A multi-proxy investigation of sediment core GeoB7165-1 and AMS 14C dating points from sediment cores off Conceptión (~ 36°S)

A high-resolution sea surface temperature and paleoproductivity reconstruction on a sedimentary record collected at 36°S off central-south Chile (GeoB 7165-1, 36°33'S, 73°40'W, 797 m water depth, core length 750 cm) indicates that paleoceanographic conditions changed abruptly between 18 and 17 ka. Comparative analysis of several cores along the Chilean continental margin (30°-41°S) suggests that the onset and the pattern of deglacial warming was not uniform off central-south Chile due to the progressive southward migration of the Southern Westerlies and local variations in upwelling. Marine productivity augmented rather abruptly at 13-14 ka, well after the oceanographic changes.We suggest that the late deglacial increase in paleoproductivity off central-south Chile reflects the onset of an active upwelling system bringing nutrient-rich, oxygen-poor Equatorial SubsurfaceWater to the euphotic zone, and a relatively higher nutrient load of the Antarctic Circumpolar Current. During the Last Glacial Maximum, when the Southern Westerlies were located further north, productivity off central-south Chile, in contrast to off northern Chile, was reduced due to direct onshore-blowing winds that prevented coastal upwelling and export production.

Organic geochemistry of two sediment cores from the Kara Sea

Within the Russian-German research project on "Siberian River Run-off (SIRRO)" devoted to the freshwater discharge and its influence on biological, geochemical, and geological processes in the Kara Sea, sedimentological and organic-geochemical investigations were carried-out on two well-dated sediment cores from the Yenisei Estuary area. The main goal of this study was to quantify the terrigenous organic carbon accumulation based on biomarker and bulk accumulation rate data, and its relationship to Yenisei river discharge and climate change through Holocene times. The biomarker data at both cores clearly indicate the predominance of terrigenous organic matter, reaching 70 to 100% and 50 to 80% of the total organic carbon within and directly north of the estuary, respectively. During the last about 9 Cal. kyrs. BP represented in the studied sediment section, siliciclastic sediment and (terrigenous) organic carbon input was strongly influenced by postglacial sea-level rise and climate-related changes in river discharge. The mid-Holocene Climatic Optimum is documented by maximum river discharge between 8.2 and 7.3 Cal. kyrs. BP. During the last 2000 years river discharge probably became reduced, and accumulation of both terrigenous and marine organic carbon increased due to increased coagulation of fine-grained material.

Age determination and n-Alkane concentration of Arctic Ocean sediment cores

We have reconstructed the surface water environment of the Arctic Ocean over the last ? 50,000 years using measurements of the organic nitrogen and carbon isotope ratios, carbonate and total organic carbon concentrations (TOC), and terrestrial biomarkers (lignin and long-chain n-alkanes) in four multicores. Variations in nitrogen isotope ratios that are concordant with TOC and carbonate concentrations (representing foraminifera and excluding ice-rafted-debris) reflect differences in relative nutrient utilization of phytoplankton in the surface waters. However, d15N variations also appear to be dependent on the stratification of the water column and therefore potentially track the exchange of nutrients between deep and surface waters. Low Last Glacial Maximum (LGM) d15N values and higher Holocene values are opposite to those recorded in the Southern Ocean. The Arctic Ocean with higher nutrient utilization today compared to the LGM therefore acts as a counterpart to the Southern Ocean, although the global impact on carbon dioxide variations compared to the Southern Ocean is probably low.

Biomarker proxies on sediment cores in the central Arctic Ocean

Although the permanently to seasonally ice-covered Arctic Ocean is a unique and sensitive component in the Earth's climate system, the knowledge of its long-term climate history remains very limited due to the restricted number of pre-Quaternary sedimentary records. During Polarstern Expedition PS87/2014, we discovered multiple submarine landslides over a distance of >350 km along Lomonosov Ridge. Removal of younger sediments from steep headwalls has led to exhumation of Miocene to early Quaternary sediments close to the seafloor, allowing the retrieval of such old sediments with gravity cores. Multi-proxy biomarker analyses of these gravity cores reveal for the first time that the late Miocene central Arctic Ocean was relatively warm (4-7°C) and ice-free during summer, whereas sea ice occurred during spring and autumn/winter. A comparison of our proxy data with Miocene climate simulations seems to favour relatively high late Miocene atmospheric CO2 concentrations. These new findings from the Arctic region provide new benchmarks for groundtruthing global climate reconstructions and modeling.

