Organic geochemistry from different DSDP Holes in the subtropical South Atlantic Ocean

Organic matter has been characterized in samples of Pleistocene, Pliocene, and Miocene sediments from seven Deep Sea Drilling Project sites in the subtropical South Atlantic Ocean. Organic carbon concentrations average 0.3% for most samples, and n-alkanoic acid, n-alkanol, and alkane biomarkers indicate extensive microbial reworking of organic matter in these organic-carbon-lean sediments. Samples from the easternmost parts of the South Atlantic contain an average of 4.1% organic carbon and reflect the high productivity associated with the Benguela Current. Lipid biomarkers show less microbial reworking in these sediments. Eolian transport of land-derived hydrocarbons is evident at most of these oceanic locations.

(Table 1) Sample descriptions and results: Carbon, lipid, and kerogen analyses, at DSDP Leg 64 Holes

Pleistocene sediments in the Guaymas Basin, Gulf of California, have been intruded by sills and their organic matter thus subjected to thermal stress. Sediment samples from DSDP/IPOD Sites 477, 478, and 481, and samples of thermally unaltered materials from Sites 474 and 479 were analyzed to characterize the lipids and kerogens and to evaluate the effects of the intrusive thermal stresses. The lipids of the thermally unaltered samples are derived from microbial and terrestrial higher-plant detritus. The samples from the sill proximities contain the distillates, and those adjacent to the sills contain essentially no lipids. The pyrograms of the kerogens from the unaltered samples reflect their predominantly autochthonous microbial origin. When compared with the unaltered samples, the pyrograms of the altered kerogen samples reflect the thermal effects by a reduction in the complexity of the products. Kerogens adjacent to the sills produced little or no pyrolysis products. The effects of intrusions into unconsolidated, wet sediments resulted in in situ pyrolysis of the organic matter, as confirmed by these data.

Geochemistry of carbon at DSDP Legs 58 and 59 Holes

I obtained 68 quarter sections of cores from the JOIDES Organic Geochemistry Panel for studying type, distribution, and stages of organic diagenesis of sedimentary organic matter in the West Philippine and Parece Vela basins and Mariana Trough area (Figure 1). The present chapter compares (1) 11 geochemical parameters used to determine organic source and its stage of genesis within the 9 site locations in this study area and (2) compares these 11 with the same parameters reported from Leg 56, outer trench slope of the Japan Trench, and Leg 60, Mariana Trough and Trench (Schorno, in press a, b). Even though these sediments are considered pelagic, the organic content in most of the core sections appears to be hemipelagic. The sedimentary organic matter in these cores is believed to be in an early stage of diagenesis. Both conclusions are based primarily on the fl-alkane distribution within the organic matter. This particular parameter, I note later, has a major weakness. As Hunt (Hunt, 1979) and I (in press b) observed, marine organisms synthesize /z-alkanes with distributions containing neither odd nor even preferences. Thus those sediments that did contain w-alkane distributions with OEP near 1, suggesting a late stage of catagenesis, may in actuality be immature marine sediments.

(Table 1) Lipid yields for samples across the Cretaceous/Tertiary boundary in DSDP Hole 86-577

Core samples of calcareous sediments taken from above and below the proposed Cretaceous/Tertiary boundary (Sample 577-12-5, 130 cm) were examined for geochemical evidence of the mass extinctions and faunal successions that marked this period. The lipid compositions of the six core samples examined were virtually identical and were characterized by a large component of unresolved naphthenic hydrocarbons and a homologous series of an/mo-alkanes, both presumably of bacterial origin. The results of this preliminary study suggest that the lipids of sediments deposited over a several million year period encompassing the Cretaceous-Tertiary extinctions have been almost completely recycled by bacterial metabolism, which occurred under oxic depositional and/or diagenetic conditions and which left a unique bacterial signature with only minor traces of the original sedimentary lipids.

