ALBERT

Description: A valid assessment of selective aerobic degradation on organic matter (OM) and its impact on OM-based proxies is vital to produce accurate environmental reconstructions. However, most studies investigating these effects suffer from inherent environmental heterogeneities. In this study, we used surface samples collected along two meter-scale transects and one longer transect in the northeastern Arabian Sea to constrain initial OM heterogeneity, in order to evaluate selective aerobic degradation on temperature, productivity and alteration indices at the sediment-water interface. All of the studied alteration indices, the higher plant alkane index, alcohol preservation index, and diol oxidation index, demonstrated that they are sensitive indicators for changes in the oxygen regime. Several export production indices, a cholesterol-based stanol/stenol index and dinoflagellate lipid- and cyst-based ratios, showed significant (more than 20%) change only over the lateral oxygen gradients. Therefore, these compounds do not exclusively reflect surface water productivity, but are significantly altered after deposition. Two of the proxies, glycerol dibiphytanyl glycerol tetraether-based TEX86 sea surface temperature indices and indices based on phytol, phytane and pristane, did not show any trends related to oxygen. Nevertheless, unrealistic sea surface temperatures were obtained after application of the TEX86, TEX86L, and TEX86H proxies. The phytol-based ratios were likely affected by the sedimentary production of pristane. Our results demonstrate the selective impact of aerobic organic matter degradation on the lipid and palynomorph composition of surface sediments along a short lateral oxygen gradient and suggest that some of the investigated proxies may be useful tracers of changing redox conditions at the sediment-water interface.

Description: Twelve submarine mud volcanoes (MV) in the Kumano forearc basin within the Nankai Trough subduction zone were investigated for hydrocarbon origins and fluid dynamics. Gas hydrates diagnostic for methane concentrations exceeding solubilities were recovered from MVs 2, 4, 5, and 10. Molecular ratios (C1/C2〈250) and stable carbon isotopic compositions (d13C-CH4 〉-40 per mil V-PDB) indicate that hydrate-bound hydrocarbons (HCs) at MVs 2, 4, and 10 are derived from thermal cracking of organic matter. Considering thermal gradients at the nearby IODP Sites C0009 and C0002, the likely formation depth of such HCs ranges between 2300 and 4300 m below seafloor (mbsf). With respect to basin sediment thickness and the minimum distance to the top of the plate boundary thrust we propose that the majority of HCs fueling the MVs is derived from sediments of the Cretaceous to Tertiary Shimanto belt below Pliocene/Pleistocene to recent basin sediments. Considering their sizes and appearances hydrates are suggested to be relicts of higher MV activity in the past, although the sporadic presence of vesicomyid clams at MV 2 showed that fluid migration is sufficient to nourish chemosynthesis-based organisms in places. Distributions of dissolved methane at MVs 3, 4, 5, and 8 pointed at fluid supply through one or few MV conduits and effective methane oxidation in the immediate subsurface. The aged nature of the hydrates suggests that the major portion of methane immediately below the top of the methane-containing sediment interval is fueled by current hydrate dissolution rather than active migration from greater depth.

Description: Methane, a potent greenhouse gas, is abundant in marine sediments**1, 2. Submarine seepage of methane-dominated hydrocarbons is heterogeneous in space and time, and mechanisms that can trigger episodic seep events are poorly understood**2, 3, 4. For example, critical gas pressures have been predicted to develop beneath impermeable sediments that bear gas hydrates, making them susceptible to mechanical failure and gas release**5, 6. Gas hydrates often occur in seismically active regions, but the role of earthquakes as triggers of hydrocarbon seepage through gas-hydrate-bearing sediments has been only superficially addressed**7, 8. Here we present geochemical analyses of sediment cores retrieved from the convergent margin off Pakistan. We find that a substantial increase in the upward flux of gas occurred within a few decades of a Mw 8.1 earthquake in 1945-the strongest earthquake reported for the Arabian Sea. Our seismic reflection data suggest that co-seismic shaking fractured gas-hydrate-bearing sediments, creating pathways for the free gas to migrate from a shallow reservoir within the gas hydrate stability zone into the water column. We conservatively estimate that 3.26×10**8 mol of methane have been discharged from the seep site since the earthquake. We therefore suggest that hydrocarbon seepage triggered by earthquakes needs to be considered in local and global carbon budgets at active continental margins.

Description: 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.