Physico-chemical parameters of sediment core PG1972-1 (09-Tik-03) from a Tundra Lake, Northeastern Siberia

Thermokarst lakes in the Siberian Arctic contain sediment archives that can be used for paleoenvironmental inference. Until now, however, there has been no study from the inner Lena River Delta with a focus on diatoms. The objective of this study was to investigate how the diatom community in a thermokarst lake responded to past limnogeological changes and what specific factors drove variations in the diatom assemblage. We analysed fossil diatom species, organic content, grain-size distribution and elemental composition in a sediment core retrieved in 2009 from a shallow thermokarst lake in the Arga Complex, western Lena River Delta. The core contains a 3,000-year record of sediment accumulation. Shifts in the predominantly benthic and epiphytic diatom species composition parallel changes in sediment characteristics. Paleoenvironmental and limnogeological development, inferred from multiple biological and sedimentological variables, are discussed in the context of four diatom zones, and indicate a strong relation between changes in the diatom assemblage and thermokarst processes. We conclude that limnogeological and thermokarst processes such as lake drainage, rather than direct climate forcing, were the main factors that altered the aquatic ecosystem by influencing, for example, habitat availability, hydrochemistry, and water level.

Geochemistry and soil characteristics of sediment core GeoB4234

Stable isotopes of sedimentary nitrogen and organic carbon are widely used as proxy variables for biogeochemical parameters and processes in the water column. In order to investigate alterations of the primary isotopic signal by sedimentary diagenetic processes, we determined concentrations and isotopic compositions of inorganic nitrogen (IN), organic nitrogen (ON), total nitrogen (TN), and total organic carbon (TOC) on one short core recovered from sediments of the eastern subtropical Atlantic, between the Canary Islands and the Moroccan coast. Changes with depth in concentration and isotopic composition of the different fractions were related to early diagenetic conditions indicated by pore water concentrations of oxygen, nitrate, and ammonium. Additionally, the nature of the organic matter was investigated by Rock-Eval pyrolysis and microscopic analysis. A decrease in ON during aerobic organic matter degradation is accompanied by an increase of the 15N/14N ratio. Changes in the isotopic composition of ON can be described by Rayleigh fractionation kinetics which are probably related to microbial metabolism. The influence of IN depleted in 15N on the bulk sedimentary (TN) isotope signal increases due to organic matter degradation, compensating partly the isotopic changes in ON. In anoxic sediments, fixation of ammonium between clay lattices results in a decrease of stable nitrogen isotope ratio of IN and TN. Changes in the carbon isotopic composition of TOC have to be explained by Rayleigh fractionation in combination with different remineralization kinetics of organic compounds with different isotopic composition. We have found no evidence for preferential preservation of terrestrial organic carbon. Instead, both TOC and refractory organic carbon are dominated by marine organic matter. Refractory organic carbon is depleted in 13C compared to TOC.

Biogeochemical investigation of the benthic nitrogen cycle in the Arabian Sea off Pakistan

