Sedimentation rate calculations and isotopic analysis on sediment cores along the IODP Expedition 311 transect

The oceanographic and tectonic conditions of accretionary margins are well-suited for several potential processes governing methane generation, storage and release. To identify the relevant methane evolution pathways in the northern Cascadia accretionary margin, a four-site transect was drilled during Integrated Ocean Drilling Program Expedition 311. The d13C values of methane range from a minimum value of -82.2 per mil on an uplifted ridge of accreted sediment near the deformation front (Site U1326, 1829 mbsl, meters below sea level) to a maximum value of -39.5 per mil at the most landward location within an area of steep canyons near the shelf edge (Site U1329, 946 mbsl). An interpretation based solely on methane isotope values might conclude the 13C-enrichment of methane indicates a transition from microbially- to thermogenically-sourced methane. However, the co-existing CO2 exhibits a similar trend of 13C-enrichment along the transect with values ranging from -22.5 per mil to +25.7 per mil. The magnitude of the carbon isotope separation between methane and CO2 (Ec = 63.8 ± 5.8) is consistent with isotope fractionation during microbially mediated carbonate reduction. These results, in conjunction with a transect-wide gaseous hydrocarbon content composed of > 99.8% (by volume) methane and uniform dDCH4 values (-172 per mil ± 8) that are distinct from thermogenic methane at a seep located 60 km from the Expedition 311 transect, suggest microbial CO2 reduction is the predominant methane source at all investigated sites. The magnitude of the intra-site downhole 13C-enrichment of CO2 within the accreted ridge (Site U1326) and a slope basin nearest the deformation front (Site U1325, 2195 mbsl) is ~ 5 per mil. At the mid-slope site (Site U1327, 1304 mbsl) the downhole 13C-enrichment of the CO2 is ~ 25 per mil and increases to ~ 40 per mil at the near-shelf edge Site U1329. This isotope fractionation pattern is indicative of more extensive diagenetic alteration at sites with greater 13C-enrichment. The magnitude of the 13C-enrichment of CO2 correlates with decreasing sedimentation rates and a diminishing occurrence of stratigraphic gas hydrate. We suggest the decreasing sedimentation rates increase the exposure time of sedimentary organic matter to aerobic and anaerobic degradation, during burial, thereby reducing the availability of metabolizable organic matter available for methane production. This process is reflected in the occurrence and distribution of gas hydrate within the northern Cascadia margin accretionary prism. Our observations are relevant for evaluating methane production and the occurrence of stratigraphic gas hydrate within other convergent margins.

Methane concentration in sediment cores during METEOR cruise M92

We studied the concurrence of methanogenesis and sulfate reduction in surface sediments (0-25 cm below sea floor, cmbsf) at six stations (70, 145, 253, 407, 770 and 1024 m) along the Peruvian margin (12° S). This oceanographic region is characterized by high carbon export to the seafloor, creating an extensive oxygen minimum zone (OMZ) on the shelf, both factors that could favor surface methanogenesis. Sediments sampled along the depth transect traversed areas of anoxic and oxic conditions in the bottom-near water. Net methane production (batch incubations) and sulfate reduction (35S-sulfate radiotracer incubation) were determined in the upper 0-25 cmbsf of multicorer cores from all stations, while deep hydrogenotrophic methanogenesis (> 30 cmbsf, 14C-bicarbonate radiotracer incubation) was determined in two gravity cores at selected sites (78 and 407 m). Furthermore, stimulation (methanol addition) and inhibition (molybdate addition) experiments were carried out to investigate the relationship between sulfate reduction and methanogenesis. Highest rates of methanogenesis and sulfate reduction in the surface sediments, integrated over 0-25 cmbsf, were observed on the shelf (70-253 m, 0.06-0.1 and 0.5-4.7 mmol m-2 d-1, respectively), while lowest rates were discovered at the deepest site (1024 m, 0.03 and 0.2 mmol m-2 d-1, respectively). The addition of methanol resulted in significantly higher surface methanogenesis activity, suggesting that the process was mostly based on non-competitive substrates, i.e., substrates not used by sulfate reducers. In the deeper sediment horizons, where competition was probably relieved due to the decline of sulfate, the usage of competitive substrates was confirmed by the detection of hydrogenotrophic activity in the sulfate-depleted zone at the shallow shelf station (70 m). Surface methanogenesis appeared to be correlated to the availability of labile organic matter (C / N ratio) and organic carbon degradation (DIC production), both of which support the supply of methanogenic substrates. A negative correlation of methanogenesis rates with dissolved oxygen in the bottom-near water was not obvious, however, anoxic conditions within the OMZ might be advantageous for methanogenic organisms at the sediment-water interface. Our results revealed a high relevance of surface methanogenesis on the shelf, where the ratio between surface to deep (below sulfate penetration) methanogenic activity ranged between 0.13 and 105. In addition, methane concentration profiles indicate a partial release of surface methane into the water column as well as a partial consumption of methane by anaerobic methane oxidation (AOM) in the surface sediment. The present study suggests that surface methanogenesis might play a greater role in benthic methane budgeting than previously thought, especially for fueling AOM above the sulfate-methane transition zone.

Geochemistry and stratigraphy on sediment cores from Leg198 and Leg 208

The first complete cyclic sedimentary successions for the early Paleogene from drilling multiple holes have been retrieved during two ODP expeditions: Leg 198 (Shatsky Rise, NW Pacific Ocean) and Leg 208 (Walvis Ridge, SE Atlantic Ocean). These new records allow us to construct a comprehensive astronomically calibrated stratigraphic framework with an unprecedented accuracy for both the Atlantic and the Pacific Oceans covering the entire Paleocene epoch based on the identification of the stable long-eccentricity cycle (405-kyr). High resolution X-ray fluorescence (XRF) core scanner and non-destructive core logging data from Sites 1209 through1211 (Leg 198) and Sites 1262, 1267 (Leg 208) are the basis for such a robust chronostratigraphy. Former investigated marine (ODP Sites 1001 and 1051) and land-based (e.g., Zumaia) sections have been integrated as well. The high-fidelity chronology is the prerequisite for deciphering mechanisms in relation to prominent transient climatic events as well as completely new insights into Greenhouse climate variability in the early Paleogene. We demonstrate that the Paleocene epoch covers 24 long eccentricity cycles. We also show that no definite absolute age datums for the K/Pg boundary or the Paleocene - Eocene Thermal Maximum (PETM) can be provided by now, because of still existing uncertainties in orbital solutions and radiometric dating. However, we provide two options for tuning of the Paleocene which are only offset by 405-kyr. Our orbitally calibrated integrated Leg 208 magnetostratigraphy is used to revise the Geomagnetic Polarity Time Scale (GPTS) for Chron C29 to C25. We established a high-resolution calcareous nannofossil biostratigraphy for the South Atlantic which allows a much more detailed relative scaling of stages with biozones. The re-evaluation of the South Atlantic spreading rate model features higher frequent oscillations in spreading rates for magnetochron C28r, C27n, and C26n.