Ketones in hydrothermal petroleums and sediments from Guaymas Basin

The polar compound (NSO) fractions of seabed petroleums and sediment extracts from the Guaymas Basin hydrothermal system have been analyzed by gas chromatography and gas chromatography-mass spectrometry. The oils were collected from the interiors and exteriors of high temperature hydrothermal vents and represent hydrothermal pyrolysates that have migrated to the seafloor by hydrothermal fluid circulation. The downcore samples are representative of both thermally unaltered and thermally altered sediments. The survey has revealed the presence of oxygenated compounds correlated with samples exhibiting a high degree of thermal maturity. Several homologous series of related ketone isomers are enriched in the interiors of the hydrothermal vent samples or in hydrothermally-altered sequences of the downcore sediments (DSDP Holes 477 and 481A). The n-alkanones range in carbon number from C11 to C33 with a Cmax from 14 to 23, distributions that are similar to those of the n-alkanes. The alkan-2-ones are usually in highest concentrations, with lower amounts of 3-, 4-, 5-, 6-, 7- (and higher) alkanones, and they exhibit no carbon number preference (there is an odd carbon number preference of alkanones observed for downcore samples). The alkanones are enriched in the interiors of the hydrothermal vent spires or in downcore hydrothermally-altered sediments, indicating an origin at depth or in the hydrothermal fluids and not from an external biogenic deposition. Minor amounts of C13 and C18 isoprenoid ketones are also present. Simulation of the natural hydrothermal alternation process by laboratory hydrous pyrolysis techniques provided information regarding the mode of alkanone formation. Hydrous pyrolysis of n-C32H66 at 350°C for 72 h with water only or water with inorganic additives has been studied using a stainless steel reaction vessel. In each experiment oxygenated hydrocarbons, including alkanones, were formed from the n-alkane. The product distributions indicate a reaction pathway consisting of n-alkanes and a-olefins as primary cracking products with internal olefins and alkanones as secondary reaction products. Hydrous pyrolyses of Messel shale spiked with molecular probes have been performed under similar time and temperature constraints to produce alkanone distributions like those found in the hydrothermal vent petroleums.

Mapping of C4 plant input from North West Africa into North East Atlantic sediments

Mapping the abundance of 13C in leaf-wax components in surface sediments recovered from the seafloor off northwest Africa (0-35°N) reveals a clear pattern of delta13C distribution, indicating systematic changes in the proportions of terrestrial C3 and C4 plant input. At 20°N latitude, we find that isotopically enriched products characteristic of C4 plants account for more than 50% of the terrigenous inputs. This signal extends westward beneath the path of the dust-laden Sahara Air Layer (SAL). High C4 contributions, apparently carried by January trade winds, also extend far into the Gulf of Guinea. Similar distributions are obtained if summed pollen counts for the Chenopodiaceae-Amaranthaceae and the Poaceae are used as an independent C4 proxy. We conclude that the specificity of the latitudinal distribution of vegetation in North West Africa and the pathways of the wind systems (trade winds and SAL) are responsible for the observed isotopic patterns observed in the surface sediments. Molecular-isotopic maps on the marine-sedimentary time horizons (e.g., during the last glacial maximum) are thus a robust tool for assessing the phytogeographic changes on the tropical and sub-tropical continents, which have important implications for the changes in climatic and atmospheric conditions.

