Rare earth elements of modern seeps from the Gulf of Mexico, the Black Sea, and the Congo Fan

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.

Methane concentrations in the central North Sea

We investigated dissolved methane distributions along a 6 km transect crossing active seep sites at 40 m water depth in the central North Sea. These investigations were done under conditions of thermal stratification in summer (July 2013) and homogenous water column in winter (January 2014). Dissolved methane accumulated below the seasonal thermocline in summer with a median concentration of 390 nM, whereas during winter, methane concentrations were typically much lower (median concentration of 22 nM). High-resolution methane analysis using an underwater mass-spectrometer confirmed our summer results and was used to document prevailing stratification over the tidal cycle. We contrast estimates of methane oxidation rates (from 0.1 to 4.0 nM day**-1) using the traditional approach scaled to methane concentrations with microbial turnover time values and suggest that the scaling to concentration may obscure the ecosystem microbial activity when comparing systems with different methane concentrations. Our measured and averaged rate constants (k') were on the order of 0.01 day**-1, equivalent to a turnover time of 100 days, even when summer stratification led to enhanced methane concentrations in the bottom water. Consistent with these observations, we could not detect known methanotrophs and pmoA genes in water samples collected during both seasons. Estimated methane fluxes indicate that horizontal transport is the dominant process dispersing the methane plume. During periods of high wind speed (winter), more methane is lost to the atmosphere than oxidized in the water. Microbial oxidation seems of minor importance throughout the year.

Chemical and isotopic analysis of bulk organic matter and hydrocarbon biomarkers from IODP Holes 311-U1327C, 311-U1328B and 311-U1328C

The chemical and isotopic compositions of sedimentary organic matter (SOM) from two mid-slope sites of the northern Cascadia margin were investigated during Integrated Ocean Drilling Program (IODP) Expedition 311 to elucidate the organic matter origins and identify potential microbial contributions to SOM. Gas hydrate is present at both locations (IODP Sites U1327 and U1328), with distinct patterns of near-seafloor structural accumulations at the cold seep Site U1328 and deeper stratigraphic accumulations at the slope-basin Site U1327. Source characterization and evidence that some components of the organic matter have been diagenetically altered are determined from the concentrations and isotopic compositions of hydrocarbon biomarkers, total organic carbon (TOC), total nitrogen (TN) and total sulfur (TS). The carbon isotopic compositions of TOC (d13C TOC = -26 to -22 per mil) and long-chain n-alkanes (C27, C29 and C31, d13C = -34 to -29 per mil) suggest the organic matter at both sites is a mixture of 1) terrestrial plants that employ the C3 photosynthetic pathway and 2) marine algae. In contrast, the d15N TN values of the bulk sediment (+4 to +8 per mil) are consistent with a predominantly marine source, but these values most likely have been modified during microbial organic matter degradation. The d13C values of archaeal biomarker pentamethylicosane (PMI) (-46.4 per mil) and bacterial-sourced hopenes, diploptene and hop-21-ene (-40.9 to -34.7 per mil) indicate a partial contribution from methane carbon or a chemoautotrophic pathway. Our multi-isotope and biomarker-based conclusions are consistent with previous studies, based only on the elemental composition of bulk sediments, that suggested a mixed marine-terrestrial organic matter origin for these mid-slope sites of the northern Cascadia margin.

