Methane and hydrogen sulfide in porewater of sediment cores from the upwelling area off Namibia

Porewater concentrations of sulfate, methane, and other relevant constituents were determined on four sediment cores from the high productivity upwelling area off Namibia which were recovered from the continental slope at water depths of 1300 and 2000 m. At all four stations a distinct sulfate-methane transition zone was observed several meters below the seafloor in which both sulfate and methane are consumed. Nutrient porewater concentration profiles do not show gradient slope changes at the depths of the transition zones. Flux calculations carried out on the basis of the determined porewater profiles revealed that anaerobic methane oxidation accounts for 100% of deep sulfate reduction within the sulfate-methane transition zone and consumes the total net diffusive sulfate flux. A significant contribution of organic carbon oxidation to the reduction of sulfate at these depths could, therefore, be excluded. We state that porewater profiles of sulfate with constant gradients above the transition zones are indicative for anaerobic methane oxidation controlling sulfate reduction.

Some hydrophysical and hydrochemical parameters of the upper part of the hydrogen sulfide zone in the Black Sea, September 11-22, 1994

Features of spatial variability of hydrogen sulfide in the northeastern part of the Black Sea are estimated. Some technical aspects of H2S concentration determination in the anoxic zone are discussed: in its upper part at H2S concentration <30 µmol/l, the photometric method is recommended, while for deeper layers the iodometric method should be used. With linearity of vertical distribution of hydrogen sulfide and ammonium taken into account their vertical gradients are estimated as 0.49+/-0.04 µmol/m and 0.19+/-0.06 µmol/m respectively. It is shown that the upper boundary of the H2S layer corresponds to the isopycnal surface with Sigma_t = 16.19+/-0.05 arbitrary units. Special attention is paid to relationship of hydrogen sulfide distribution with hydrophysical features in the region under study, in particular in the coastal zone. It is shown that hydrodynamic conditions control spatial distribution of hydrogen sulfide. On the basis of isopycnal treatment of the H2S field existence of a coastal convergence zone is proved, and peculiarities are recognized of vertical circulation in the main Black Sea gyre and coastal anticyclonic eddies; here hydrogen sulfide serves as a tracer of hydrophysical mixing processes.

Sulfide petrology of basalts at DSDP Holes 69-504B and 69-505B

Primary sulfide mineralization in basalts of the Costa Rica Rift occurs mainly in chrome-spinel-bearing olivine tholeiites. Primary sulfides form both globules, consisting of quenched single-phase solid solutions, and irregular polymineralic segregations of pyrrhotite, chalcopyrite, cubanite, and pentlandite. Two types of sulfide solid solutions - iron-nickel (Mss) and iron-copper (Iss) - were found among sulfide globules. These types appear to have formed because of sulfide-sulfide liquid immiscibility in the host magmas; as proved by the presence of globules with a distinct phase boundary between Mss and Iss. Such two-phase globules are associated with large olivine phenocrysts. Inhomogeneties among the globule composition likewise are caused by sulfide-sulfide immiscibility. Secondary sulfides form irregular segregations and veins consisting of pyrite, marcasite, and chalcopyrite.

Consistent increase in dimethyl sulfide (DMS) in response to high CO2 in five shipboard bioassays from contrasting NW European waters

The ubiquitous marine trace gas dimethyl sulfide (DMS) comprises the greatest natural source of sulfur to the atmosphere and is a key player in atmospheric chemistry and climate. We explore the short-term response of DMS production and cycling and that of its algal precursor dimethyl sulfoniopropionate (DMSP) to elevated carbon dioxide (CO2) and ocean acidification (OA) in five 96 h shipboard bioassay experiments. Experiments were performed in June and July 2011, using water collected from contrasting sites in NW European waters (Outer Hebrides, Irish Sea, Bay of Biscay, North Sea). Concentrations of DMS and DMSP, alongside rates of DMSP synthesis and DMS production and consumption, were determined during all experiments for ambient CO2 and three high-CO2 treatments (550, 750, 1000 µatm). In general, the response to OA throughout this region showed little variation, despite encompassing a range of biological and biogeochemical conditions. We observed consistent and marked increases in DMS concentrations relative to ambient controls (110% (28-223%) at 550 µatm, 153% (56-295%) at 750 µatm and 225% (79-413%) at 1000 µatm), and decreases in DMSP concentrations (28% (18-40%) at 550 µatm, 44% (18-64%) at 750 µatm and 52% (24-72%) at 1000 µatm). Significant decreases in DMSP synthesis rate constants (µDMSP /d) and DMSP production rates (nmol/d) were observed in two experiments (7-90% decrease), whilst the response under high CO2 from the remaining experiments was generally indistinguishable from ambient controls. Rates of bacterial DMS gross consumption and production gave weak and inconsistent responses to high CO2. The variables and rates we report increase our understanding of the processes behind the response to OA. This could provide the opportunity to improve upon mesocosm-derived empirical modelling relationships and to move towards a mechanistic approach for predicting future DMS concentrations.