Organic geochemistry of sediments from sapropel 94 of ODP Hole 161-974C

Analysis of the molecular composition of the organic matter (OM) from whole sediment samples can avoid analytical bias that might result from isolation of components from the sediment matrix, but has its own analytical challenges. We evaluated the use of GC * GC-ToFMS to analyze the pyrolysis products of six whole sediment samples obtained from above, within and below a 1 million year old OM-rich Mediterranean sapropel layer. We found differences in pyrolysis products

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.

Alkenone accumulation rates, stable carbon isotope record, and sea surface temperature reconstruction for IODP Site 306-U1313

Here we present orbitally-resolved records of terrestrial higher plant leaf wax input to the North Atlantic over the last 3.5 Ma, based on the accumulation of long-chain n-alkanes and n-alkanl-1-ols at IODP Site U1313. These lipids are a major component of dust, even in remote ocean areas, and have a predominantly aeolian origin in distal marine sediments. Our results demonstrate that around 2.7 million years ago (Ma), coinciding with the intensification of the Northern Hemisphere glaciation (NHG), the aeolian input of terrestrial material to the North Atlantic increased drastically. Since then, during every glacial the aeolian input of higher plant material was up to 30 times higher than during interglacials. The close correspondence between aeolian input to the North Atlantic and other dust records indicates a globally uniform response of dust sources to Quaternary climate variability, although the amplitude of variation differs among areas. We argue that the increased aeolian input at Site U1313 during glacials is predominantly related to the episodic appearance of continental ice sheets in North America and the associated strengthening of glaciogenic dust sources. Evolutional spectral analyses of the n-alkane records were therefore used to determine the dominant astronomical forcing in North American ice sheet advances. These results demonstrate that during the early Pleistocene North American ice sheet dynamics responded predominantly to variations in obliquity (41 ka), which argues against previous suggestions of precession-related variations in Northern Hemisphere ice sheets during the early Pleistocene.

14C specific radiocarbon ages and bulk ages accompanied by geochemical proxys from surface sediment samples in the Black Sea

Transfer of organic carbon (OC) from the terrestrial to the oceanic carbon pool is largely driven by riverine and aeolian transport. Before transport, however, terrigenous organic matter can be retained in intermediate terrestrial reservoirs such as soils. Using compound-specific radiocarbon analysis of terrigenous biomarkers their average terrestrial residence time can be evaluated. Here we show compound-specific radiocarbon (14C) ages of terrigenous biomarkers and bulk 14C ages accompanied by geochemical proxy data from core top samples collected along transects in front of several river mouths in the Black Sea. 14C ages of long chain n-alkanes, long chain n-fatty acids and total organic carbon (TOC) are highest in front of the river mouths, correlating well with BIT (branched and isoprenoid tetraether) indices, which indicates contribution of pre-aged, soil-derived terrigenous organic matter. The radiocarbon ages decrease further offshore towards locations where organic matter is dominated by marine production and aeolian input potentially contributes terrigenous organic matter. Average terrestrial residence times of vascular plant biomarkers deduced from n-C29+31 alkanes and n-C28+30 fatty acids ages from stations directly in front of the river mouths range from 900 ± 70 years to 4400 ± 170 years. These average residence times correlate with size and topography in climatically similar catchments, whereas the climatic regime appears to control continental carbon turnover times in morphologically similar drainage areas of the Black Sea catchment. Along-transect data imply petrogenic contribution of n-C29+31 alkanes and input via different terrigenous biomarker transport modes, i.e., riverine and aeolian, resulting in aged biomarkers at offshore core locations. Because n-C29+31 alkanes show contributions from petrogenic sources, n-C28+30 fatty acids likely provide better estimates of average terrestrial residence times of vascular plant biomarkers. Moreover, sedimentary n-C28 and n-C30 fatty acids appear clearly much less influenced by autochthonous sources than n-C24 and n-C26 fatty acids as indicated by increasing radiocarbon ages with increasing chain-length and are, thus, more representative as vascular plant biomarkers.

