Accumulation rates of ODP Site 177-1090

Dust has the potential to modify global climate by influencing the radiative balance of the atmosphere and by supplying iron and other essential limiting micronutrients to the ocean (Martin et al., 1990, doi:10.1038/345156a0; Martin, 1990, doi:10.1029/PA005i001p00001). Indeed, dust supply to the Southern Ocean increases during ice ages, and 'iron fertilization' of the subantarctic zone may have contributed up to 40 parts per million by volume (p.p.m.v.) of the decrease (80-100 p.p.m.v.) in atmospheric carbon dioxide observed during late Pleistocene glacial cycles (Watson et al., 2000, doi:10.1038/35037561; Kohfeld et al., 2005, doi:10.1126/science.1105375; Martínez-Garcia et al., 2009, doi:10.1029/2008PA001657; Sigman et al., 2010, doi:10.1038/nature09149; Hain et al., 2010, doi:10.1029/2010gb003790). So far, however, the magnitude of Southern Ocean dust deposition in earlier times and its role in the development and evolution of Pleistocene glacial cycles have remained unclear. Here we report a high-resolution record of dust and iron supply to the Southern Ocean over the past four million years, derived from the analysis of marine sediments from ODP Site 1090, located in the Atlantic sector of the subantarctic zone. The close correspondence of our dust and iron deposition records with Antarctic ice core reconstructions of dust flux covering the past 800,000 years (Lambert et al., 2008, doi:10.1038/nature06763; Wolf et al., 2006, doi:10.1038/nature04614) indicates that both of these archives record large-scale deposition changes that should apply to most of the Southern Ocean, validating previous interpretations of the ice core data. The extension of the record beyond the interval covered by the Antarctic ice cores reveals that, in contrast to the relatively gradual intensification of glacial cycles over the past three million years, Southern Ocean dust and iron flux rose sharply at the Mid-Pleistocene climatic transition around 1.25 million years ago. This finding complements previous observations over late Pleistocene glacial cycles (Martínez-Garcia et al., 2009; Lambert et al., 2008; Wolff et al., 2006), providing new evidence of a tight connection between high dust input to the Southern Ocean and the emergence of the deep glaciations that characterize the past one million years of Earth history.

Organic geochemistry of sediment cores from the Arbian Sea

Two deep-sea sediment cores from the northeastern and the southeastern Arabian Sea were studied in order to reconstruct the palaeoenvironments of the past glacial cycles. Core 136KL was recovered from the high-productivity area off Pakistan within the modern oxygen-minimum zone (OMZ). By contrast, modern primary productivity at the site of MD900963 close to Maldives is moderate and bottom waters are today well oxygenated. For both cores, we reconstructed the changes in palaeoproductivity using a set of biomarkers (alkenones, dinosterol and brassicasterol); the main result is that primary productivity is enhanced during glacial stages and lowered during interstadials. The proxies associated with productivity show a 23 kyr cyclicity corresponding to the precession-related insolation cycle. Palaeoredox conditions were studied in both cores using a new organic geochemical parameter (C35/C31-n-alkane ratio) developed by analysing surface sediments from a transect across the OMZ off Pakistan. The value of this ratio in core 136KL shows many variations during the last 65 kyr, indicating that the OMZ was not stable during this time: it disappeared completely during Heinrich- and the Younger Dryas events, pointing to a connection between global oceanic circulation and the stability of the OMZ. The C35/C31 ratio determined in sediments of core MD900963 shows that bottom waters remained rather well oxygenated over the last 330 kyr, which is confirmed by comparison with authigenic metal concentrations in the same sediments. A zonally averaged, circulation-biogeochemical ocean model was used to explore how the intermediate Indian Ocean responds to a freshwater flux anomaly at the surface of the North Atlantic. As suggested by the geochemical time series, both the abundance of Southern Ocean Water and the oxygen concentration are significantly increased in response to this freshwater perturbation.

Biomarkers, stable carbon isotope record and pollen distribution of the soutwest African continental margin