Mineralogy and geochemistry of sulfide minerals and bulk rocks from ODP Hole 176-735B

Ocean Drilling Program (ODP) Leg 176 built upon the work of ODP Leg 118 wherein the 500-m section that was sampled represented the most complete recovery of an intact portion of lower oceanic crust ever described. During Leg 176, we deepened Hole 735B to >1500 m below seafloor in an environment where gabbroic rocks have been tectonically exposed at the Southwest Indian Ridge. This new expedition extended the remarkable recovery (>85%) that allowed unprecedented investigations into the nature of the lower oceanic crust as a result of Leg 118. Sulfide mineral and bulk rock compositions were determined from samples in the 1000-m section of oceanic gabbros recovered during Leg 176. The sulfide assemblage of pyrrhotite, chalcopyrite, pentlandite, and troilite is present throughout this section, as it is throughout the 500-m gabbroic section above that was sampled during Leg 118. Troilite is commonly present as lamellae, and the only interval where troilite was not observed is from the uppermost 150 m of the section sampled during Leg 118, which is intensely metamorphosed. The common presence of troilite indicates that much of the sulfide assemblage from Hole 735B precipitated from a magmatic system and subsequently underwent low-temperature reequilibration. Evaluation of geochemical trends in bulk rock and sulfides indicates that the combined effects of olivine accumulation in troctolites and high pentlandite to pyrrhotite ratios account for the sporadic bulk rock compositions high in Ni. Bulk rock and sulfide mineral geochemical indicators that are spatially coincident with structural and physical properties anomalies indicate a heretofore unrecognized lithologic unit boundary in this section. Platinum-group element (PGE) compositions were also determined for 36 samples from throughout the section that were recovered during Leg 176. Whereas most samples had low (<0.4 ppb) PGE concentrations, rare samples had elevated PGE values, but no unique common trend between these samples is evident.

The distributions, C- and O-isotopic compositions, and frequency of giant-ooids

Early Triassic oceans were characterized by deposition of a number of "anachronistic facies", including microbialites, seafloor carbonate cement fans, and giant ooids. Giant ooids were particularly prevalent in Lower Triassic sections across South China and exhibit unusual features that may provide insights into marine environmental conditions following the end-Permian mass extinction. The section at Moyang (Guizhou Province) contains abundant giant ooids ranging in size between 2 and 6 mm (maximum 12 mm) and exhibiting various cortical structures, including regular, deformed, compound, regenerated and "domed". Preservation of ooid cortical structure is generally good as indicated by petrographic observations, and trace element and carbon isotope analyses suggest that diagenesis occurred in a closed diagenetic system. All ooids exhibit fine concentric laminae, frequently alternating between light-colored coarsely crystalline and dark-colored finely crystalline layers probably reflecting variation in organic content or original mineralogy. Under scanning electron microscope, biomineralized filaments or biofilms and tiny carbonate fluorapatite (CFA) crystals are commonly found in the finely crystalline layers. We infer that the precipitation of CFA was related to adsorption of P via microbial activity on the surfaces of ooids following episodic incursions of deep waters rich in carbon dioxide, hydrogen sulfide and phosphate into shallow-marine environments. Giant ooid precipitation may have been promoted in shallow ramp settings during these events by increased watermass agitation and supersaturation with respect to calcium carbonate, as well as reduced carbonate removal rates through biotic skeletal formation. Spatio-temporal distribution data reveal that giant ooids were widespread in the Tethyan region during the Early Triassic, and that they were most abundant immediately after the end-Permian crisis and disappeared gradually as metazoans repopulated marine environments.