Stable carbon isotopes, Methane Index, and distributions of different GDGTs

Gas hydrates represent one of the largest pools of readily exchangeable carbon on Earth's surface. Releases of the greenhouse gas methane from hydrates are proposed to be responsible for climate change at numerous events in geological history. Many of these inferred events, however, were based on carbonate carbon isotopes which are susceptible to diagenetic alterations. Here we propose a molecular fossil proxy, i.e., the "Methane Index (MI)", to detect and document the destabilization and dissociation of marine gas hydrates. MI consists of the relative distribution of glycerol dibiphytanyl glycerol tetraethers (GDGTs), the core membrane lipids of archaea. The rational behind MI is that in hydrate-impacted environments, the pool of archaeal tetraether lipids is dominated by GDGT-1, -2 and -3 due to the large contribution of signals from the methanotrophic archaeal community. Our study in the Gulf of Mexico cold-seep sediments demonstrates a correlation between MI and the compound-specific carbon isotope of GDGTs, which is strong evidence supporting the MI-methane consumption relationship. Preliminary applications of MI in a number of hydrate-impacted and/or methane-rich environments show diagnostic MI values, corroborating the idea that MI may serve as a robust indicator for hydrate dissociation that is useful for studies of global carbon cycling and paleoclimate change.

Isotopic composition of ground ice, ebullition gases and thermokarst lake water, North America

Thermokarst lakes are thought to have been an important source of methane (CH4) during the last deglaciation when atmospheric CH4 concentrations increased rapidly. Here we demonstrate that meltwater from permafrost ice serves as an H source to CH4 production in thermokarst lakes, allowing for region-specific reconstructions of dD-CH4 emissions from Siberian and North American lakes. dD CH4 reflects regionally varying dD values of precipitation incorporated into ground ice at the time of its formation. Late Pleistocene-aged permafrost ground ice was the dominant H source to CH4 production in primary thermokarst lakes, whereas Holocene-aged permafrost ground ice contributed H to CH4 production in later generation lakes. We found that Alaskan thermokarst lake dD-CH4 was higher (-334 ± 17 per mil) than Siberian lake dD-CH4 (-381 ± 18 per mil). Weighted mean dD CH4 values for Beringian lakes ranged from -385 per mil to -382 per mil over the deglacial period. Bottom-up estimates suggest that Beringian thermokarst lakes contributed 15 ± 4 Tg CH4 /yr to the atmosphere during the Younger Dryas and 25 ± 5 Tg CH4 /yr during the Preboreal period. These estimates are supported by independent, top-down isotope mass balance calculations based on ice core dD-CH4 and d13C-CH4 records. Both approaches suggest that thermokarst lakes and boreal wetlands together were important sources of deglacial CH4.

Biogeochemical measurements associated to deep-sea wood falls

Large organic food falls to the deep sea - such as whale carcasses and wood logs - support the development of reduced, sulfidic niches in an otherwise oxygenated, oligotrophic deep-sea environment. These transient hot spot ecosystems may serve the dispersal of highly adapted chemosynthetic organisms such as thiotrophic bivalves and siboglinid worms. Here we investigated the biogeochemical and microbiological processes leading to the development of sulfidic niches. Wood colonization experiments were carried out for the duration of one year in the vicinity of a cold seep area in the Nile deep-sea fan (Eastern Mediterranean) at depths of 1690 m. Wood logs were deployed in 2006 during the BIONIL cruise (RV Meteor M70/2 with ROV Quest, Marum, Germany) and sampled in 2007 during the Medeco-2 cruise (RV Pourquoi Pas? with ROV Victor 6000, Ifremer, France). Wood-boring bivalves played a key role in the initial degradation of the wood, the dispersal of wood chips and fecal matter around the wood log, and the provision of colonization surfaces to other organisms. Total oxygen uptake measured with a ROV-operated benthic chamber module was higher at the wood (0.5 m away) in contrast to 10 m away at a reference site (25 mmol m-2 d-1 and 1 mmol m-2 d-1, respectively), indicating an increased activity of sedimentary communities around the wood falls. Bacterial cell numbers associated with wood increased substantially from freshly submerged wood to the wood chip/fecal matter layer next to the wood experiments, as determined with Acridine Orange Direct Counts (AODC) and DAPI-stained counts. Microsensor measurements of sulfide, oxygen and pH were conducted ex situ. Sulfide fluxes were higher at the wood experiments when compared to reference measurements (19 and 32 mmol m-2 d-1 vs. 0 and 16 mmol -2 d-1, respectively). Sulfate reduction (SR) rates at the wood experiments were determined in ex situ incubations (1.3 and 2.0 mmol m-2 d-1) and fell into the lower range of SR rates previously observed from other chemosynthetic habitats at cold seeps. There was no influence of wood deposition on phosphate, silicate and nitrate concentrations, but ammonium concentrations were elevated at the wood chip-sediment boundary layer. Concentrations of dissolved organic carbon were much higher at the wood experiments (wood chip-sediment boundary layer) in comparison to measurements at the reference sites, which may indicate that cellulose degradation was highest under anoxic conditions and hence enabled by anaerobic benthic bacteria, e.g. fermenters and sulfate reducers. Our observations demonstrate that, after one year, the presence of wood at the seafloor had led to the creation of sulfidic niches, comparable to what has been observed at whale falls, albeit at lower rates.

