Carbon geochemistry in serpentinites from and beneath the Lost City Hydrothermal Field

The carbon geochemistry of serpentinized peridotites and gabbroic rocks recovered at the Lost City Hydrothermal Field (LCHF) and drilled at IODP Hole 1309D at the central dome of the Atlantis Massif (Mid-Atlantic Ridge, 30°N) was examined to characterize carbon sources and speciation in oceanic basement rocks affected by long-lived hydrothermal alteration. Our study presents new data on the geochemistry of organic carbon in the oceanic lithosphere and provides constraints on the fate of dissolved organic carbon in seawater during serpentinization. The basement rocks of the Atlantis Massif are characterized by total carbon (TC) contents of 59 ppm to 1.6 wt% and 17863_TC values ranging from -28.7? to +2.3?. In contrast, total organic carbon (TOC) concentrations and isotopic compositions are relatively constant (d13C_TOC: -28.9? to -21.5?) and variations in d13CTC reflect mixing of organic carbon with carbonates of marine origin. Saturated hydrocarbons extracted from serpentinites beneath the LCHF consist of n-alkanes ranging from C15 to C30. Longer-chain hydrocarbons (up to C40) are observed in olivine-rich samples from the central dome (IODP Hole 1309D). Occurrences of isoprenoids (pristane, phytane and squalane), polycyclic compounds (hopanes and steranes) and higher relative abundances of n-C16 to n-C20 alkanes in the serpentinites of the southern wall suggest a marine organic input. The vent fluids are characterized by high concentrations of methane and hydrogen, with a putative abiotic origin of hydrocarbons; however, evidence for an inorganic source of n-alkanes in the basement rocks remains equivocal. We propose that high seawater fluxes in the southern part of the Atlantis Massif likely favor the transport and incorporation of marine dissolved organic carbon and overprints possible abiotic geochemical signatures. The presence of pristane, phytane and squalane biomarkers in olivine-rich samples associated with local faults at the central dome implies fracture-controlled seawater circulation deep into the gabbroic core of the massif. Thus, our study indicates that hydrocarbons account for an important proportion of the total carbon stored in the Atlantis Massif basement and suggests that serpentinites may represent an important (as yet unidentified) reservoir for dissolved organic carbon (DOC) from seawater.

Geochemistry of sediment cores GeoB13820-1 and GeoB13863-1 from the western South Atlantic

Here, we present results from sediments collected in the Argentine Basin, a non-steady state depositional marine system characterized by abundant oxidized iron within methane-rich layers due to sediment reworking followed by rapid deposition. Our comprehensive inorganic data set shows that iron reduction in these sulfate and sulfide-depleted sediments is best explained by a microbially mediated process-implicating anaerobic oxidation of methane coupled to iron reduction (Fe-AOM) as the most likely major mechanism. Although important in many modern marine environments, iron-driven AOM may not consume similar amounts of methane compared with sulfate-dependent AOM. Nevertheless, it may have broad impact on the deep biosphere and dominate both iron and methane cycling in sulfate-lean marine settings. Fe-AOM might have been particularly relevant in the Archean ocean, >2.5 billion years ago, known for its production and accumulation of iron oxides (in iron formations) in a biosphere likely replete with methane but low in sulfate. Methane at that time was a critical greenhouse gas capable of sustaining a habitable climate under relatively low solar luminosity, and relationships to iron cycling may have impacted if not dominated methane loss from the biosphere.

Boron, carbonate carbon and oxygen isotope analyses of samples from the Yangtze Platform (China), Congo craton (Namibia), and Karatau microcontinent (Kazakhstan) of the Marinoan glaciation

Boron isotope patterns preserved in cap carbonates deposited in the aftermath of the younger Cryogenian (Marinoan, ca. 635 Ma) glaciation confirm a temporary ocean acidification event on the continental margin of the southern Congo craton, Namibia. To test the significance of this acidification event and reconstruct Earth's global seawater pH states at the Cryogenian-Ediacaran transition, we present a new boron isotope data set recorded in cap carbonates deposited on the Yangtze Platform in south China and on the Karatau microcontinent in Kazakhstan. Our compiled d11B data reveal similar ocean pH patterns for all investigated cratons and confirm the presence of a global and synchronous ocean acidification event during the Marinoan deglacial period, compatible with elevated postglacial pCO2 concentrations. Differences in the details of the ocean acidification event point to regional distinctions in the buffering capacity of Ediacaran seawater.

Pore water and solid phase sulfur, carbon and iron data from samples collected in the Argentine Basin during expedition M78

Sulfur phases in the Argentine Basin.