Chemistry of sulfide deposits from ODP Site 106-649

In Snake Pit massive sulfide fragments and friable, unconsolidated material recovered during ODP Leg 106, isocubanite and pyrite are generally the predominant phases, followed by marcasite, chalcopyrite, sphalerite, and pyrrhotite. Detailed analyses of paragenetic relations of minerals indicate that isocubanite first precipitated together with pyrrhotite. With decreasing temperature, chalcopyrite and sphalerite precipitated, and at the latest stage colloform sphalerite-pyrite (or colloform marcasite) formed. Isocubanite usually has exsolution lamellae of chalcopyrite and less commonly of pyrrhotite. The average bulk chemical composition of the friable, unconsolidated material indicates that it is rich in copper, reflecting the dominance of isocubanite in the specimens, and is characterized by high Co, low Pb, and Ag contents. Sulfur isotope ratios are very uniform, ranging in d34S from +1.2 to +2.8 per mil. The obtained values are apparently low, compared to those for the eastern Pacific sulfide samples, reflecting a smaller contribution of seawater sulfate in the Snake Pit sulfide deposit.

Chemistry of sulfide deposites of ODP Site 106-649

The Snake Pit active hydrothermal field was discovered at 23°22'N on the Mid-Atlantic Ridge during ODP Leg 106. Among the ten holes drilled in the mound at the foot of an active chimney, only three (649B, 649F, and 649G) had substantial recovery, and produced cores of unconsolidated hydrothermal deposit made up of porous sulfide fragments with minor talc pellets and biological debris, and a few pieces of brassy massive sulfides. Eight representative samples from the 6.5-m-long core from Hole 649B were analyzed for bulk chemistry, both by XRF (major elements) and NAA (trace elements). Major elements average compositions show high Fe (36 wt%), S (37 wt%), and Cu (12 wt%) contents, and minor Zn (6.7 wt%), reflecting a mostly high-temperature deposit. Trace elements are characterized by a high Au content (600 ppb) which could express the maturity of the mound. Mineralogical assemblages show evidence of sequential precipitation, and absence of equilibrium. Major sulfide phases are pyrrhotite, pyrite, Fe, Cu sulfides, marcasite, and sphalerite. Three types of samples are distinguished on the basis of textures and mineral assemblages: type 1, rich in pyrrhotite, with approximately equivalent amounts of Cu, Fe sulfides, and sphalerite and minor pyrite; type 2, rich in Cu, Fe sulfides, which are cubic cubanite with exsolutions and rims of chalcopyrite; and type 3, essentially made up of sphalerite. Type 2 samples likely represent fragments of the inner chimney wall. The presence of talc intergrown with cubic cubanite/chalcopyrite in one big piece from Hole 649G is probably related to mixing of the hydrothermal fluid with seawater.

Initial vegetation, and spore density, diversity and evenness of different arbuscular mycorrhizal fungi morphotaxa 29,36 and 39 months after experimental vegetation removal, central Argentina

1. Dominant plant functional types (PFTs) are expected to be primary determinants of communities of other above- and below-ground organisms. Here, we report the effects of the experimental removal of different PFTs on arbuscular mycorrhizal fungi (AMF) communities in a shrubland ecosystem in central Argentina. 2. On the basis of the biomass-ratio hypothesis and plant resource use strategy theory, we expected the effect of removal of PFTs on AMF colonization and spores to be proportional to the biomass removed and to be stronger when more conservative PFTs were removed. The treatments applied were: undisturbed control (no plant removed), disturbed control (mechanical disturbance), no shrub (removal of deciduous shrubs), no perennial forb (removal of perennial forbs), no graminoid (removal of graminoids) and no annual forb (removal of annual forbs). AMF colonization was assessed after 5,17 and 29 months. Total density of AMF spores, richness and evenness of morpho-taxa, and AMF functional groups were quantified after 5,17,29,36 and 39 months. 3. Five months after the initial removal we found a significant reduction in total AMF colonization in all plots subjected to PFT removals and in the disturbed control plots, as compared with the undisturbed controls. This effect disappeared afterwards and no subsequent effect on total colonization and colonization by arbuscules was observed. In contrast, a significant increase in colonization by vesicles was observed in months 17 and 29, mainly in no graminoid plots. In general, treatments did not significantly affect AMF spores in the soil. On the other hand, no annual forb promoted transient (12-18 months) higher ammonia availability, and no shrub promoted lower nitrate availability in the longer term (24-28 months). 4. Synthesis. Our experiment, the first to investigate the effects of the removal of different PFTs on AMF communities in natural ecosystems, indicates that AMF communities are resilient to changes in the soil and in the functional composition of vegetation. Furthermore, it does not provide consistent evidence in support of the biomass-ratio hypothesis or differential trait-based direct or indirect effects of different PFTs on AMF in this particular system.