2S donor). In vitro studies used excised rat skin superfused on the subcutaneous surface with a H2S solution. H2S was detected in a stream of N2 gas flowing through a sealed chamber on the epidermal side both by GC/MS measurement and with the sensor only when the superfusing solution contained an H2S donor demonstrating that H2S diffuses through the skin. The diffusion rate of H2S through excised abdominal skin from a male Sprague‐Dawley rat is approximately 1.42×10−9 μmol/s/cm2/μM. The device also detected increases in H2S on the skin surface in anesthetized rats within seconds of intra‐venous injection of Na2S at doses that caused a fall in arterial pressure, with an estimated average diffusion rate of 4×10−8 μmol/s/cm2/μM. Therefore, this noninvasive, highly‐sensitive and portable device has the potential to transform diagnosis and monitoring of early stage PAD and to monitor H2S biosynthesis or exposure in vivo.

Effects of soluble sulfide on zebrafish (Danio rerio) embryonic development.

Zebrafish embryos were used to investigate the developmental effects of sulfide. Mortality, teratogenic effects, and developmental parameters of early developmental embryos were recorded. The biodistribution of sulfide in developing zebrafish embryos and larvae were measured through fluorescence imaging. The influences of sulfide on the cardiac function and development velocity of zebrafish embryos were dependent on sulfide concentration. Heart rate and development velocity increased with exposure to lower sulfide concentrations, which may be attributed to the cardioprotective properties of H2S. Meanwhile, heart rate and development velocity decreased, whereas pericardial edema, yolk sac edema, and trunk abnormalities occurred with exposure to higher sulfide concentrations. Sulfide accumulated in the blastoderm of early developmental embryos and was then transported to the yolk sac and yolk extension with the embryonic development. Finally, sulfide was transferred from the yolk to the eyes of zebrafish larvae. The details of mechanism of sulfide toxicity require further research.

계사 및 우사 내 암모니아 및 황화수소 노출농도 평가

Objectives: There are many hazardous agents at livestock farms. In particular, gases can be detrimental to both workers and animals. This study evaluated ammonia and hydrogen sulfide concentrations in broiler hen barns and beef cattle barns according to sampling location and height. Methods: Three broiler hen barns and three beef cattle barns were selected for gas monitoring in this study. Ammonia and hydrogen sulfide concentrations were measured using a direct-reading instrument which could measure the target gases simultaneously. Gas monitoring was conducted at human breathing height and animal breathing height at three points in each livestock farm. Results: Ammonia concentrations at the broiler hen barns ranged from 3.3 to 12.5 ppm by sampling location and height, but hydrogen sulfide was not detected. In the beef cattle barns, ammonia ranged from 3.1 to 16.3 ppm and low concentrations of hydrogen sulfide were detected at some animal breathing heights. The gas concentrations detected at each livestock farm were significantly higher in the animal breathing zones than in human breathing zones (p<0.0001). Conclusions: We found a difference in gas concentrations between human breathing zones and animal breathing zones. Gas monitoring should be conducted to improve the related environment considering both workers' and animals' health and safety.

Tailings Weathering and Arsenic Mobility at the Abandoned Zgounder Silver Mine, Morocco

The abandoned Zgounder Mine (Morocco) was exploited for Ag from 1982 to 1990 and generated nearly 490,000 t of mill tailings before it was closed without being reclaimed. The tailings contain low concentrations of sulfide (mainly as pyrite, sphalerite, and galena) and carbonates (mainly dolomite). Silicates (muscovite, albite, chlorite, labradorite, actinolite, and orthoclase) occur in high concentrations. The most abundant trace elements are As, Ti, Fe, Mn, Zn, and Pb. We studied the geochemical behavior of the mine wastes to identify the main factors controlling drainage water chemistry. Particular emphasis was put on sorption phenomena to explain the low As concentrations in the leachates despite significant As levels in the tailings. Weathering cell tests carried out on various tailings produced two types of contaminated drainage: acidic and neutral. The kinetic test leachates contained high concentrations of some contaminants, including As (0.8 mg L−1), Co (11 mg L−1), Cu (34 mg L−1), Fe (70 mg L−1), Mn (126 mg L−1), and Zn (314 mg L−1). Acidity and contaminants in the leachates were controlled by dissolution of soluble salts and Fe hydrolysis rather than sulfide oxidation. Batch sorption tests quantified the significance of As sorption, and sequential extraction showed that most of the As sorption was associated with the reducible fractions (Fe and Mn oxides and oxyhydroxides).