AMS 14C ages and isotopic compositions of samples from the Derugin Basin, Sea of Okhotsk

An area of massive barite precipitations was studied at a tectonic horst in 1500 m water depth in the Derugin Basin, Sea of Okhotsk. Seafloor observations and dredge samples showed irregular, block- to column-shaped barite build-ups up to 10 m high which were scattered over the seafloor along an observation track 3.5 km long. High methane concentrations in the water column show that methane expulsion and probably carbonate precipitation is a recently active process. Small fields of chemoautotrophic clams (Calyptogena sp., Acharax sp.) at the seafloor provide additional evidence for active fluid venting. The white to yellow barites show a very porous and often layered internal fabric, and are typically covered by dark-brown Mn-rich sediment; electron microprobe spectroscopy measurements of barite sub-samples show a Ba substitution of up to 10.5 mol% of Sr. Rare idiomorphic pyrite crystals (~1%) in the barite fabric imply the presence of H2S. This was confirmed by clusters of living chemoautotrophic tube worms (1 mm in diameter) found in pores and channels within the barite. Microscopic examination showed that micritic aragonite and Mg-calcite aggregates or crusts are common authigenic precipitations within the barite fabric. Equivalent micritic carbonates and barite carbonate cemented worm tubes were recovered from sediment cores taken in the vicinity of the barite build-up area. Negative d13C values of these carbonates (>-43.5 per mill PDB) indicate methane as major carbon source; d18O values between 4.04 and 5.88 per mill PDB correspond to formation temperatures, which are certainly below 5°C. One core also contained shells of Calyptogena sp. at different core depths with 14C-ages ranging from 20 680 to >49 080 yr. Pore water analyses revealed that fluids also contain high amounts of Ba; they also show decreasing SO4**2- concentrations and a parallel increase of H2S with depth. Additionally, S and O isotope data of barite sulfate (d34S: 21.0-38.6 per mill CDT; d18O: 9.0-17.6 per mill SMOW) strongly point to biological sulfate reduction processes. The isotope ranges of both S and O can be exclusively explained as the result of a mixture of residual sulfate after a biological sulfate reduction and isotopic fractionation with 'normal' seawater sulfate. While massive barite deposits are commonly assumed to be of hydrothermal origin, the assemblage of cheomautotrophic clams, methane-derived carbonates, and non-thermally equilibrated barite sulfate strongly implies that these barites have formed at ambient bottom water temperatures and form the features of a Giant Cold Seep setting that has been active for at least 49 000 yr.

Tephrostratigraphy and radiometric dating of authigenic carbonates

At convergent margins, fluids rise through the forearc in response to consolidation of the upper plate and dewatering of the subducting plate, and produce various cold-seep-related features on the seafloor (mud diapirs, mud mounds). At the Central American forearc, authigenic carbonates precipitated from rising fluids within such structures during active venting while typical mixed-mud sediments were ejected onto the surrounding seafloor where they became intercalated with normal pelagic background sediments, indicating that mud mounds evolved unsteadily through alternating active and inactive phases. Intercalated regional ash layers from Plinian eruptions at the Central American volcanic arc provide time marks that constrain the ages of mud ejection activity. U/Th dating of drill core samples of authigenic carbonate caps of mud mounds yields ages agreeing well with those constrained by ash layers and showing that carbonate caps grow inward rather than outward during active venting. Both dating approaches show that offshore Nicaragua and Costa Rica (1) active and inactive phases can occur simultaneously at neighboring mounds, (2) mounds along the forearc have individual histories of activity, but there are distinct time intervals when nearly all mounds have been active or inactive, (3) lifetimes of mounds reach several hundred thousand years, and (4) highly active periods last 10-50 k.y. with intervening periods of >10 k.y. of relative quiescence.