(Table 1) Lipid and kerogen content at DSDP Leg 64 Holes

Diatomaceous mud and an organically-rich claystone from holes at Sites 474 and 476 at the mouth of the Gulf of California were analyzed by organic geochemical methods to characterize their organic matter. The lipids of all three samples are primarily marine autochthonous, with the exception of Sample 474-5-3, 105-107 cm, which also contains some vascular plant wax. Based on the lipid composition, the sediment was deposited mainly under oxic environmental conditions. The kerogens were aliphatic and autochthonous marine. Two lignite fragments were also analyzed, and the data indicate that they are driftwood that absorbed marine bitumen from the surrounding sediment during coalification.

Stable oxygen and carbon isotopes ratios of sediment core GeoB9528-3

The carbon isotopic composition of individual plant leaf waxes (a proxy for C3 vs. C4 vegetation) in a marine sediment core collected from beneath the plume of Sahara-derived dust in northwest Africa reveals three periods during the past 192,000 years when the central Sahara/Sahel contained C3 plants (likely trees), indicating substantially wetter conditions than at present. Our data suggest that variability in the strength of Atlantic meridional overturning circulation (AMOC) is a main control on vegetation distribution in central North Africa, and we note expansions of C3 vegetation during the African Humid Period (early Holocene) and within Marine Isotope Stage (MIS) 3 (approx. 50-45 ka) and MIS 5 (approx. 120-110 ka). The wet periods within MIS 3 and 5 coincide with major human migration events out of sub-Saharan Africa. Our results thus suggest that changes in AMOC influenced North African climate and, at times, contributed to amenable conditions in the central Sahara/Sahel, allowing humans to cross this otherwise inhospitable region.

Decadal-to-centennial scale variations during the Holocene reconstructed from sediment core D13902

Sea surface temperature (SST), marine productivity, and fluvial input have been reconstructed for the last 11.5 calendar (cal) ka B.P. using a high-resolution study of C37 alkenones, coccolithophores, iron content, and higher plant n-alkanes and n-alkan-1-ols in sedimentary sequences from the inner shelf off the Tagus River Estuary in the Portuguese Margin. The SST record is marked by a continuous decrease from 19C, at 10.5 and 7 ka, to 15C at present. This trend is interrupted by a fall from 18C during the Roman and Medieval Warm Periods to 16C in the Little Ice Age. River input was very low in the early Holocene but increased in the last 3 cal ka B.P. in association with an intensification of agriculture and deforestation and possibly the onset of the North Atlantic Oscillation/Atlantic Multidecadal Oscillation modes of variability. River influence must have reinforced the marine cooling trend relative to the lower amplitude in similar latitude sites of the eastern Atlantic. The total concentration of alkenones reflects river-induced productivity, being low in the early Holocene but increasing as river input became more important. Rapid cooling, of 1-2C occurring in 250 years, is observed at 11.1, 10.6, 8.2, 6.9, and 5.4 cal ka B.P. The estimated age of these events matches the ages of equivalent episodes common in the NE Atlantic- Mediterranean region. This synchronicity reveals a common widespread climate feature, which considering the twentieth century analog between colder SSTs and negative North Atlantic Oscillation (NAO), is likely to reflect periods of strong negative NAO.