This is part 2 of a study examining southwest African continental margin sediments from nine sites on a north-south transect from the Congo Fan (4°S) to the Cape Basin (30°S) representing two glacial (MIS 2 and 6a) and two interglacial stages (MIS 1 and 5e). Contents, distribution patterns, and molecular stable carbon isotope signatures of long-chain n-alkanes (C27-C33) and n-alkanols (C22-C32) as indicators of land plant vegetation of different biosynthetic types were correlated with concentrations and distributions of pollen taxa in sediments of the same time horizons. Selected single pollen type data reveal details of vegetation changes, but the overall picture is best illustrated by summing pollen known to predominantly derive from C4 plants or C4 plus CAM plants. The C4 plant signals in the biomarkers are recorded in the delta13C data and in the abundances of C31 and C33 n-alkanes, and the C32 n-alkanol. Calculated clusters of wind trajectories for austral summer and winter situations for the Holocene and the Last Glacial Maximum afford information on the source areas for the lipids and pollen and their transport pathways to the ocean. This multidisciplinary approach provides clear evidence of latitudinal differences in leaf wax lipid and pollen composition, with the Holocene sedimentary data paralleling the current major phytogeographic zonations. The northern sites (Congo Fan area and northern Angola Basin) get most of their terrestrial material from the Congo Basin and the Angolan highlands dominated by C3 plants. Airborne particulates derived from the western and central South African hinterland dominated by deserts, semideserts, and savannah regions are rich in organic matter from C4 plants. As can be expected from the present and glacial positions of the phytogeographic zones, the carbon isotopic signatures of n-alkanes and n-alkanols both become isotopically more enriched in 13C from north to south. In the northern part of the transect the relative importance of C4 plant indicators is higher during the glacials than in the interglacials, indicating a northward extension of arid zones favoring grass vegetation. In the south, where grass-rich vegetation merges into semidesert and desert, the difference in C4 plant indicators is small.

Western Arabian Sea SST estimation

Millennial-scale records of planktonic foraminiferal Mg/Ca, bulk sediment UK37', and planktonic foraminiferal d18O are presented across the last two deglaciations in sediment core NIOP929 from the Arabian Sea. Mg/Ca-derived temperature variability during the penultimate and last deglacial periods falls within the range of modern day Arabian Sea temperatures, which are influenced by monsoon-driven upwelling. The UK37'-derived temperatures in MIS 5e are similar to modern intermonsoon values and are on average 3.5°C higher than the Mg/Ca temperatures in the same period. MIS 5e UK37' and Mg/Ca temperatures are 1.5°C warmer than during the Holocene, while the UK37'-Mg/Ca temperature difference was about twice as large during MIS 5e. This is surprising as, nowadays, both proxy carriers have a very similar seasonal and depth distribution. Partial explanations for the MIS 5e UK37'-Mg/Ca temperature offset include carbonate dissolution, the change in dominant alkenone-producing species, and possibly lateral advection of alkenone-bearing material and a change in seasonal or depth distribution of proxy carriers. Our findings suggest that (1) Mg/Ca of G. ruber documents seawater temperature in the same way during both studied deglaciations as in the present, with respect to, e.g., season and depth, and (2) UK37'-based temperatures from MIS 5 (or older) represent neither upwelling SST nor annual average SST (as it does in the present and the Holocene) but a higher temperature, despite alkenone production mainly occurring in the upwelling season. Further we report that at the onset of the deglacial warming, the Mg/Ca record leads the UK37' record by 4 ka, of which a maximum of 2 ka may be explained by postdepositional processes. Deglacial warming in both temperature records leads the deglacial decrease in the d18O profile, and Mg/Ca-based temperature returns to lower values before d18O has reached minimum interglacial values. This indicates a substantial lead in Arabian Sea warming relative to global ice melting.

Elemental and isotope compositions of lipids, kerogens and asphaltenes from samples of DSDP Hole 41-368

The thermal effects of three (one major and two minor) Miocene diabase intrusions on Cretaceous black shales from DSDP site 41-368 have been analyzed. A concentration gradient was observed, especially for the hydrocarbons, decreasing towards the major intrusion and between the three sills. The thermally-altered samples in the proximity of and between the sills contained elemental sulfur and an excess of thermally-derived pristane over phytane. whereas, the unaltered sediments contained no elemental sulfur, and more phytane than pristane. A maximum yield of the extractable hydrocarbons was observed at a depth of 7 m below the major sill. Two classes of molecular markers were present in this bitumen suite. The first was sesqui-, di- and triterpenoids and steranes. which could be correlated with both terrigenous and autochthonous sources. They were geologically mature and showed no significant changes due to the thermal stress. The second class was found in the altered samples, which contained only polynuclear aromatic hydrocarbons with low alkyl substitution and sulfur and oxygen heterocyclic aromatic compounds. These compounds were derived from pyrolytic reactions during the thermal event. Kerogen was isolated from all of these samples, but only traces of humic substances were present. The H/C, N/C, d13C, d34S and dD all exhibit the expected effects of thermal stress. The kerogen becomes more aromatized and richer in 13C, 34S and D in the proximity of and between the sills. Maturation trends were also measured by the vitrinite reflectance and electron spin resonance, where the thermal stress could be correlated with an elevated country rock temperature and an increased degree of aromaticity. The effects of in situ thermal stress on the organic-rich shales resulted in the generation and expulsion of petroliferous material from the vicinity of the sills.

