Molecular composition in surface and subsurface sediments of the Helgoland mud area, North Sea

The role of microorganisms in the cycling of sedimentary organic carbon is a crucial one. To better understand relationships between molecular composition of a potentially bioavailable fraction of organic matter and microbial populations, bacterial and archaeal communities were characterized using pyrosequencing-based 16S rRNA gene analysis in surface (top 30 cm) and subsurface/deeper sediments (30-530 cm) of the Helgoland mud area, North Sea. Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) was used to characterize a potentially bioavailable organic matter fraction (hot-water extractable organic matter, WE-OM). Algal polymer-associated microbial populations such as members of the Gammaproteobacteria, Bacteroidetes, and Verrucomicrobia were dominant in surface sediments while members of the Chloroflexi (Dehalococcoidales and candidate order GIF9) and Miscellaneous Crenarchaeota Groups (MCG), both of which are linked to degradation of more recalcitrant, aromatic compounds and detrital proteins, were dominant in subsurface sediments. Microbial populations dominant in subsurface sediments (Chloroflexi, members of MCG, and Thermoplasmata) showed strong correlations to total organic carbon (TOC) content. Changes of WE-OM with sediment depth reveal molecular transformations from oxygen-rich [high oxygen to carbon (O/C), low hydrogen to carbon (H/C) ratios] aromatic compounds and highly unsaturated compounds toward compounds with lower O/C and higher H/C ratios. The observed molecular changes were most pronounced in organic compounds containing only CHO atoms. Our data thus, highlights classes of sedimentary organic compounds that may serve as microbial energy sources in methanic marine subsurface environments.

Dissolved organic matter in the Lena Delta in 2009

Large Arctic rivers discharge significant amounts of dissolved organic matter (DOM) into the Arctic Ocean. We sampled natural waters of the Lena River, the Buor-Khaya Bay (Laptev Sea), permafrost melt water creeks, ice complex melt water creeks and a lake. The goal of this study was to characterize the molecular DOM composition with respect to different water bodies within the Lena Delta. We aimed at an identification of source-specific DOM molecular markers and their relative contribution to DOM of different origin. The molecular characterization was performed for solid-phase extracted DOM by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Average dissolved organic carbon concentrations in the original samples were 490±75 µmol C/L for riverine and bay samples and 399±115 µmol C/L for permafrost melt water creeks. Average TDN concentrations were elevated in the permafrost melt waters (19.7±7.1 µmol N/L) in comparison to the river and the bay (both 13.2±2.6 µmol N/L). FT-ICR MS and statistical tools demonstrated that the origin of DOM in the Lena Delta was systematically reflected in its molecular composition. Magnitude weighted parameters calculated from MS data (O/Cwa, H/Cwa, C/Nwa) highlighted preliminary sample discrimination. The highest H/Cwa of 1.315 was found for DOM in melt water creeks in comparison to 1.281 for river and 1.230 for the bay samples. In the bay samples we observed a higher fraction of oxygen-rich components which was reflected in an O/Cwa ratio of 0.445 in comparison to 0.425 and 0.427 in the river and creeks, respectively. From the southernmost location to the bay a relative depletion of nitrogenous molecular markers and an enrichment of oxidized DOM components occurred. The highest contribution of nitrogenous components was indicative for creeks reflected in a C/Nwa of 104 in comparison to 143 and 176 in the river and bay, respectively. These observations were studied on a molecular formula level using principal component and indicator value analyses. The results showed systematic differences with respect to water origin and constitute an important basis for a better mechanistic understanding of DOM transformations in the changing Arctic rivers.

