ALBERT

Description: This is a dataset from an in situ experiment at station S2 from the LTER monitoring site HAUSGARTEN, performed in June-July 2013 during Maria S Merian expedition MSM29. The in situ responses of Arctic deep-sea benthos to input of phytodetritus of a diatom (Thalassiosira sp.) as opposed to a coccolithophorid (Emiliania huxleyi) were investigated in incubation chambers of benthic landers. Using 13C and 15N labelled phytodetritus harvested from cultures of these species, we traced the fate of the respective phytodetritus into different parts of the food web (respiration, assimilation by bacteria and infauna 〉250 µm), in a short (4d) and long (14d) term experiment. The benthic landers were lowered to the sea floor, where they enclosed ~ 20cm of sediment and ~10 cm of overlying water. During respectively 4d and 14d, the temperature and concentrations of O2, DIC, 13C-DIC, NHx, NOx, 15N-NH4, 15N-NOx were measured. Upon recovery of the landers, the sediment was retrieved and subsampled in vertical horizons to measure pigment, TOC and TN, 13C-POC and 15N-PN concentrations, pore water concentrations of DIC, 13C-DIC, NHx, NOx, 15N-NH4 and 15N-NOx and the assimilation of 13C in bacterial fatty acids (iC15:0 and aiC15:0) and in fauna 〉 250 µm

Description: Low-molecular-weight (LMW) alcohols are produced during the microbial degradation of organic matter from precursors such as lignin, pectin, and carbohydrates. The biogeochemical behavior of these alcohols in marine sediment is poorly constrained but potentially central to carbon cycling. Little is known about LMW alcohols in sediment pore waters because of their low concentrations and high water miscibility, both of which pose substantial analytical challenges. In this study, three alternative methods were adapted for the analysis of trace amounts of methanol and ethanol in small volumes of saline pore waters: direct aqueous injection (DAI), solid-phase microextraction (SPME), and purge and trap (P&T) in combination with gas chromatography (GC) coupled to either a flame ionization detector (FID) or a mass spectrometer (MS). Key modifications included the desalination of samples prior to DAI, the use of a threaded midget bubbler to purge small-volume samples under heated conditions and the addition of salt during P&T. All three methods were validated for LMW alcohol analysis, and the lowest detection limit (60 nM and 40 nM for methanol and ethanol, respectively) was achieved with the P&T technique. With these methods, ambient concentrations of volatile alcohols were determined for the first time in marine sediment pore waters of the Black Sea and the Gulf of Mexico. A strong correlation between the two compounds was observed and tentatively interpreted as being controlled by similar sources and sinks at the examined stations.

Description: Methylated amines and sulfides are ubiquitous organic nitrogen and sulfur compounds in the marine environment and could serve as important energy substrates to methanogens inhabiting anoxic sediments. However, their abundance and isotopic values remain largely unconstrained in marine sediments. In this study, we investigated the distribution of trimethylamine (TMA), dimethylsulfide (DMS) and dimethylsulfoniopropionate (DMSP) in Aarhus Bay, Denmark and provided the first report for their stable carbon isotopic composition. Simultaneous measurement of those two compounds in small volumes of pore waters and sediments was accomplished with gas chromatography in combination with either a purge and trap system for quantification or a headspace method for carbon isotopic analysis. TMA in the solid phase (exchangeable pool, 0.3-6.6 µmol/kg wet sediment; base-extractable pool, 2-18 µmol/kg) was much more abundant than the dissolved pool (〈 20 nM), indicating strong adsorption of TMA to sediments. Likewise, total base-hydrolyzable DMS(P)t (including DMS and base-released DMS from DMSP) in sediment was at least three orders of magnitude higher (11-65 µmol/kg) than the dissolved pool of DMS(P)d in the pore water (including DMS and dissolved DMSP; 1-12 nM). TMA and DMS(P) contents in the solid phase peaked in the surface sediment, consistent with their phytodetrital origin. TMA was more 13C-depleted than DMS(P) (TMA: -36.4 per mil to -39.2 per mil; DMS: -18.6 per mil to -23.4 per mil), presumably due to different biological or biosynthetic origins of the respective methyl groups. Both compounds showed a downcore decrease in their solid-phase concentration, a feature that was attributed to microbial degradation, but progressive enrichment in 13C (up to 4 per mil) with depth was observed only for DMS(P). The considerable pool size of TMA and DMS(P) outlined in this study and geochemical evidence of their degradability suggested these two compounds could be potentially important substrates for methane production in sulfate-reducing environments.