A pronounced deficit of nitrogen (N) in the oxygen minimum zone (OMZ) of the Arabian Sea suggests the occurrence of heavy N-loss that is commonly attributed to pelagic processes. However, the OMZ water is in direct contact with sediments on three sides of the basin. Contribution from benthic N-loss to the total N-loss in the Arabian Sea remains largely unassessed. In October 2007, we sampled the water column and surface sediments along a transect cross-cutting the Arabian Sea OMZ at the Pakistan continental margin, covering a range of station depths from 360 to 1430 m. Benthic denitrification and anammox rates were determined by using 15N-stable isotope pairing experiments. Intact core incubations showed declining rates of total benthic N-loss with water depth from 0.55 to 0.18 mmol N m**-2 day**-1. While denitrification rates measured in slurry incubations decreased from 2.73 to 1.46 mmol N m**-2 day**-1 with water depth, anammox rates increased from 0.21 to 0.89 mmol N m**-2 day**-1. Hence, the contribution from anammox to total benthic N-loss increased from 7% at 360 m to 40% at 1430 m. This trend is further supported by the quantification of cd1-containing nitrite reductase (nirS), the biomarker functional gene encoding for cytochrome cd1-Nir of microorganisms involved in both N-loss processes. Anammox-like nirS genes within the sediments increased in proportion to total nirS gene copies with water depth. Moreover, phylogenetic analyses of NirS revealed different communities of both denitrifying and anammox bacteria between shallow and deep stations. Together, rate measurement and nirS analyses showed that anammox, determined for the first time in the Arabian Sea sediments, is an important benthic N-loss process at the continental margin off Pakistan, especially in the sediments at deeper water depths. Extrapolation from the measured benthic N-loss to all shelf sediments within the basin suggests that benthic N-loss may be responsible for about half of the overall N-loss in the Arabian Sea.

Climate proxies in sediment core MD95-2010

High-amplitude, rapid climate fluctuations are common features of glacial times. The prominent changes in air temperature recorded in the Greenland ice cores (Dansgaard et al., 1993, doi:10.1038/339532a0; Grootes et al., 1993 doi:10.1038/366552a0) are coherent with shifts in the magnitude of the northward heat flux carried by the North Atlantic surface ocean (Bond et al., 1993, doi:10.1038/365143a0; Bond and Lotti, 1995, doi:10.1126/science.267.5200.1005); changes in the ocean's thermohaline circulation are a key component in many explanations of this climate flickering (Broecker, 1997, doi:10.1126/science.278.5343.1582). Here we use stable-isotope and other sedimentological data to reveal specific oceanic reorganizations during these rapid climate-change events. Deep water was generated more or less continuously in the Nordic Seas during the latter part of the last glacial period (60 to 10 thousand years ago), but by two different mechanisms. The deep-water formation occurred by convection in the open ocean during warmer periods (interstadials). But during colder phases (stadials), a freshening of the surface ocean reduced or stopped open-ocean convection, and deep-water formation was instead driven by brine-release during sea-ice freezing. These shifting magnitudes and modes nested within the overall continuity of deep-water formation were probably important for the structuring and rapidity of the prevailing climate changes.

Particle flux studies of sediment traps from the northern and equatorial Indian Ocean

The Asian monsoon system governs seasonality and fundamental environmental characteristics in the study area from which two distinct peculiarities are most notable: upwelling and convective mixing in the Arabian Sea and low surface salinity and stratification in the Bay of Bengal due to high riverine input and monsoonal precipitation. The respective oceanography sets the framework for nutrient availability and productivity. Upwelling ensures high nitrate concentration with temporal/spatial Si limitation; freshwater-induced stratification leads to reduced nitrogen input from the subsurface but Si enrichment in surface waters. Ultimately, both environments support high abundance of diatoms, which play a central role in the export of organic matter. It is speculated that, additional to eddy pumping, nitrogen fixation is a source of N in stratified waters and contributes to the low-d15N signal in sinking particles formed under riverine impact. Organic carbon fluxes are best correlated to opal but not to carbonate, which is explained by low foraminiferal carbonate fluxes within the river-impacted systems. This observation points to the necessity of differentiating between carbonate sources for carbon flux modeling. As evident from a compilation of previously published and new data on labile organic matter composition (amino acids and carbohydrates), organic matter fluxes are mainly driven by direct input from marine production, except the site off Pakistan where sedimentary input of (marine) organic matter is dominant during the NE monsoon. The explanation of apparently different organic carbon export efficiency calls for further investigations of, for example, food web structure and water column processes.