Hydrocarbon analyses of submarine mud volcanoes (MV) in the Kumano forearc basin

Twelve submarine mud volcanoes (MV) in the Kumano forearc basin within the Nankai Trough subduction zone were investigated for hydrocarbon origins and fluid dynamics. Gas hydrates diagnostic for methane concentrations exceeding solubilities were recovered from MVs 2, 4, 5, and 10. Molecular ratios (C1/C2<250) and stable carbon isotopic compositions (d13C-CH4 >-40 per mil V-PDB) indicate that hydrate-bound hydrocarbons (HCs) at MVs 2, 4, and 10 are derived from thermal cracking of organic matter. Considering thermal gradients at the nearby IODP Sites C0009 and C0002, the likely formation depth of such HCs ranges between 2300 and 4300 m below seafloor (mbsf). With respect to basin sediment thickness and the minimum distance to the top of the plate boundary thrust we propose that the majority of HCs fueling the MVs is derived from sediments of the Cretaceous to Tertiary Shimanto belt below Pliocene/Pleistocene to recent basin sediments. Considering their sizes and appearances hydrates are suggested to be relicts of higher MV activity in the past, although the sporadic presence of vesicomyid clams at MV 2 showed that fluid migration is sufficient to nourish chemosynthesis-based organisms in places. Distributions of dissolved methane at MVs 3, 4, 5, and 8 pointed at fluid supply through one or few MV conduits and effective methane oxidation in the immediate subsurface. The aged nature of the hydrates suggests that the major portion of methane immediately below the top of the methane-containing sediment interval is fueled by current hydrate dissolution rather than active migration from greater depth.

Standing stocks and carbon isotopes of live benthic foraminifera from the South Atlantic

Live (Rose Bengal stained) and dead benthic foraminifera of surface and subsurface sediments from 25 stations in the eastern South Atlantic Ocean and the Atlantic sector of the Southern Ocean were analyzed to decipher a potential influence of seasonally and spatially varying high primary productivity on the stable carbon isotopic composition of foraminiferal tests. Therefore, stations were chosen so that productivity strongly varied, whereas conservative water mass properties changed only little. To define the stable carbon isotopic composition of dissolved inorganic carbon (d13CDIC) in ambient water masses, we compiled new and previously published d13CDIC data in a section running from Antarctica through Agulhas, Cape and Angola Basins, via the Guinea Abyssal Plain to the Equator. We found that intraspecific d13C variability of all species at a single site is constantly low throughout their distribution within the sediments, i.e. species specific and site dependent mean values calculated from all subbottom depths on average only varied by +/-0.09 per mil. This is important because it makes the stable carbon isotopic signal of species independent of the particular microhabitat of each single specimen measured and thus more constant and reliable than has been previously assumed. So-called vital and/or microhabitat effects were further quantified: (1) d13C values of endobenthic Globobulimina affinis, Fursenkoina mexicana, and Bulimina mexicana consistently are by between -1.5 and -1.0 per mil VPDB more depleted than d13C values of preferentially epibenthic Fontbotia wuellerstorfi, Cibicidoides pachyderma, and Lobatula lobatula. (2) In contrast to the Antarctic Polar Front region, at all stations except one on the African continental slope Fontbotia wuellerstorfi records bottom water d13CDIC values without significant offset, whereas L. lobatula and C. pachyderma values deviate from bottom water values by about -0.4 per mil and -0.6 per mil, respectively. This adds to the growing amount of data on contrasting cibicid d13C values which on the one hand support the original 1:1-calibration of F. wuellerstorfi and bottom water d13CDIC, and on the other hand document severe depletions of taxonomically close relatives such as L. lobatula and C. pachyderma. At one station close to Bouvet Island at the western rim of Agulhas Basin, we interpret the offset of -1.5 per mil between bottom water d13CDIC and d13C values of infaunal living Bulimina aculeata in contrast to about -0.6 +/- 0.1 per mil measured at eight stations close-by, as a direct reflection of locally increased organic matter fluxes and sedimentation rates. Alternatively, we speculate that methane locally released from gas vents and related to hydrothermal venting at the mid-ocean ridge might have caused this strong depletion of 13C in the benthic foraminiferal carbon isotopic composition. Along the African continental margin, offsets between deep infaunal Globobulimina affinis and epibenthic Fontbotia wuellerstorfi as well as between shallow infaunal Uvigerina peregrina and F. wuellerstorfi, d13C values tend to increase with generally increasing organic matter decomposition rates. Although clearly more data are needed, these offsets between species might be used for quantification of biogeochemical paleogradients within the sediment and thus paleocarbon flux estimates. Furthermore, our data suggest that in high-productivity areas where sedimentary carbonate contents are lower than 15 weight %, epibenthic and endobenthic foraminiferal d13C values are strongly influenced by 13C enrichment probably due to carbonate-ion undersaturation, whereas above this sedimentary carbonate threshold endobenthic d13C values reflect depleted pore water d13CDIC values.

