Laura Mariana Wehrmann

Resistance of Lophelia pertusa to coverage by sediment and petroleum drill cuttings

In laboratory experiments, the cold-water coral Lophelia pertusa was exposed to settling particles. The effects of reef sediment, petroleum drill cuttings and a mix of both, on the development of anoxia at the coral surface were studied using O2, pH and H2S microsensors and by assessing coral polyp mortality. Due to the branching morphology of L. pertusa and the release of coral mucus, accumulation rates of settling material on coral branches were low. Microsensors detected H2S production in only a few samples, and sulfate reduction rates of natural reef sediment slurries were low (<0.3 nmol S cm(-3) d(-1)). While the exposure to sediment clearly reduced the corals accessibility to oxygen, L. pertusa tolerated both partial low-oxygen and anoxic conditions without any visible detrimental short-term effect, such as tissue damage or death. However, complete burial of coral branches for >24 h in reef sediment resulted in suffocation.

Sulfur Cycling in an Iron Oxide-Dominated, Dynamic Marine Depositional System: The Argentine Continental Margin

The interplay between sediment deposition patterns, organic matter type and the quantity and quality of reactive mineral phases determines the accumulation, speciation and isotope composition of pore water and solid phase sulfur constituents in marine sediments. Here, we present the sulfur geochemistry of siliciclastic sediments from two sites along the Argentine continental slope—a system characterized by dynamic deposition and reworking, which result in non-steady state conditions. The two investigated sites have different depositional histories but have in common that reactive iron phases are abundant and that organic matter is refractory—conditions that result in low organoclastic sulfate reduction rates. Deposition of reworked, isotopically light pyrite and sulfurized organic matter appear to be important contributors to the sulfur inventory, with only minor addition of pyrite from organoclastic sulfate reduction above the sulfate-methane transition (SMT). Pore-water sulfide is limited to a narrow zone at the SMT. The core of that zone is dominated by pyrite accumulation. Iron monosulfide and elemental sulfur accumulate above and below this zone. Iron monosulfide precipitation is driven by the reaction of low amounts of hydrogen sulfide with ferrous iron and is in competition with the oxidation of sulfide by iron (oxyhydr)oxides to form elemental sulfur. The intervals marked by precipitation of intermediate sulfur phases at the margin of the zone with free sulfide are bordered by two distinct peaks in total organic sulfur. Organic matter sulfurization appears to precede pyrite formation in the iron-dominated margins of the sulfide zone, potentially linked to the presence of polysulfides formed by reaction between dissolved sulfide and elemental sulfur. Thus, SMTs can be hotspots for organic matter sulfurization in sulfide-limited, reactive iron-rich marine sedimentary systems. Furthermore, existence of elemental sulfur and iron monosulfide phases meters below the SMT demonstrates that in sulfide-limited systems metastable sulfur constituents are not readily converted to pyrite but can be buried to deeper sediment depths. Our data show that in non-steady state systems, redox zones do not occur in sequence but can reappear or proceed in inverse sequence throughout the sediment column, causing similar mineral alteration processes to occur at the same time at different sediment depths.

Calcium–ammonium exchange experiments on clay minerals using a 45Ca tracer technique in marine pore water

Understanding cation exchange processes is important for evaluating early diagenetic and synsedimentary processes taking place in marine sediments. To quantify calcium (Ca) exchange and Ca–ammonium exchange in a seawater environment, we performed experiments with a radioactive 45Ca tracer on clay mineral standards (Fithian illite, montmorillonite and kaolinite) and marine sediments from the North Atlantic Integrated Ocean Drilling Program Site U1306A in artificial seawater (ASW). The results show that equilibrium during the initial attachment of Ca as well as the exchange of Ca by is attained in less than 2 min. On average 8–20% of the exchangeable sites of the clay minerals were occupied by Ca in a seawater medium. The conditional selectivity coefficient, describing the exchange in ASW is mineral specific and it was determined to be 0.07 for montmorillonite, 0.05 for a natural marine sediment and 0.013 for Fithian illite.

Biogeochemical Consequences of the Sedimentary Subseafloor Biosphere

Abstract The water buried with sediment comprises by volume a substantial portion of the Earths ocean. We explore the biogeochemical consequences of microbial activity in this subseafloor sedimentary ocean, the geochemistry of those sediments, and the overall biogeochemical cycles affecting the ocean. Biogeochemical processes resulting from deep subseafloor microbial activity, principally driven by organic carbon deposition and burial, leave a fundamental imprint on the interstitial water composition, the lithogenic and biogenic components of marine sediments, for example, the formation of diagenetic carbonate phases. Such non-steady state diagenetic formation of minerals and alteration of primary components by secondary reactions of metabolic products can reveal changes of the environmental conditions in the overlying water column over geological time. Furthermore, the long-term biogeochemical evolution of deep subseafloor sediment basins will expectedly affect the redox state of the ocean over geological timescales.