Description: We mapped, sampled, and quantified gas emissions at the continental margin west of Svalbard during R/V Heincke cruise He-387 in late summer 2012. Hydroacoustic mapping revealed that gas emissions were not limited to a zone just above 396 m below sea level (m b.s.l.). Flares from this depth gained significant attention in the scientific community in recent years because they may be caused by bottom water-warming induced hydrate dissolution in the course of global warming and/or by recurring seasonal hydrate formation and decay. We found that gas emissions occurred widespread between about 80 and 415 m b.s.l. which indicates that hydrate dissolution might only be one of several triggers for active hydrocarbon seepage in that area. Gas emissions were remarkably intensive at the main ridge of the forlandet moraine complex in 80 to 90 m water depths, and may be related to thawing permafrost. Focused seafloor investigations were performed with the remotely operated vehicle (ROV) "Cherokee". Geochemical analyses of gas bubbles sampled at about 240 m b.s.l. as well as at the 396 m gas emission sites revealed that the vent gas is primarily composed of methane (〉 99.70%) of microbial origin (average d13C = -55.7 per mil V-PDB). Estimates of the regional gas bubble flux from the seafloor to the water column in the area of possible hydrate decomposition were achieved by combining flare mapping using multibeam and single beam echosounder data, bubble stream mapping using a ROV-mounted horizontally-looking sonar, and quantification of individual bubble streams using ROV imagery and bubble counting. We estimated that about 53 × 10**6 mol methane were annually emitted at the two areas and allow a large range of uncertainty due to our method (9 to 118 × 10**6 mol yr**-1). These amounts, first, show that gas emissions at the continental margin west of Svalbard were in the same order of magnitude as bubble emissions at other geological settings, and second, may be used to calibrate models predicting hydrate dissolution at present and in the future, third, may serve as baseline (year 2012) estimate of the bubble flux that will potentially increase in future due to ever-increasing global-warming induced bottom water-warming and hydrate dissolution.

Description: The concentrations of rare earth elements (REEs), sulphate, hydrogen sulphide, total alkalinity, calcium, magnesium and phosphate were measured in shallow (〈12 cm below seafloor) pore waters from cold-seep sediments on the northern and southern summits of Hydrate Ridge, offshore Oregon. Downward-decreasing sulphate and coevally increasing sulphide concentrations reveal sulphate reductionas dominant early diagenetic process from ~2 cm depth downwards. A strong increase of total dissolved REE concentrations is evident immediately below the sediment-water interface, which can be related to early diagenetic release of REEs into pore water resulting from the remineralization of particulate organic matter. The highest pore water REE concentrations were measured close to the sediment-water interface at ~2 cm depth. Distinct shale normalized REE patterns point to particulate organic matter and iron oxides as main REE sources in the upper ~2-cm depth interval. In general, the pore waters have shalenormalized patterns reflecting heavy REE (HREE) enrichment, which suggests preferential complexation of HREEs with carbonate ions. Below ~2 cm depth, a downward decrease in REE correlates with a decrease in pore water calcium concentrations. At this depth, the anaerobic oxidation of methane (AOM) coupled to sulphate reduction increases carbonate alkalinity through the production of bicarbonate, which results in the precipitation of carbonate minerals. It seems therefore likely that the REEs and calcium are consumed during vast AOM-induced precipitation of carbonate in shallow Hydrate Ridge sediments. The analysis of pore waters from Hydrate Ridge shed new light on early diagenetic processes at cold seeps, corroborating the great potential of REEs to identify geochemical processes and to constrain environmental conditions.

Description: Evidence for twelve sites with gas bubble emissions causing hydroacoustic anomalies in 18 kHz echosounder records ('flares') was obtained at the convergent Makran continental margin. The hydroacoustic anomalies originating from hydrocarbon seeps at water depths between 575 and 2870 m disappeared after rising up to 2000 m in the water column. Dives with the remotely operated vehicle 'Quest 4000 m' revealed that several individual bubble vents contributed to one hydroacoustic anomaly. Analyzed gas samples suggest that bubbles were mainly composed of methane of microbial origin. Bubble size distributions and rise velocities were determined and the volume flux was estimated by counting the emitted bubbles and using their average volume. We found that a low volume flux (Flare 1 at 575 mbsl: 90 ml/min) caused a weak hydroacoustic signal in echograms whereas high volume fluxes (Flare 2 at 1027 mbsl: 1590 ml/min; Flare 5 C at 2870 mbsl: 760 ml/min) caused strong anomalies. The total methane bubble flux in the study area was estimated by multiplying the average methane flux causing a strong hydroacoustic anomaly in the echosounder record with the total number of equivalent anomalies. An order-of-magnitude estimate further considers the temporal variability of some of the flares, assuming a constant flux over time, and allows a large range of uncertainty inherent to the method. Our results on the fate of bubbles and the order-of-magnitude estimate suggest that all of the ?40 ± 32 ? 106 mol methane emitted per year within the gas hydrate stability zone remain in the deep ocean.

Description: At marine seeps, methane is microbially oxidized resulting in the precipitation of carbonates close to the seafloor. Methane oxidation leads to sulfate depletion in sediment pore water, which induces a change in redox conditions. Rare earth element (REE) patterns of authigenic carbonate phases collected from modern seeps of the Gulf of Mexico, the Black Sea, and the Congo Fan were analyzed. Different carbonate minerals including aragonite and calcite with different crystal habits have been selected for analysis. Total REE content (SumREE) of seep carbonates varies widely, from 0.1 ppm to 42.5 ppm, but a common trend is that the SumREE in microcrystalline phases is higher than that of the associated later phases including micospar, sparite and blocky cement, suggesting that SumREE may be a function of diagenesis. The shale-normalized REE patterns of the seep carbonates often show different Ce anomalies even in samples from a specific site, suggesting that the formation conditions of seep carbonates are variable and complex. Overall, our results show that apart from anoxic, oxic conditions are at least temporarily common in seep environments.