Organic geochemistry of ODP Leg 135 sediment samples

The average total organic carbon (TOC) content obtained after Rock-Eval/TOC analysis of 156 sediment samples from the eight sites cored during Leg 135 is 0.05%. Hence, the TOC content of Leg 135 sediments is extremely low. The organic matter that is present in these samples is probably mostly reworked and oxidized material. Ten sediment samples were selected for extraction and analysis by gas chromatography and gas chromatography-mass spectrometry. Very low amounts of extractable hydrocarbons were obtained and some aspects of the biomarker distributions suggest that these hydrocarbons are not representative of the organic matter indigenous to the samples. A sample of an oil seep from Pili, Tongatapu was also analyzed. The seep is a biodegraded, mature oil that shows many characteristics in common with previously published analyses of oil seeps from Tongatapu. Biomarker evidence indicates that its source is a mature, marine carbonate of probable Late Cretaceous-Early Tertiary age. The source rock responsible for the Tongatapu oil seeps remains unknown.

Temperature proxies of sediment cores from the Sea of Marmara

Reconstructing ocean temperature values is a major target in paleoceanography and climate research. However, most temperature proxies are organism-based and thus suffer from an "ecological bias". Multiproxy approaches can potentially overcome this bias but typically require more investment in time and resources, while being susceptible to errors induced by sample preparation steps necessary before analysis. Three lipid-based temperature proxies are widely used: UK'37 (based on long chain alkenones from phytoplanktonic haptophytes), TEX86 [based on glycerol dialkyl glycerol tetraethers (GDGTs) from pelagic archaea] and LDI (based on long chain diols from phytoplanktonic eustigmatophytes). So far, separate analytical methods, including gas chromatography (GC) and liquid chromatography (LC), have been used to determine these proxies. Here we present a sensitive method for determining all three in a single normal phase high performance LC-atmospheric pressure chemical ionization mass spectrometry (NP-HPLC-APCI-MS) analysis. Each of the long chain alkenones and long chain diols was separated and unambiguously identified from the accurate masses and characteristic fragmentation during multiple stage MS analysis (MS2). Comparison of conventional GC and HPLC-MS methods showed similar results for UK'37 and LDI, respectively, using diverse environmental samples and an Emiliania huxleyi culture. Including the three sea surface temperature (SST) proxies; the NP-HPLC-APCI-MS method in fact allows simultaneous determination of nine paleoenvironmental proxies. The extent to which the ecology of the source organisms (ecological bias) influences lipid composition and thereby the reconstructed temperature values was demonstrated by applying the new method to a sediment core from the Sea of Marmara, covering the last 21 kyr BP. Reconstructed SST values differed considerably between the proxies for the Last Glacial Maximum (LGM) and the period of Sapropel S1 formation at ca. 10 kyr BP, whereas the trends during the late Holocene were similar. Changes in the composition of alkenone-producing species at the transition from the LGM to the Bølling/Allerød (B/A) were inferred from unreasonably high UK'37-derived SST values (ca. 20 °C) during the LGM. We ascribe discrepancies between the reconstructed temperature records during S1 deposition to habitat change, e.g. a different depth due to changes in nutrient availability.

Microcharcoal concentration and elongation, and age model of sediment core MD96-2098

Although grassland and savanna occupy only a quarter of the world's vegetation, burning in these ecosystems accounts for roughly half the global carbon emissions from fire. However, the processes that govern changes in grassland burning are poorly understood, particularly on time scales beyond satellite records. We analyzed microcharcoal, sediments, and geochemistry in a high-resolution marine sediment core off Namibia to identify the processes that have controlled biomass burning in southern African grassland ecosystems under large, multimillennial-scale climate changes. Six fire cycles occurred during the past 170,000 y in southern Africa that correspond both in timing and magnitude to the precessional forcing of north-south shifts in the Intertropical Convergence Zone. Contrary to the conventional expectation that fire increases with higher temperatures and increased drought, we found that wetter and cooler climates cause increased burning in the study region, owing to a shift in rainfall amount and seasonality (and thus vegetation flammability). We also show that charcoal morphology (i.e., the particle's length-to-width ratio) can be used to reconstruct changes in fire activity as well as biome shifts over time. Our results provide essential context for understanding current and future grassland-fire dynamics and their associated carbon emissions.