Contents of organic compounds in sediments from DSDP Legs 1 and 4

Fifteen sediment samples were studied from five drill sites recovered by the Glomar Challenger on Legs I and IV in the Gulf of Mexico and western Atlantic. This study concentrated on compounds derived from biogenic precursors, namely: (1) hydrocarbons, (2) fatty acids, (3) pigments and (4) amino acids. Carbon isotope (dC13) data [values <(-26)?, relative to PDB], long-chain n-alkyl hydrocarbons (>>C27) with odd carbon numbered molecules dominating even carbon numbered species, and presence of perylene proved useful as possible indicators for terrigenous contributions to the organic matter in some samples. Apparently land-derived organic matter can be transported for distances over 1000 km into the ocean and their source still recognized. The study was primarily designed to investigate: (i) the sources of the organic matter present in the sediment, (ii) their stability with time of accumulation and (iii) the conditions necessary for in situ formation of new compounds.

Lipids and polycyclic aromatic hydrocarbons in bottom sediments from the Atlantic sector of the Southern Ocean

Distribution and composition of lipids and contents of alkanes and polycyclic aromatic hydrocarbons(PAHs) in bottom sediments of the Scotia and Weddell seas are discussed. Comparatively low concentrations of organic carbon (average 0.35%) and lipids (average 0.024%) result from rapid decomposition of organic matter in upper layers of the water column. Composition of alkanes indicates that lipids are of autochthonous origin, and stable concentrations of PAHs (average 25.8 ppb, sigma 15.3 ppb) indicate that they represent the background level for bottom sediments. Higher concentrations of PAHs in sediments near the King George Island (252.1 ppb) and different distributions of individual polyarenes are produced there by the heating systems of the Polish Antarctic Station.

Organic geochemistry of sediments at DSDP Leg 63 Holes

Selected core samples from the California Continental Borderland (Sites 467-469) were analyzed to evaluate the nature and composition of the lipids and kerogens in terms of their genetic origin and geological maturity. The lipids were of a multiple origin. On the basis of the homolog distributions of the n-alkanes and n-fatty acids, with the shape and magnitude of the unresolved branched and cyclic hydrocarbons, and the structural and stereochemical compositions of the molecular markers, these lipids were derived from primary autochthonous marine (microbial), from allochthonous terrigenous (higher plant wax), and from recycled (geologically mature organic matter) sources. The kerogens were composed of principally marine microbial detritus with a minor input of allochthonous terrestrial material. For the most part, the samples had undergone a thermal maturation according to a normal geothermal gradient, except in the proximity of intrusives. Such additional thermal stress was evident for the samples from Site 469 and to some extent for Site 467 at about a sub-bottom depth of 700 to 800 meters.

Isotopic composition of terrestrial plant waxes (dD and d13C of n-alkanes) of sediment core SO188_342 from the Northern Bay of Bengal for the last 18 ka

The Indian Summer Monsoon (ISM) is a major global climatic phenomenon. Long-term precipitation proxy records of the ISM, however, are often fragmented and discontinuous, impeding an estimation of the magnitude of precipitation variability from the Last Glacial to the present. To improve our understanding of past ISM variability, we provide a continuous reconstructed record of precipitation and continental vegetation changes from the lower Ganges-Brahmaputra-Meghna catchment and the Indo-Burman ranges over the last 18,000 years (18 ka). The records derive from a marine sediment core from the northern Bay of Bengal (NBoB), and are complemented by numerical model results of spatial moisture transport and precipitation distribution over the Bengal region. The isotopic composition of terrestrial plant waxes (dD and d13C of n-alkanes) are compared to results from an isotope-enabled general atmospheric circulation model (IsoCAM) for selected time slices (pre-industrial, mid-Holocene and Heinrich Stadial 1). Comparison of proxy and model results indicate that past changes in the dD of precipitation and plant waxes were mainly driven by the amount effect, and strongly influenced by ISM rainfall. Maximum precipitation is detected for the Early Holocene Climatic Optimum (EHCO; 10.5-6 ka BP), whereas minimum precipitation occurred during the Heinrich Stadial 1 (HS1; 16.9-15.4 ka BP). The IsoCAM model results support the hypothesis of a constant moisture source (i.e. the NBoB) throughout the study period. Relative to the pre-industrial period the model reconstructions show 20% more rain during the mid-Holocene (6 ka BP) and 20% less rain during the Heinrich Stadial 1 (HS1), respectively. A shift from C4-plant dominated ecosystems during the glacial to subsequent C3/C4-mixed ones during the interglacial took place. Vegetation changes were predominantly driven by precipitation variability, as evidenced by the significant correlation between the dD and d13C alkane records. When compared to other records across the ISM domain, precipitation and vegetation changes inferred from our records and the numerical model results provide evidence for a coherent regional variability of the ISM from the Last Glacial to the present.