Hydrocarbon concentrations from pressurized cores in the northern Gulf of Mexico

Two newly developed coring devices, the Multi-Autoclave-Corer and the Dynamic Autoclave Piston Corer were deployed in shallow gas hydrate-bearing sediments in the northern Gulf of Mexico during research cruise SO174 (Oct-Nov 2003). For the first time, they enable the retrieval of near-surface sediment cores under ambient pressure. This enables the determination of in situ methane concentrations and amounts of gas hydrate in sediment depths where bottom water temperature and pressure changes most strongly influence gas/hydrate relationships. At seep sites of GC185 (Bush Hill) and the newly discovered sites at GC415, we determined the volume of low-weight hydrocarbons (C1 through C5) from nine pressurized cores via controlled degassing. The resulting in situ methane concentrations vary by two orders of magnitudes between 0.031 and 0.985 mol kg**-1 pore water below the zone of sulfate depletion. This includes dissolved, free, and hydrate-bound CH4. Combined with results from conventional cores, this establishes a variability of methane concentrations in close proximity to seep sites of five orders of magnitude. In total four out of nine pressure cores had CH4 concentrations above equilibrium with gas hydrates. Two of them contain gas hydrate volumes of 15% (GC185) and 18% (GC415) of pore space. The measurements prove that the highest methane concentrations are not necessarily related to the highest advection rates. Brine advection inhibits gas hydrate stability a few centimeters below the sediment surface at the depth of anaerobic oxidation of methane and thus inhibits the storage of enhanced methane volumes. Here, computerized tomography (CT) of the pressure cores detected small amounts of free gas. This finding has major implications for methane distribution, possible consumption, and escape into the bottom water in fluid flow systems related to halokinesis.

Environmental characteristics and gas composition of Lost Hammer, Canadian Arctic

We report the first microbiological characterization of a terrestrial methane seep in a cryo-environment in the form of an Arctic hypersaline (~24% salinity), subzero (-5 C), perennial spring, arising through thick permafrost in an area with an average annual air temperature of -15 C. Bacterial and archaeal 16S rRNA gene clone libraries indicated a relatively low diversity of phylotypes within the spring sediment (Shannon index values of 1.65 and 1.39, respectively). Bacterial phylotypes were related to microorganisms such as Loktanella, Gillisia, Halomonas and Marinobacter spp. previously recovered from cold, saline habitats. A proportion of the bacterial phylotypes were cultured, including Marinobacter and Halomonas, with all isolates capable of growth at the in situ temperature (-5 C). Archaeal phylotypes were related to signatures from hypersaline deep-sea methane-seep sediments and were dominated by the anaerobic methane group 1a (ANME-1a) clade of anaerobic methane oxidizing archaea. CARD-FISH analyses indicated that cells within the spring sediment consisted of ~84.0% bacterial and 3.8% archaeal cells with ANME-1 cells accounting for most of the archaeal cells. The major gas discharging from the spring was methane (~50%) with the low CH4/C2 + ratio and hydrogen and carbon isotope signatures consistent with a thermogenic origin of the methane. Overall, this hypersaline, subzero environment supports a viable microbial community capable of activity at in situ temperature and where methane may behave as an energy and carbon source for sustaining anaerobic oxidation of methane-based microbial metabolism. This site also provides a model of how a methane seep can form in a cryo-environment as well as a mechanism for the hypothesized Martian methane plumes.