Sedimentary climate indicators of sediment core MD08-3167 and GeoB1711-4, southwestern Africa

The past climate evolution of southwestern Africa is poorly understood and interpretations of past hydrological changes are sometimes contradictory. Here we present a record of leaf-wax dD and View the MathML source taken from a marine sediment core at 23°S off the coast of Namibia to reconstruct the hydrology and C3 versus C4 vegetation of southwestern Africa over the last 140 000 years (140 ka). We find lower leaf-wax dD and higher View the MathML source (more C4 grasses), which we interpret to indicate wetter Southern Hemisphere (SH) summer conditions and increased seasonality, during SH insolation maxima relative to minima and during the last glacial period relative to the Holocene and the last interglacial period. Nonetheless, the dominance of C4 grasses throughout the record indicates that the wet season remained brief and that this region has remained semi-arid. Our data suggest that past precipitation increases were derived from the tropics rather than from the winter westerlies. Comparison with a record from the Congo Basin indicates that hydroclimate in southwestern Africa has evolved in antiphase with that of central Africa over the last 140 ka.

Phosphate d18O pore-water profiles of sediment core GeoB11807-2 and GeoB11804-4

Phosphorus cycling in the ocean is influenced by biological and geochemical processes that are reflected in the oxygen isotope signature of dissolved inorganic phosphate (Pi). Extending the Pi oxygen isotope record from the water column into the seabed is difficult due to low Pi concentrations and small amounts of marine porewaters available for analysis. We obtained porewater profiles of Pi oxygen isotopes using a refined protocol based on the original micro-extraction designed by Colman (2002). This refined and customized method allows the conversion of ultra-low quantities (0.5 - 1 µmol) of porewater Pi to silver phosphate (Ag3PO4) for routine analysis by mass spectrometry. A combination of magnesium hydroxide co-precipitation with ion exchange resin treatment steps is used to remove dissolved organic matter, anions, and cations from the sample before precipitating Ag3PO4. Samples as low as 200 µg were analyzed in a continuous flow isotope ratio mass spectrometer setup. Tests with external and laboratory internal standards validated the preservation of the original phosphate oxygen isotope signature (d18OP) during micro extraction. Porewater data on d18OP has been obtained from two sediment cores of the Moroccan margin. The d18OP values are in a range of +19.49 to +27.30 per mill. We apply a simple isotope mass balance model to disentangle processes contributing to benthic P cycling and find evidence for Pi regeneration outbalancing microbial demand in the upper sediment layers. This highlights the great potential of using d18OP to study microbial processes in the subseafloor and at the sediment water interface.

Organic matter and sediment properties of samples from site GeoB15105 from the Black Sea

Dissolved organic matter (DOM) in marine sediments is a complex mixture of thousands of individual constituents that participate in biogeochemical reactions and serve as substrates for benthic microbes. Knowledge of the molecular composition of DOM is a prerequisite for a comprehensive understanding of the biogeochemical processes in sediments. In this study, interstitial water DOM was extracted with Rhizon samplers from a sediment core from the Black Sea and compared to the corresponding water-extractable organic matter fraction (<0.4 µm) obtained by Soxhlet extraction, which mobilizes labile particulate organic matter and DOM. After solid phase extraction (SPE) of DOM, samples were analyzed for the molecular composition by Fourier Transform Ion-Cyclotron Resonance Mass Spectrometry (FT-ICR MS) with electrospray ionization in negative ion mode. The average SPE extraction yield of the dissolved organic carbon (DOC) in interstitial water was 63%, whereas less than 30% of the DOC in Soxhlet-extracted organic matter was recovered. Nevertheless, Soxhlet extraction yielded up to 4.35% of the total sedimentary organic carbon, which is more than 30-times the organic carbon content of the interstitial water. While interstitial water DOM consisted primarily of carbon-, hydrogen- and oxygen-bearing compounds, Soxhlet extracts yielded more complex FT-ICR mass spectra with more peaks and higher abundances of nitrogen- and sulfur-bearing compounds. The molecular composition of both sample types was affected by the geochemical conditions in the sediment; elevated concentrations of HS- promoted the early diagenetic sulfurization of organic matter. The Soxhlet extracts from shallow sediment contained specific three- and four-nitrogen-bearing molecular formulas that were also detected in bacterial cell extracts and presumably represent proteinaceous molecules. These compounds decreased with increasing sediment depth while one- and two-nitrogen-bearing molecules increased, resulting in a higher similarity of both sample types in the deep sediment. In summary, Soxhlet extraction of sediments accessed a larger and more complex pool of organic matter than present in interstitial water DOM.