Description: Tubular carbonate conduits (TCC) represent the termination of fluid plumbing systems in environments of hydrocarbon seepage and play a relevant role in the discharge of methane from sub-seafloor sediments to the water column. However, the biogeochemical reactions and biological activities involved in their formation are not fully understood. To address this, TCC samples were collected with a remotely operated vehicle from the seabed on the SW flank of the Athina mud volcano in the eastern Mediterranean Sea. Petrographic, mineralogical, stable carbon and oxygen isotope and lipid biomarker analyses were performed to elucidate the formation processes of the tubular carbonates. Clotted and fibrous aragonite form the internal lining of the cavities, while the outer portion of the tubes is formed by micritic Mg-calcite cementing hemipelagic sediment. 13C-depleted Mg-calcite and aragonite (as low as −14.4‰ V-PDB) and lipid biomarkers (archaeol, −89.8‰ V-PDB) indicate that carbonate precipitation was influenced by sulfate-dependent anaerobic oxidation of methane (AOM). AOM locally enhances aragonite precipitation, thereby facilitating early lithification of the conduits within the mud volcano sediments. The size and morphology of the TCC comparable with the buried portion of tubeworm colonies found in the proximity of the sampling site. However, our results suggest that TCC likely formed by the action of burrowing organism rather than being mineralizations of the tubeworm colonies. This study provides new insights into the interpretation and understanding of TCC, highlighting the role of macrofaunal activity in the formation of migration pathways for hydrocarbon-rich fluids on the flank of a mud volcano.

Description: Polar lipid-derived fatty acids (PLFAs) and their stable carbon isotopes are frequently combined to characterize microbial populations involved in the degradation of organic matter, offering a link to biogeochemical processes and carbon sources used. However, PLFA patterns derive from multiple species and may be influenced by substrate types. Here, we investigated such dependencies by monitoring the transformation of position-specifically 13C-labeled amino acids (AAs) in coastal marine sediments dominated by heterotrophic bacteria. Alanine was assimilated into straight-chain FAs, while valine and leucine incorporation led to the characteristic production of even- and odd-numbered iso-series FAs. This suggests that identical microbial communities adjust lipid biosynthesis according to substrate availability. Transformation into precursor molecules for FA biosynthesis was manifested in increased 13C recoveries of the corresponding volatiles acetate, isobutyrate and isovalerate of up to 39.1%, much higher than for PLFAs (〈0.9%). A significant fraction of 13C was found in dissolved inorganic carbon (up to 37.9%), while less was recovered in total organic carbon (up to 17.3%). We observed a clear discrimination against the carboxyl C, whereby C2 and C3 positions were preferentially incorporated into PLFAs. Therefore, position-specific labeling is an appropriate tool for reconstructing the metabolic fate of protein-derived AAs in marine environments.

Description: Pore water and solid phase concentration in samples collected during RV Heincke expeditions HE406, HE443 and, HE461

Description: Hydrocarbon seeps are ubiquitous at gas-prone Cenozoic deltas such as the Nile Deep Sea Fan (NDSF) where seepage into the bottom water has been observed at several mud volcanoes (MVs) including North Alex MV (NAMV). Here we investigated the sources of hydrocarbon gases and sedimentary organic matter together with biomarkers of microbial activity at four locations of NAMV to constrain how venting at the seafloor relates to the generation of hydrocarbon gases in deeper sediments. At the centre, high upward flux of hot (70 °C) hydrocarbon-rich fluids is indicated by an absence of biomarkers of Anaerobic Oxidation of Methane (AOM) and nearly constant methane (CH4) concentration depth-profile. The presence of lipids of incompatible thermal maturities points to mixing between early-mature petroleum and immature organic matter, indicating that shallow mud has been mobilized by the influx of deep-sourced hydrocarbon-rich fluids. Methane is enriched in the heavier isotopes, with values of d13C ~-46.6 per mil VPDB and dD ~-228 per mil VSMOW, and is associated with high amounts of heavier homologues (C2+) suggesting a co-genetic origin with the petroleum. On the contrary at the periphery, a lower but sustained CH4 flux is indicated by deeper sulphate-methane transition zones and the presence of 13C-depleted biomarkers of AOM, consistent with predominantly immature organic matter. Values of d13C-CH4 ~-60 per mil VPDB and decreased concentrations of 13C-enriched C2+ are typical of mixed microbial CH4 and biodegraded thermogenic gas from Plio-Pleistocene reservoirs of the region. The maturity of gas condensate migrated from pre-Miocene sources into Miocene reservoirs of the Western NDSF is higher than that of the gas vented at the centre of NAMV, supporting the hypothesis that it is rather released from the degradation of oil in Neogene reservoirs. Combined with the finding of hot pore water and petroleum at the centre, our results suggest that clay mineral dehydration of Neogene sediments, which takes place posterior to reservoir filling, may contribute to intense gas generation at high sedimentation rate deltas.