(Figure 1 and 2) Phosphorus pools in the investigated sediments quantified by SEDEX sequential extraction and distribution of recovered 33P spike between sedimentary P pools after incubation

Phosphorus is an essential nutrient for life. In the ocean, phosphorus burial regulates marine primary production**1, 2. Phosphorus is removed from the ocean by sedimentation of organic matter, and the subsequent conversion of organic phosphorus to phosphate minerals such as apatite, and ultimately phosphorite deposits**3, 4. Bacteria are thought to mediate these processes**5, but the mechanism of sequestration has remained unclear. Here, we present results from laboratory incubations in which we labelled organic-rich sediments from the Benguela upwelling system, Namibia, with a 33P-radiotracer, and tracked the fate of the phosphorus. We show that under both anoxic and oxic conditions, large sulphide-oxidizing bacteria accumulate 33P in their cells, and catalyse the nearly instantaneous conversion of phosphate to apatite. Apatite formation was greatest under anoxic conditions. Nutrient analyses of Namibian upwelling waters and sediments suggest that the rate of phosphate-to-apatite conversion beneath anoxic bottom waters exceeds the rate of phosphorus release during organic matter mineralization in the upper sediment layers. We suggest that bacterial apatite formation is a significant phosphorus sink under anoxic bottom-water conditions. Expanding oxygen minimum zones are projected in simulations of future climate change**6, potentially increasing sequestration of marine phosphate, and restricting marine productivity.

Seafloor spreading magnetic anomaly isochron map compilation for the Weddell Sea and Scotia Sea

The deep sea sedimentary record is an archive of the pre-glacial to glacial development of Antarctica and changes in climate, tectonics and ocean circulation. Identification of the pre-glacial, transitional and full glacial components in the sedimentary record is necessary for ice sheet reconstruction and to build circum-Antarctic sediment thickness grids for past topography and bathymetry reconstructions, which constrain paleoclimate models. A ~3300 km long Weddell Sea to Scotia Sea transect consisting of multichannel seismic reflection data from various organisations, were used to interpret new horizons to define the initial basin-wide seismostratigraphy and to identify the pre-glacial to glacial components. We mapped seven main units of which three are in the inferred Cretaceous-Paleocene pre-glacial regime, one in the Eocene-Oligocene transitional regime and three units in the Miocene-Pleistocene full glacial climate regime. Sparse borehole data from ODP leg 113 and SHALDRIL constrain the ages of the upper three units. Compiled seafloor spreading magnetic anomalies constrain the basement ages and the hypothetical age model. In many cases, the new horizons and stratigraphy contradict the interpretations in local studies. Each seismic sedimentary unit and its associated base horizon are continuous and traceable for the entire transect length, but reflect a lateral change in age whilst representing the same deposition process. The up to 1240 m thick pre-glacial seismic units form a mound in the central Weddell Sea basin and, in conjunction with the eroded flank geometry, support the interpretation of a Cretaceous proto-Weddell Gyre. The base reflector of the transitional seismic unit, which marks the initial ice sheet advances to the outer shelf, has a lateral model age of 26.6-15.5 Ma from southeast to northwest. The Pliocene-Pleistocene glacial deposits reveals lower sedimentations rates, indicating a reduced sediment supply. Sedimentation rates for the pre-glacial, transitional and full glacial components are highest around the Antarctic Peninsula, indicating higher erosion and sediment supply of a younger basement. We interpret an Eocene East Antarctic Ice Sheet expansion, Oligocene grounding of the West Antarctic Ice Sheet and Early Miocene grounding of the Antarctic Peninsula Ice Sheet.