Linking sedimentary sulfur and iron biogeochemistry to growth patterns of a cold-water coral mound in the Porcupine Basin, S.W. Ireland (IODP Expedition 307).

Challenger Mound, a 150-m-high cold-water coral mound on the eastern flank of the Porcupine Seabight off SW Ireland, was drilled during Expedition 307 of the Integrated Ocean Drilling Program (IODP). Retrieved cores offer unique insight into an archive of Quaternary paleo-environmental change, long-term coral mound development, and the diagenetic alteration of these carbonate fabrics over time. To characterize biogeochemical carbon-iron-sulfur transformations in the mound sediments, the contents of dithionite- and HCl-extractable iron phases, iron monosulfide and pyrite, and acid-extractable calcium, magnesium, manganese, and strontium were determined. Additionally, the stable isotopic compositions of pore-water sulfate and solid-phase reduced sulfur compounds were analyzed. Sulfate penetrated through the mound sequence and into the underlying Miocene sediments, where a sulfate-methane transition zone was identified. Small sulfate concentration decreases (<7 mM) within the top 40 m of the mound suggested slow net rates of present-day organoclastic sulfate reduction. Increasing δ(34)S-sulfate values due to microbial sulfate reduction mirrored the decrease in sulfate concentrations. This process was accompanied by oxygen isotope exchange with water that was indicated by increasing δ(18)O-sulfate values, reaching equilibrium with pore-water at depth. Below 50 mbsf, sediment intervals with strong (34)S-enriched imprints on chromium-reducible sulfur (pyrite S), high degree-of-pyritization values, and semi-lithified diagenetic carbonate-rich layers characterized by poor coral preservation, were observed. These layers provided evidence for the occurrence of enhanced microbial sulfate-reducing activity in the mound in the past during periods of rapid mound aggradation and subsequent intervals of non-deposition or erosion when geochemical fronts remained stationary. During these periods, especially during the Early Pleistocene, elevated sulfate reduction rates facilitated the consumption of reducible iron oxide phases, coral dissolution, and the subsequent formation of carbonate cements.

Mineralogical and geochemical analysis of Fe-phases in drill-cores from the Triassic Stuttgart Formation at Ketzin CO2 storage site before CO2 arrival

Abstract Reactive iron (Fe) oxides and sheet silicate-bound Fe in reservoir rocks may affect the subsurface storage of CO2 through several processes by changing the capacity to buffer the acidification by CO2 and the permeability of the reservoir rock: (1) the reduction of three-valent Fe in anoxic environments can lead to an increase in pH, (2) under sulphidic conditions, Fe may drive sulphur cycling and lead to the formation of pyrite, and (3) the leaching of Fe from sheet silicates may affect silicate diagenesis. In order to evaluate the importance of Fe-reduction on the CO2 reservoir, we analysed the Fe geochemistry in drill-cores from the Triassic Stuttgart Formation (Schilfsandstein) recovered from the monitoring well at the CO2 test injection site near Ketzin, Germany. The reservoir rock is a porous, poorly to moderately cohesive fluvial sandstone containing up to 2–4 wt% reactive Fe. Based on a sequential extraction, most Fe falls into the dithionite-extractable Fe-fraction and Fe bound to sheet silicates, whereby some Fe in the dithionite-extractable Fe-fraction may have been leached from illite and smectite. Illite and smectite were detected in core samples by X-ray diffraction and confirmed as the main Fe-containing mineral phases by X-ray absorption spectroscopy. Chlorite is also present, but likely does not contribute much to the high amount of Fe in the silicate-bound fraction. The organic carbon content of the reservoir rock is extremely low (<0.3 wt%), thus likely limiting microbial Fe-reduction or sulphate reduction despite relatively high concentrations of reactive Fe-mineral phases in the reservoir rock and sulphate in the reservoir fluid. Both processes could, however, be fuelled by organic matter that is mobilized by the flow of supercritical CO2 or introduced with the drilling fluid. Over long time periods, a potential way of liberating additional reactive Fe could occur through weathering of silicates due to acidification by CO2.

The Sedimentary Deep Subseafloor Biosphere

Abstract Deep subseafloor sediments represent an intriguing marine habitat, populated by genetically diverse -yet poorly characterized- microbial communities. Microbially mediated processes in subseafloor sediments constitute an important component of a network of (bio)geochemical redox reactions that leave a strong imprint on pore water and solid phase compositions, alter inorganic sedimentary paleoceanographic records, and ultimately affect global biogeochemical element cycles. Here we give a brief overview of the abundance and diversity of microbes in deep subseafloor environments. Furthermore, we discuss the (bio)geochemical aspects of the sedimentary deep subseafloor biosphere with excursions into the carbon, sulfur, and silica cycles, and look at the causes and impacts of non-steady state conditions on the marine sedimentary system.