Accumulation and composition of terrigenous material on Ceara rise over the past 55 Ma

Ceara Rise, located east the Amazon River mouth, is covered with a thick blanket of pelagic carbonate and hemipelagic terrigenous sediment. The terrigenous component has been extracted from 57 bulk sediment samples at Ocean Drilling Program (ODP) Sites 925 and 929 on Ceara Rise to obtain a Cenozoic record of riverine discharge from northern South America. From the early Eocene to early Miocene (55-20 Ma), terrigenous accumulation was dominated by moderate amounts of generally large-grained, gray to green sediment especially depleted in elements that are enriched in post-Archaean shale (e.g. Cs, Th, Yb). However, pulsed inputs of relatively small-grained, gray to green terrigenous sediment less depleted in the above elements occurred in the late Eocene and Oligocene. The accumulation of terrigenous sediment decreased significantly until 16.5 Ma. In the middle Miocene (16.5-13 Ma), terrigenous accumulation was dominated by small amounts of small-grained, tan sediment notably depleted in Na and heavy rare earth elements. The accumulation rate of terrigenous sediment increased markedly from the latest Miocene (10 Ma) to the present day, a change characterized by deposition of gray-green sediment enriched in elements that are enriched in post-Archaean shale. Observed changes in terrigenous sediment at Ceara Rise record tectonism and erosion in northern South America. The Brazil and Guyana shields supplied sediment to the eastern South American margin until the middle Miocene (20-16.5 Ma) when a period of thrusting, shortening and uplift changed the source region, probably first to highly weathered and proximal Phanerozoic sediments. By the late Miocene (9 Ma), there was a transcontinental connection between the Andes and eastern South America. Weathering products derived from the Andes have increasingly dominated terrigenous deposition at Ceara Rise since the Late Miocene and especially since the late Pliocene.

Ba, Mn, and Mg record derived from Hoeglundina elegans of sediment core SLA-9

The evolution of productivity, redox conditions, temperature, and ventilation during the deposition of an Aegean sapropel (S1) is independently constrained using bulk sediment composition and high-resolution single specimen benthic foraminiferal trace metal and stable isotope data. The occurrence of benthic foraminifer, Hoeglundina elegans (H. elegans), through a shallow water (260 m) sapropel, permits for the first time a comparison between dissolved and particulate concentrations of Ba and Mn and the construction of a Mg/Ca-based temperature record through sapropel S1. The simultaneous increase in sedimentary Ba and incorporated Ba in foraminiferal test carbonate, (Ba/Ca)H. elegans, points to a close coupling between Ba cycling and export productivity. During sapropel deposition, sedimentary Mn content ((Mn/Al)sed) is reduced, corresponding to enhanced Mn2+ mobilization from sedimentary Mn oxides under suboxic conditions. The consequently elevated dissolved Mn2+ concentrations are reflected in enhanced (Mn/Ca)H. elegans levels. The magnitude and duration of the sapropel interruption and other short-term cooling events are constrained using Mg/Ca thermometry. Based on integrating productivity and ventilation records with the temperature record, we propose a two-mode hysteresis model for sapropel formation.

Chemical and isotopic compositions of altered MORB from ODP Holes 187-1154A, 187-1155B, and 187-1160B

Boron and Pb isotopic compositions together with B-U-Th-Pb concentrations were determined for Pacific and Indian mantle-type mid-ocean ridge basalts (MORB) obtained from shallow drill holes near the Australian Antarctic Discordance (AAD). Boron contents in the altered samples range from 29.7 to 69.6 ppm and are extremely enriched relative to fresh MORB glass with 0.4-0.6 ppm B. Similarly the d11B values range from 5.5? to 15.9? in the altered basalts and require interaction with a d11B enriched fluid similar to seawater ~39.5? and/or boron isotope fractionation during the formation of secondary clays. Positive correlations between B concentrations and other chemical indices of alteration such as H2O CO2, K2O, P2O5, U and 87Sr/86Sr indicate that B is progressively enriched in the basalts as they become more altered. Interestingly, d11B shows the largest isotopic shift to +16? in the least altered basalts, followed by a continual decrease to +5-6? in the most altered basalts. These observations may indicate a change from an early seawater dominated fluid towards a sediment-dominated fluid as a result of an increase in sediment cover with increasing age of the seafloor. The progression from heavy d11B towards lighter values with increasing degrees of alteration may also reflect increased formation of clay minerals (e.g., saponite). A comparison of 238U/204Pb and 206Pb/204Pb in fresh glass and variably altered basalt from Site 1160B shows extreme variations that are caused by secondary U enrichment during low temperature alteration. Modeling of the U-Pb isotope system confirms that some alteration events occurred early in the 21.5 Ma history of these rocks, even though a significant second pulse of alteration happened at ~12 Ma after formation of the crust. The U-Pb systematics of co-genetic basaltic glass and variably low temperature altered basaltic whole rocks are thus a potential tool to place age constraints on the timing of alteration and fluid flow in the ocean crust.