Alkenones in the Mediterranean Sea

Time-series of downward alkenone fluxes have been investigated at 200 m depth over a one year sediment trap experiment, in the Northwestern Mediterranean Sea. Alkenone flux maxima occurred in autumn and to a lesser extent in May, during the spring bloom. Temperature estimates calculated from the UK'37 index revealed that alkenone producers preferentially develop in subsurface waters (at about 50 m) in spring, whereas the autumn alkenone production occurred upper in the water column (around 30 m). Examination of the core-top UK'37 index values at various sites of the Northwestern Mediterranean basin, suggested that the spring bloom period do not significantly imprint the temperatures recorded in the sediments. The sedimentary temperature estimates would rather reflect annually integrated SST, with a major influence of the autumnal post-bloom development of the coccolithophores in the euphotic zone.

Analyses of hydrocarbon gases and sulphate in sediments from the King George Basin, Antarctica

Thermogenic hydrocarbons, formed by the thermal alteration of organic matter, are encountered in several piston core stations in the King George Basin, Anatarctica. These hemipelagic sediments are being deposited in an area of active hydrothermalism, associated with the back-arc spreading in the Bransfield Strait. The lateral extent of sediments infiltrated by the hydrothermally influenced interstitial fluids is characterized by basalt diapiric intrusions and is delineated by an acoustically turbid zone in the sediments of the eastern part of the basin. Iron-sulphide-bearing veins and fractures cut across the sediment in several cores; they appear to be conduits for flow of hydrothermally altered fluids. These zones have the highest C2+ and ethene contents. The thermogenic hydrocarbons have molecular C1/(C2 + C3) ratios typically < 50 and delta13CH4 values between -38? and -48?, indicating an organic source which has undergone strong thermal stress. Several sediment cores also have mixed gas signatures, which indicate the presence of substantial amounts of bacterial gas, predominantly methane. Hydrocarbon generation in the King George Basin is thought to be a local phenomenon, resulting from submarine volcanism with temperatures in the range 70-150°C. There are no apparent seepages of hydrocarbons into the water column, and it is not believed that significant accumulation of thermogenic hydrocarbons reside in the basin.

Organic carbon and nitrogen, sediment composition, and clay mineralogy of Deep Sea Drilling Project Site 603, western Atlantic Ocean

Sediment and interstitial water samples recovered during DSDP Leg 93 at Site 603 (lower continental rise off Cape Hatteras) were analyzed for a series of geochemical facies indicators to elucidate the nature and origin of the sedimentary material. Special emphasis was given to middle Cretaceous organic-matter-rich turbidite sequences of Aptian to Turanian age. Organic carbon content ranges from nil in pelagic claystone samples to 4.2% (total rock) in middle Cretaceous carbonaceous mudstones of turbiditic origin. The organic matter is of marine algal origin with significant contributions of terrigenous matter via turbidites. Maturation indices (vitrinite reflectance) reveal that the terrestrial humic material is reworked. Maturity of autochthonous material (i.e., primary vitrinite) falls in the range of 0.3 to 0.6% Carbohydrate, hydrocarbon, and microscopic investigations reveal moderate to high microbial degradation. Unlike deep-basin black shales of the South and North Atlantic, organic-carbon-rich members of the Hatteras Formation lack trace metal enrichment. Dissolved organic carbon (DOC) in interstitial water samples ranges from 34.4 ppm in a sandstone sample to 126.2 ppm in an organic-matter-rich carbonaceous claystone sample. One to two percent of DOC is carbohydratecarbon.