Description: Arctic lakes and wetlands contribute a substantial amount of methane to the contemporary atmosphere, yet profound knowledge gaps remain regarding the intensity and climatic control of past methane emissions from this source. In this study, we reconstruct methane turnover and environmental conditions, including estimates of mean annual and summer temperature, from a thermokarst lake (Lake Qalluuraq) on the Arctic Coastal Plain of northern Alaska for the Holocene by using source-specific lipid biomarkers preserved in a radiocarbon-dated sediment core. Our results document a more prominent role for methane in the carbon cycle when the lake basin was an emergent fen habitat between ~12,300 and ~10,000 cal yr BP, a time period closely coinciding with the Holocene Thermal Maximum (HTM) in North Alaska. Enhanced methane turnover was stimulated by relatively warm temperatures, increased moisture, nutrient supply, and primary productivity. After ~10,000 cal yr BP, a thermokarst lake with abundant submerged mosses evolved, and through the mid-Holocene temperatures were approximately 3°C cooler. Under these conditions, organic matter decomposition was attenuated, which facilitated the accumulation of submerged mosses within a shallower Lake Qalluuraq. Reduced methane assimilation into biomass during the mid-Holocene suggests that thermokarst lakes are carbon sinks during cold periods. In the late-Holocene from ~2700 cal yr BP to the most recent time, however, temperatures and carbon deposition rose and methane oxidation intensified, indicating that more rapid organic matter decomposition and enhanced methane production could amplify climate feedback via potential methane emissions in the future.

Description: Analytical data of an anaerobic litter decomposition experiment in three waterlogged organic wetland soils. Samples include Phragmites australis leaves, harvested in autumn 2012 from three peatlands in northeastern Germany, i.e. the oligotrophic kettle-hole mire Kablow-Ziegelei, the mesotrophic terrestrialization mire Töpchin Süd, and the rewetted fen Stangenhagen. Phragmites australis rhizomes samples from the same three sites were harvested from living plants in June 2013. Waterlogged organic soils from the three sites were sampled at the same day in June 2013. The decomposition experiment was performed in the laboratory at 20 °C in polyethylene containers (80 cm × 60 cm × 43 cm) filled with the submerged organic soils. The leaf litterbags (1g litter per litterbag) and rhizome litterbags (3 g litter per litterbag) were placed close to bottom of each container for 75 days. At the end of the decomposition time, the litterbags were recovered and gently rinsed with distilled water. After weighting, litters were milled and stored at -20°C. This publication series includes data of the subsequent chemical analyses. These include litter CN-data, determined with an elemental analyzer, mass loss data, determined gravimetrically before milling, data on the peak intensity of the proteinaceous bands Amide I and Amide II, determined via peak fitting of the vector normalized FTIR spectra (Origin Peak Analyzer), the increase of the asymmetric phosphodiester band due to litter decomposition, determined as the peak height of the second derivative difference spectra at 1220 cm-1, lignin phenol concentrations, determined by gas chromatography mass spectrometry after alkaline CuO oxidation of litter and soil substrates, as well as vector normalized FTIR absorption spectra (.abs) and second derivative spectra (.2der) of Phragmites australis plant litters.

Description: Vector normalized FTIR absorption spectra (.abs) and second derivative spectra (.2der) of Phragmites australis plant litter, collected from three wetlands in northeast Germany.