Growth and activity of ANME clades with different sulfate and sulfide concentrations in the presence of methane.

Extensive geochemical data showed that significant methane oxidation activity exists in marine sediments. The organisms responsible for this activity are anaerobic methane-oxidizing archaea (ANME) that occur in consortia with sulfate-reducing bacteria. A distinct zonation of different clades of ANME (ANME-1, ANME-2a/b, and ANME-2c) exists in marine sediments, which could be related to the localized concentrations of methane, sulfate, and sulfide. In order to test this hypothesis we performed long-term incubation of marine sediments under defined conditions with methane as a headspace gas: low or high sulfate (±4 and ±21 mM, respectively) in combination with low or high sulfide (±0.1 and ±4 mM, respectively) concentrations. Control incubations were also performed, with only methane, high sulfate, or high sulfide. Methane oxidation was monitored and growth of subtypes ANME-1, ANME-2a/b, and ANME-2c assessed using qPCR analysis. A preliminary archaeal community analysis was performed to gain insight into the ecological and taxonomic diversity. Almost all of the incubations with methane had methane oxidation activity, with the exception of the incubations with combined low sulfate and high sulfide concentrations. Sulfide inhibition occurred only with low sulfate concentrations, which could be due to the lower Gibbs free energy available as well as sulfide toxicity. ANME-2a/b appears to mainly grow in incubations which had high sulfate levels and methane oxidation activity, whereas ANME-1 did not show this distinction. ANME-2c only grew in incubations with only sulfate addition. These findings are consistent with previously published in situ profiling analysis of ANME subclusters in different marine sediments. Interestingly, since all ANME subtypes also grew in incubations with only methane or sulfate addition, ANME may also be able to perform anaerobic methane oxidation under substrate limited conditions or alternatively perform additional metabolic processes.

Role of pockmarks in diversity and species assemblages of coastal macrobenthic communities

We used existing bathymetric data to study the macrofauna of a geophysical pockmark field restricted to a benthic habitat engineered by the tubiculous amphipod Haploops nirae in South Brittany (France). Stations inside and outside pockmarks of different morphometric characteristics (location, size, depression depth) were sampled for macrofauna and environmental parameters (sediment characteristics, organic matter, chl a, hydrogen sulfide and methane concentrations). Diversity indices showed higher species richness inside pockmarks, especially for species with medium to high abundances. Most sediment cores showed low methane but high hydrogen sulfide concentrations. We hypothesised that after eruption, the remaining residual methane from pockmark sediments is oxidised by seawater sulfate and accounts for the high sulfide concentrations found at increasing depth in our samples and the low methane concentrations. We found no relationship between sediment profiles and morphometric features of the pockmarks. Macrofauna assemblages inside vs. outside pockmarks appeared to be different. Pockmarks appear to increase connectivity among habitats and heterogeneity within habitats, thereby creating local hotspots that allow the settlement of species that cannot otherwise develop in Haploops tube mats. Multivariate analyses distinguished 4 groups of pockmarks and control stations. We assumed that deeper pockmarks were created more recently than shallow pockmarks and that each pockmark is at a different stage of evolution, hence explaining the large variability in the characteristics of pockmark groups. This explains why previous investigations have found contradictory results when comparing macrofauna species diversity and composition between areas inside and outside pockmarks. Finally, we propose and discuss a successional stage model for pockmarks.