Chlorine concentrations and stable isotope ratios in Izu Bonin tephra

d37Cl values were determined for Izu Bonin arc magmas erupted 0-44 Ma in order to better understand the time-dependent processing of volatiles in subduction zones. Pristine ash-sized particles (glass, pumice, scoria, and rock fragments) were handpicked from tephra drilled at ODP Site 782. d37Cl values for these particles span a large range from -2.1 to +1.7 per mil (error = ± 0.3 per mil) vs. SMOC (Standard Mean Ocean Chloride, defined as 0 per mil). The temporal data extend the previously reported range of d37Cl values of -2.6 to 0.4 per mil (bulk ash) and -5.4 to -0.1 per mil (volcanic gases) from the Quaternary Izu Bonin-Mariana volcanic front to more positive values. Overall, the temporal data indicate a time-progressive evolution, from isotopically negative Eocene and Oligocene magmas (-0.7 ± 1.1 per mil, n = 10) to Neogene magmas that have higher ?37Cl values on average (+0.3 ± 1.1 per mil; n = 13). The increase is due to the emergence of positive d37Cl values in the Neogene, while minimum d37Cl values are similar through time. The range in d37Cl values cannot be attributed to fractionation during melt formation and differentiation, and must reflect the diversity of Cl present in the arc magma sources. Cl clearly derives from the slab (> 96% Cl in arc magmas), but d37Cl values do not correlate with isotope tracers (e.g. 207Pb/204Pb and 87Sr/86Sr) that are indicative of the flux from subducting sedimentary and igneous crust. Given the steady, high Cl flux since at least 42 Ma, the temporal variability of d37Cl values is best explained by a flux from subducting isotopically positive and negative serpentinite formed in the ocean basins that mingles with and possibly overprints the isotopically negative flux from sediment and igneous crust at arc front depths. The change in the d37Cl values before and after backarc spreading may reflect either a tectonically induced change in the mechanism of serpentinite formation on the oceanic plate, or possibly the integration of isotopically positive wedge serpentinite as arc fluid source during the Neogene. Our study suggests that serpentinites are important fluid sources at arc front depth, and implies the return of isotopically positive and negative Cl from the Earth surface to the mantle.

G. bulloides dissolution index of surface sediments

The Atlantic is regarded as a huge carbonate depocenter due to an on average deep calcite lysocline. However, calculations and models that attribute the calcite lysocline to the critical undersaturation depth (hydrographic or chemical lysocline) and not to the depth at which significant calcium carbonate dissolution is observed (sedimentary calcite lysocline) strongly overestimate the preservation potential of calcareous deep-sea sediments. Significant calcium carbonate dissolution is expected to begin firstly below 5000 m in the deep Guinea and Angola Basin and below 4400 m in the Cape Basin. Our study that is based on different calcium carbonate dissolution stages of the planktic foraminifera Globigerina bulloides clearly shows that it starts between 400 and 1600 m shallower depending on the different hydrographic settings of the South Atlantic Ocean. In particular, coastal areas are severely affected by increased supply of organic matter and the resultant production of metabolic CO2 which seems to create microenvironments favorable for dissolution of calcite well above the hydrographic lysocline.

(Table S1) Trace element and isotopic compositions of anhydrites sampled in the Manus Basin, Papua New Guinea

