Description: The interplay between sediment deposition patterns, organic matter type and the quantity and quality of reactive mineral phases determines the accumulation, speciation and isotope composition of pore water and solid phase sulfur constituents in marine sediments. Here, we present the sulfur geochemistry of siliciclastic sediments from two sites along the Argentine continental slope--a system characterized by dynamic deposition and reworking, which result in non-steady state conditions. The two investigated sites have different depositional histories but have in common that reactive iron phases are abundant and that organic matter is refractory--conditions that result in low organoclastic sulfate reduction rates. Deposition of reworked, isotopically light pyrite and sulfurized organic matter appear to be important contributors to the sulfur inventory, with only minor addition of pyrite from organoclastic sulfate reduction above the sulfate-methane transition (SMT). Pore-water sulfide is limited to a narrow zone at the SMT. The core of that zone is dominated by pyrite accumulation. Iron monosulfide and elemental sulfur accumulate above and below this zone. Iron monosulfide precipitation is driven by the reaction of low amounts of hydrogen sulfide with ferrous iron and is in competition with the oxidation of sulfide by iron (oxyhydr)oxides to form elemental sulfur. The intervals marked by precipitation of intermediate sulfur phases at the margin of the zone with free sulfide are bordered by two distinct peaks in total organic sulfur. Organic matter sulfurization appears to precede pyrite formation in the iron-dominated margins of the sulfide zone, potentially linked to the presence of polysulfides formed by reaction between dissolved sulfide and elemental sulfur. Thus, SMTs can be hotspots for organic matter sulfurization in sulfide-limited, reactive iron-rich marine sedimentary systems. Furthermore, existence of elemental sulfur and iron monosulfide phases meters below the SMT demonstrates that in sulfide-limited systems metastable sulfur constituents are not readily converted to pyrite but can be buried to deeper sediment depths. Our data show that in non-steady state systems, redox zones do not occur in sequence but can reappear or proceed in inverse sequence throughout the sediment column, causing similar mineral alteration processes to occur at the same time at different sediment depths.

Description: The carbonate-free abyss of the North Pacific defies most paleoceanographic proxy methods and hence remains a "blank spot" in ocean and climate history. Paleomagnetic and rock magnetic, geochemical, and sedimentological methods were combined to date and analyze seven middle to late Pleistocene northwest Pacific sediment cores from water depths of 5100 to 5700 m. Besides largely coherent tephra layers, the most striking features of these records are nearly magnetite-free zones corresponding to glacial marine isotope stages (MISs) 22, 12, 10, 8, 6, and 2. Magnetite depletion is correlated with organic carbon and quartz content and anticorrelated with biogenic barite and opal content. Within interglacial sections and mid-Pleistocene transition glacial stages MIS 20, 18, 16, and 14, magnetite fractions of detrital, volcanic, and bacterial origin are all well preserved. Such alternating successions of magnetic iron mineral preservation and depletion are known from sapropel-marl cycles, which accumulated under periodically changing bottom water oxygen and redox conditions. In the open central northwest Pacific Ocean, the only conceivable mechanism to cause such abrupt change is a modified glacial bottom water circulation. During all major glaciations since MIS 12, oxygen-depleted Antarctic Bottom Water (AABW)-sourced bottom water seems to have crept into the abyssal northwest Pacific below ~5000 m depth, thereby changing redox conditions in the sediment, trapping and preserving dissolved and particulate organic matter and, in consequence, reducing and dissolving both, biogenic and detrital magnetite. At deglaciation, a downward progressing oxidation front apparently remineralized and released these sedimentary carbon reservoirs without replenishing the magnetite losses.

Description: 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.

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

Description: In dieser Arbeit wurde das Zeitintervall zwischen 20 und 10 ka vor heute einschließlich des Heinrichevent 1 und der Younger Dryas am Kern GeoB 3910-2 neu untersucht. An organischen Parametern, basierend auf der Verteilung von bakteriellen GDGTs, und Elementkonzentrationen wurde eine Rekonstruktion der klimatischen Bedingungen und Veränderungen im Hinterland von NO Brasilien durchgeführt. Es zeigt sich, dass sich die durchschnittliche Landtemperatur gleich der Oberflächenwassertemperatur verhält und im Gegensatz zu den Phasen von H6 bis H2 dem antarktischen Erwärmungstrend ab 17 ka vor heute folgt. Weiterhin konnte gezeigt werden, dass durch die südwärts Verlagerung der ITCZ während H1 und der YD die Niederschläge in NO Brasilen intensiviert wurden, was eine Ausbreitung der Flüsse und Änderung der Erosionsgebiete zur Folge hatte.

Description: Subglacial lakes are widespread beneath the Antarctic ice sheet but their control on ice sheet dynamics and their ability to harbour life remain poorly characterised. Here we present the evidence for a palaeo-subglacial lake on the Antarctic continental shelf. A distinct sediment facies recovered from a bedrock basin in Pine Island Bay indicates deposition within a low-energy lake environment. Diffusive-advection modelling demonstrates that low chloride concentrations in the sediment pore water can only be explained by initial deposition of this facies in a freshwater setting. These observations indicate that an active subglacial meltwater network, similar to that observed beneath the extant ice sheet, was also active during the last glacial period. It also provides a new framework for refining exploration of these unique environments.

Description: A substantial strengthening of the South American monsoon system (SAMS) during Heinrich Stadials (HS) points toward decreased cross-equatorial heat transport as the main driver of monsoonal hydroclimate variability at millennial time-scales. In order to better constrain the exact timing and internal structure of HS1 over tropical South America we assessed two precisely dated speleothem records from central-eastern and northeastern Brazil in combination with two marine records of terrestrial organic and inorganic matter input into the western equatorial Atlantic. During HS1 we recognize at least two events of widespread intensification of the SAMS across the entire region influenced by the South Atlantic Convergence Zone (SACZ) at 16.11-14.69 kyr BP and 18.1-16.66 kyr BP (labeled as HS1a and HS1c, respectively), separated by a dry excursion from 16.66-16.11 kyr BP (HS1b). In view of the spatial structure of precipitation anomalies, the widespread increase of monsoon precipitation over the SACZ domain was termed 'Mega-SACZ'.