Plant-wax, alkenone and major element analyses of ODP Site 659 for the Last Glacial cycle and associated coretop data

We present a hydrologic reconstruction of the Sahara-Sahel transition, covering the complete last glacial cycle (130 ka), based on a combination of plant-wax-specific hydrogen (dD) and carbon isotopes (d13C). The dD and d13C signatures of long-chain n-alkanes from ODP Site 659 off NW Africa reveal a significant anti-correlation. Complementary to published pollen data, we infer that this plant-wax signal reflects sensitive responses of the vegetation cover to precipitation changes in the Sahel region, as well as varying contributions from biomes north of the Sahara (C3 domain) by North-East Trade Winds (NETW). During arid phases, especially the northern parts of the Sahel likely experienced crucial water stress, which resulted in a pronounced contraction of the vegetation cover, thus reducing the amount of C4 plant waxes from the region. The increase in NETW strength during dry periods further promoted a more pronounced C3-plant-wax signal derived from the North African C3 plant domain. During humid periods, the C4-dominated Sahelian environments spread northward into the Saharan realm, in association with lower NETW inputs of C3 plant waxes. Arid-humid cycles deduced from plant-wax dD are in accordance with concomitant changes in weathering intensity reflected in varying major element distributions. Environmental shifts are generally linked to periods with large fluctuations in Northern Hemisphere summer insolation. During Marine Isotope Stages 2 and 3, when insolation variability was low, coupling of the hydrologic regime to alkenone-based estimates of NE Atlantic sea-surface temperatures becomes apparent.

Hydrocarbons in surface layer bottom sediments from the North Dvina Riverand the southern part of the Dvina Bay, White Sea

Analysis of molecular composition of alkanes in bottom sediments of the southern part of Dvina Bay (White Sea) in October 2001 revealed the following main peculiarities of hydrocarbon behavior in the estuary: dominating of high molecular C23-C45 compounds and irregular distribution of hydrocarbons in bottom sediments as a result of high sedimentation rate and active hydrodynamics in the studied area.

Hydrogen isotope data of aquatic and terrestrial lipid biomarkers from Lake Meerfelder Maar during the Younger Dryas

Here we use compound-specific hydrogen isotope data of aquatic and terrestrial lipid biomarkers from precisely dated annually laminated sediments from Lake Meerfelder Maar (MFM) in Western Germany to reconstruct decadal resolved hydroclimatic changes during the Younger Dryas. We show that cooling at MFM begun synchronous to the onset of cooling in Greenland at 12.850 years BP. Major environmental changes at MFM however took place 170 years later as a result of substantially drier conditions.

Temporal evolution of organic carbon and lipid content and derived SST of sediment core GIK23258-2, Norwegian Sea

Lipids are used for the evaluation of the different organic matter contributions in the north eastern Norwegian sea (M23258 site; 75ºN, 14ºE) over the last 15,000 years. Development of a mass balance model based on the down core quantification of the C37 alkenones, the odd carbon numbered n-alkanes (Aodd) and the unresolved complex mixture of hydrocarbons (UCM) has allowed three main organic matter inputs involving marine, continental and ancient reworked organic matter to be recognized. The model shows a good agreement between measured and reconstructed TOC values. Similarly, a strong parallelism is observed between predicted components such as marine TOC and carbonate content (CaCO3), which was determined independently. Representation of the model results within a time-scale based on 15 AMS-14C measurements shows that the main changes in organic matter constituents are coincident with the major climatic events of the last 15,000 a. Thus, the predominance of reworked organic matter is characteristic of Termination Ia (up to 70%), continental organic matter was dominant during the Bølling-Allerød (B-A) and Younger Dryas (YD) periods (about 85%) and a strong increase of marine organic matter occurred in the Holocene (between 50 and 75%). This agreement reflects the main hydrographic changes that determined the deposition of sedimentary materials during the period studied: ice-rafted detritus from the Barents continental platform, ice-melting waters from the Arctic fluvial system discharging into the Barents sea and dominance of north Atlantic currents, respectively. In this respect, the high-resolution down core record resulting from the mass balance and lipid measurements allows the identification of millennial-scale events such as the increase of reworked organic matter at the final retreat of the Barents ice sheet at the end of the deglaciation period (Termination Ib).