Microchemical analyses of rare earth element (REE) concentrations and Sr and S isotope ratios of anhydrite are used to identify sub-seafloor processes governing the formation of hydrothermal fluids in the convergent margin Manus Basin, Papua New Guinea. Samples comprise drill-core vein anhydrite and seafloor massive anhydrite from the PACMANUS (Roman Ruins, Snowcap and Fenway) and SuSu Knolls (North Su) active hydrothermal fields. Chondrite-normalized REE patterns in anhydrite show remarkable heterogeneity on the scale of individual grains, different from the near uniform REEN patterns measured in anhydrite from mid-ocean ridge deposits. The REEN patterns in anhydrite are correlated with REE distributions measured in hydrothermal fluids venting at the seafloor at these vent fields and are interpreted to record episodes of hydrothermal fluid formation affected by magmatic volatile degassing. 87Sr/86Sr ratios vary dramatically within individual grains between that of contemporary seawater and that of endmember hydrothermal fluid. Anhydrite was precipitated from a highly variable mixture of the two. The intra-grain heterogeneity implies that anhydrite preserves periods of contrasting hydrothermal versus seawater dominant near-seafloor fluid circulation. Most sulfate d34S values of anhydrite cluster around that of contemporary seawater, consistent with anhydrite precipitating from hydrothermal fluid mixed with locally entrained seawater. Sulfate d34S isotope ratios in some anhydrites are, however, lighter than that of seawater, which are interpreted as recording a source of sulfate derived from magmatic SO2 degassed from underlying felsic magmas in the Manus Basin. The range of elemental and isotopic signatures observed in anhydrite records a range of sub-seafloor processes including high-temperature hydrothermal fluid circulation, varying extents of magmatic volatile degassing, seawater entrainment and fluid mixing. The chemical and isotopic heterogeneity recorded in anhydrite at the inter- and intra-grain scale captures the dynamics of hydrothermal fluid formation and sub-seafloor circulation that is highly variable both spatially and temporally on timescales over which hydrothermal deposits are formed. Microchemical analysis of hydrothermal minerals can provide information about the temporal history of submarine hydrothermal systems that are variable over time and cannot necessarily be inferred only from the study of vent fluids.

(Table 1) Phosphorus and carbon chemistry of ODP Holes 169-1033B and 169-1034B

Uncertainty currently exists about the removal of carbon (C) and phosphorus (P) from the oceanic reservoir, especially in low oxygen settings. In this paper, the cycling of C and P is examined in sediments from the anoxic Saanich Inlet, cored by Ocean Drilling Program (ODP) Leg 169S in 1996 at two sites. Although Corg/Porg ratios are high and increase with depth in the Saanich Inlet, this effect is due largely to a remobilization of P from an organic matter sink to an authigenic sink. Reducible sedimentary components act as temporary shuttles in this process even in this anoxic setting, with the ultimate burial sink for the remobilized P being carbonate fluorapatite. The effective Corg/Preactive molar ratio appears to be about 150-200, indicating some preferential loss of P compared to C during organic matter degradation, but not approaching previously reported values of over 3000 in black shales. Reactive P accumulation rates in this basin range from 10,000-60,000 µmol/cm**2/kyr, greatly exceeding the range of 500-8000 µmol/cm**2/kyr found in most continental-margin settings, including regions of modern phosphogenesis. The initiation of marine sedimentation in the Saanich Inlet occurred after deglaciation, and the high rates of P burial seen here may provide an end-member example of the effects of sea level and margin sedimentation on the distribution of P within the marine P cycle.

Concentrations of organic carbon and organic matter isotopic compositions of sapropels and adjacent marls from ODP Hole 161-974B in the Tyrrhenian Basin (Table 1)

Multiple layers of sapropels occur widely in the sedimentary record of the Mediterranean Sea and record repetitions of paleoclimatic conditions that favored increased production and preservation of marine organic matter. A combination of hydrogen and carbon isotope analyses of Pleistocene sapropels from the Tyrrhenian Sea reveals new aspects of the factors leading to their deposition. Organic matter dD values that are significantly more negative in sapropels than in adjacent marls indicate a combination of dilution of surface waters by meteoric waters and increased burial of lipid-rich organic matter during periods of sapropel deposition. Organic d13C values in sapropels that are less negative than those in marls suggest periods of markedly elevated marine biological production. The opposite but concordant excursions of these two isotopic parameters imply that the sapropel layers formed from increased export of marine organic matter from the photic zone to the sea floor during periods of greater fluvial delivery of continental nutrients to the Mediterranean Sea. Furthermore, the isotopic evidence indicates that periods of wetter climate were widespread in southern Europe at the same times as in northern Africa.