Gridded bathymetry from multibeam echosounder EM120 data of the cruise M72/4 (2007)

Bathymetry based on data recorded during M72-4 between 25.04.2007 and 11.05.2007 in the Black Sea. This main objective of this cruise was to gain better knowledge of the pathways of methane from their point of formation via potential intermediate deposits to the seafloor in order to understand the mechanisms leading to the submarine discharge of methane-rich fluids. Two regional Black Sea targets have been chosen: The Sorokin Trough, with focused seepage through mud volcanoes, and the Dniepr area where active gas venting occurs from very shallow water depths down to at least 1000 m.

Gridded bathymetry from multibeam echosounder EM122 data of the cruise M84/2, off Eregli (2011)

We investigated gas bubble emissions at the Don-Kuban paleo-fan in the northeastern Black Sea regarding their geological setting, quantities as well as spatial and temporal variabilities during three ship expeditions between 2007 and 2011. About 600 bubble-induced hydroacoustic anomalies in the water column (flares) originating from the seafloor above the gas hydrate stability zone (GHSZ) at ~700 m water depth were found. At about 890 m water depth a hydrocarbon seep area named "Kerch seep area" was newly discovered within the GHSZ. We propose locally domed sediments ('mounds') discovered during ultra-high resolution bathymetric mapping with an autonomous underwater vehicle (AUV) to result from gas hydrate accumulation at shallow depths. In situ measurements indicated spatially limited temperature elevations in the shallow sediment likely induced by upward fluid flow which may confine the local GHSZ to a few meters below the seafloor. As a result, gas bubbles are suspected to migrate into near-surface sediments and to escape the seafloor through small-scale faults. Hydroacoustic surveys revealed that several flares originated from a seafloor area of about 1 km**2 in size. The highest flare disappeared in about 350 m water depth, suggesting that the released methane remains in the water column. A methane flux estimate, combining data from visual quantifications during dives with a remotely operated vehicle (ROV) with results from ship-based hydroacoustic surveys and gas analysis revealed that between 2 and 87 x 10**6 mol CH4 yr-1 escaped into the water column above the Kerch seep area. Our results show that the finding of the Kerch seep area represents a so far underestimated type of hydrocarbon seep, which has to be considered in methane budget calculations.

In-situ sediment temperature and pore water chloride concentration at pockmarks of the Nigerian continental margin

A joint research expedition between the French IFREMER and the German MARUM was conducted in 2011 using the R/V 'Pourquoi pas?' to study gas hydrate distributions in a pockmark field (1141-1199 m below sea surface) at the continental margin of Nigeria. The seafloor drill rig MeBo of MARUM was used to recover sediments as deep as 56.74 m below seafloor. The presence of gas hydrates in specific core sections was deduced from temperature anomalies recorded during continuous records of infrared thermal scanning and anomalies in pore water chloride concentrations. In situ sediment temperature measurements showed elevated geothermal gradients of up to 258 °C/km in the center of the so-called pockmark A which is up to 4.6 times higher than that in the background sediment (72 °C/km). The gas hydrate distribution and thermal regime in the pockmark are largely controlled by the intensity, periodicity and direction of fluid flow. The joint interaction between fluid flow, gas hydrate formation and dissolution, and the thermal regime governs pockmark formation and evolution on the Nigerian continental margin.

Pore water geochemistry of Håkon Mosby mud volcano sediments measured at station PS74/169-1_PUC-15 (Z1-S1, new flow surface)

Pore water and turnover rates were determined for surface sediment cores obtained in 2009 and 2010. The pore water was extracted with Rhizons (Rhizon CSS: length 5 cm, pore diameter 0.15 µm; Rhizosphere Research Products, Wageningen, Netherlands) in 1 cm-resolution and immediately fixed in 5% zinc acetate (ZnAc) solution for sulfate, and sulfide analyses. The samples were diluted, filtered and the concentrations measured with non-suppressed anion exchange chromatography (Waters IC-Pak anion exchange column, waters 430 conductivity detector). The total sulfide concentrations (H2S + HS- + S**2-) were determined using the diamine complexation method (doi:10.4319/lo.1969.14.3.0454). Samples for dissolved inorganic carbon (DIC) and alkalinity measurements were preserved by adding 2 µl saturated mercury chloride (HgCl2) solution and stored headspace-free in gas-tight glass vials. DIC and alkalinity were measured using the flow injection method (detector VWR scientific model 1054) (doi:10.4319/lo.1992.37.5.1113). Dissolved sulfide was eliminated prior to the DIC measurement by adding 0.5 M molybdate solution (doi:10.4319/lo.1995.40.5.1011). Nutrient subsamples (10 - 15 ml) were stored at - 20 °C prior to concentration measurements with a Skalar Continuous-Flow Analyzer (doi:10.1002/9783527613984).

Gridded bathymetry from multibeam echosounder EM122 data of the cruise MSM35

The aim of Maria S. MERIAN voyage MSM35 was to conduct marine controlled source electromagnetic (CSEM) measurements in the Danube Delta, Black Sea, to identify suitable gas hydrate deposits for a future MEBO drilling test site for methane production and CO2 sequestration in hydrate form. Marine CSEM is a geophysical exploration method to derive the electrical properties, i.e. resistivity of the seafloor. Gas hydrates and free gas are electrically insulating and replace conductive pore fluid.