Late Oligocene rapid transformations in the South China Sea

Lithobiostratigraphic data indicate that the double reflectors on the seismic profile through Ocean Drilling Program (ODP) Site 1148 represent two unconformities that coincide, respectively, with the lower/upper Oligocene boundary at ~488 mcd, and Oligocene-Miocene boundary at 460 mcd. Two other unconformities, at ~478 and 472 mcd, respectively, were also identified within the upper Oligocene section. Together they erased a sediment record of about 3 Ma from this locality in a period of very active seafloor spreading. The existence of 32.8 Ma marine sediment at the terminated depth (850 mcd) indicates that the initial breakup of the South China Sea (SCS) was probably during 34-33 Ma, close to the Eocene-Oligocene boundary. High sedimentation rates of 60-115 m/my from the much expanded, N350 m lower Oligocene section resulted from rifting and rapid subsidence between 33 and 29 Ma. The mid-Oligocene unconformity at ~28.5 Ma, which also occurred in many parts of the Indo-West Pacific region, was probably related to a significant uplift of the Himalayan-Tibetan Plateau to the west and the initial collision between Indonesia and Australia in the south. A narrowed Indonesian seaway may have accounted for the late Oligocene warming and chalk deposition in the northern South China Sea including the Site 1148 locality. The unconformities and slumps near the Oligocene-Miocene boundary indicate a very unstable tectonic regime, probably corresponding to changes in the rotation of different land blocks and the seafloor spreading ridge from nearly E-W to NE-SW, as recognized earlier at magnetic Anomaly 7. This 25 Ma event also saw the first New Guinea terrane docking at the northern Australian craton. The low sedimentation rate of ~15 m/my in the early to middle Miocene may correspond to another period of rapid seafloor spreading and rapid widespread subsidence that effectively caused sediment source areas to retreat with a rapidly rising sea level. The isostatic nature of these late Oligocene unconformities and slumps with several major collision-uplift events indicate that the rapid changes in the early evolutionary history of the South China Sea were mainly responding to regional tectonic reconfiguration including the uplift-driven southeast extrusion of the Indochina subcontinent.

Morphometric data for Globigerinoides sacculifer and Globorotalia tumida (size and Fourier coefficients) and temperature proxy reconstructions (UK37' and Tex86H) from samples from ODP sites 165-999/165-1000 and 202-1241 spanning the last 10Ma

Sediment samples from both Site 165-999/165-1000 (Atlantic) and Site 202-1241 (Pacific) were chosen at 1Ma intervals over the period 0.3-9.3Ma. Samples were washed and sieved <150µm. Splits of the sediment fraction were picked completely to obtain, where possible, at least 30 specimens each of planktic foraminifer species Globigerinoides sacculifer and Globorotalia tumida, on which outline analysis (Fourier) was performed. Sea surface and thermocline temperatures were reconstructed from palaeoenvironmental proxies (UK37' and Tex86H respectively).

Sediment and organic matter properties, and molecular formula from sampling locations in the Northern Black Sea

Remineralization of organic matter in reactive marine sediments releases nutrients and dissolved organic matter (DOM) into the ocean. Here we focused on the molecular-level characterization of DOM by high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) in sediment pore waters and bottom waters from contrasting redox regimes in the northern Black Sea with particular emphasis on nitrogen-bearing compounds to derive an improved understanding of the molecular transformations involved in nitrogen release. The number of nitrogen-bearing molecules is generally higher in pore waters than in bottom waters. This suggests intensified degradation of nitrogen-bearing precursor molecules such as proteins in anoxic sediments: No significant difference was observed between sediments deposited under oxic vs anoxic conditions (average O/C ratios of 0.55) suggesting that the different organic matter quality induced by contrasting redox conditions does not impact protein diagenesis in the subseafloor. Compounds in the pore waters were on average larger, less oxygenated, and had a higher number of unsaturations. Applying a mathematical model, we could show that the assemblages of nitrogen-bearing molecular formulas are potential products of proteinaceous material that was transformed by the following reactions: (a) hydrolysis and deamination, both reducing the molecular size and nitrogen content of the products and intermediates; (b) oxidation and hydration of the intermediates; and (c) methylation and dehydration.