Hydrogen isotope compositions of terrestrial plant-wax n-alkanes analysed on a transect of marine surface sediment samples from 1°N to 28°S off southwest Africa

A transect of marine surface sediment samples from 1° N to 28° S off southwest Africa was analysed to verify the application of hydrogen isotope compositions of terrestrial plant-wax n-alkanes preserved in ocean sediments as a proxy for continental hydrological conditions. Conditions on the adjacent continent range from humid evergreen forests to deciduous forests, wood- and shrub land and further to arid grasslands and deserts. The hydrogen isotope values for the dominant n-alkane homologues (C29, C31 and C33) vary from -123 per mil to -141 per mil VSMOW and correlate with the modelled hydrogen isotope composition of mean annual and growing season precipitation of postulated continental source areas (r up to 0.8, p < 0.01). The apparent hydrogen isotope fractionation between alkanes and mean annual precipitation is remarkably uniform (-109 per mil on average, Sigma <= 5 per mil, n = 27). Potentially, effects of aridity on the apparent hydrogen isotope fractionation are concealed by the contribution of different plants (C3 dicotyledons vs C4 grasses). Thus, isotope ratios of leaf wax n-alkanes preserved in ocean margin sediments in these and similar tropical regions may be directly converted to dD ratios of ancient precipitation by employing a constant hydrogen isotope fractionation.

Terrigenous input and marine productivity for the Pacific sector of the Southern Ocean based on lipid biomarkers

In this study, we present a new multiproxy data set of terrigenous input, marine productivity and sea surface temperature (SST) from 52 surface sediment samples collected along E-W transects in the Pacific sector of the Southern Ocean. Allochtonous terrigenous input was characterized by the distribution of plant wax n-alkanes and soil-derived branched glycerol dialkyl glycerol tetraethers (brGDGTs). 230Th-normalized burial rates of both compound groups were highest close to the potential sources in Australia and New Zealand and are strongly related to lithogenic contents, indicating common sources and transport. Detection of both long-chain n-alkanes and brGDGTs at the most remote sites in the open ocean strongly suggests a primarily eolian transport mechanism to at least 110°W, i.e. by prevailing westerly winds. Two independent organic SST proxies were used, the UK'37 based on long-chain alkenones, and the TEX86 based on isoprenoid GDGTs. Both, UK'37 and TEX86 indices show robust relationships with temperature over a temperature range between 0.5 and 20°C, likely implying different seasonal and regional imprints on the temperature signal. While alkenone-based temperature estimates reliably reflect modern SST even at the low temperature end, large temperature residuals are observed for the polar ocean using the TEX86 index. 230Th-normalized burial rates of alkenones are highest close to the Subtropical Front and are positively related to lithogenic fluxes throughout the study area. In contrast, highest isoGDGT burial south of the Antarctic Polar Front is not related with dust flux but may be largely controlled by diatom blooms, and thus high opal fluxes during austral summer.

(Table 1) Lipid biomarkers in surface sediments from the Gulf of Genoa

A series of molecular organic markers were determined in surface sediments from the Gulf of Genoa (Ligurian Sea) in order to evaluate their potential for palaeo-environmental reconstructions. Allochthonous input can be characterized by the distributions of n-C29 and n-C31 alkanes, n-C26 and n-C28 alkanols and branched glycerol dialkyl glycerol tetraethers (GDGTs), whose concentrations are generally highest near the river mouths. In the open basin however, terrestrial n-alkanes and n-alkanols may have an additional, aeolian source. Autochthonous input is represented by crenarchaeol and isoprenoid GDGTs. Their concentrations are highest in the open basin showing the preference of Thaumarchaeota for oligotrophic waters. Indications of a significant degradation of sterols and C37 alkenones exclude these lipids as reliable productivity proxies. Using terrestrial and aquatic lipids as end-members allows estimating the percentage of terrestrial organic matter between 20% and 58% in the coastal area decreasing to 1 to 30% in the deep basin. The spatial distribution of sea surface temperature (SST) estimates using the alkenone-based UK'37 index is very similar to the autumnal (November) mean satellite-based SST distribution. Conversely, TEXH86-derived SST estimates are close to winter SSTs in the coastal area and summer SSTs in the open basin. This pattern reflects presumably a shift in the main production of Thaumarchaeota from the coastal area in winter to the open basin in summer. This study represents a major prerequisite for the future application of lipid biomarkers on sediment cores from the Gulf of Genoa.