Sea surface temperature reconstruction for sediment core KNO5103-0029GGC

We present a 15 kyr sea surface temperature (SST) record for a high sedimentation rate core (KNR51-29GGC) from the Feni Drift off of Ireland, based on an organic geochemical technique for paleotemperature estimation, U37 K'. We compare the U37 K' temperature record to planktonic foraminiferal delta18O and foraminiferal assemblage SST estimates from the same sample horizons. U37 K' gives SST estimates of 13°C for the early deglacial and 18°C for the Holocene and Recent, whereas assemblages give estimates of 9°C and 13°C, respectively. As in nearby core V23-81, we find Ash Zone 1, the Younger Dryas increase in Neogloboquadrina pachyderma sinistral abundance, and maximum abundance of this species during glaciation. N. pachyderma dextral oxygen isotopic analyses have a late glacial to interglacial range of 1.5 per mil. A reduction of about 1 per mil in delta18O occurred at about 12 ka, whereas U37 K' and the foraminiferal fauna indicate a 2°C warming. This implies a 0.9 per mil salinity effect on delta18O which we attribute to meltwater freshening. All three parameters indicate cooling during the Younger Dryas. U37 K' SST estimates show that the major shift from deglacial to interglacial temperatures occurred after the Younger Dryas in termination 1b, in contrast to the assemblage data, which show this jump in SST at the end of the glaciation during termination Ia. Differences between the two SST estimators, which may result from their different (floral versus faunal) sources, are more pronounced between transitions Ia and Ib. This may reflect different habitats under the unusual sea surface conditions of the deglaciation.

CaCO3 content, terrigenous components, foraminifera abundance and age of sediment core MD95-2006, Barra Fan, UK

Lithology, lithic petrology, planktonic foraminiferal abundances, and clastic grain sizes have been determined in a 30 m-long core recovered from the Barra Fan off northwest Scotland. The record extends back to around 45 kyr B.P., with sedimentation rates ranging between 50 and 200 cm/kyr. The abundance of ice-rafted debris indicates 16 glacimarine events, including temporal equivalents to Heinrich events 1-4. Enhanced concentrations of basaltic material derived from the British Tertiary Province suggest that the glacimarine sediments record variations in a glacial source on the Hebrides shelf margin. Glacimarine zones are separated by silty intervals with high planktonic foraminifera concentrations that reflect an interstadial circulation regime in the Rockall Trough. The results suggest that the last British Ice Sheet fluctuated with a periodicity of 2000-3000 years, in common with the Dansgaard-Oeschger climate cycle.

Sediment, isotopic and geochemical record during Marine Isotope Stages 29 to 34 of IODP Site 339-U1387

Centennial-to-millennial scale records from IODP Site U1387, drilled during IODP Expedition 339 into the Faro Drift at 558 m water depth, now allow evaluating the climatic history of the upper core of the Mediterranean Outflow (MOW) and of the surface waters in the northern Gulf of Cadiz during the early Pleistocene. This study focuses on the period from Marine Isotope Stage (MIS) 29 to 34, i.e. the interval surrounding extreme interglacial MIS 31. Conditions in the upper MOW reflect obliquity, precession and millennial-scale variations. The benthic d18O signal follows obliquity with the exception of an additional, smaller d18O peak that marks the MIS 32/31 transition. Insolation maxima (precession minima) led to poor ventilation and a sluggish upper MOW core, whereas insolation minima were associated with enhanced ventilation and often also increased bottom current velocity. Millennial-scale periods of colder sea-surface temperatures (SST) were associated with short-term maxima in flow velocity and better ventilation, reminiscent of conditions known from MIS 3. A prominent contourite layer, coinciding with insolation cycle 100, was formed during MIS 31 and represents one of the few contourites developing within an interglacial period. MIS 31 surface water conditions were characterized by an extended period (1065-1091 ka) of warm SST, but SST were not much warmer than during MIS 33. Interglacial to glacial transitions experienced 2 to 3 stadial/interstadial cycles, just like their mid-to-late Pleistocene counterparts. Glacial MIS 30 and 32 recorded periods of extremely cold (< 12°C) SST that in their climatic impact were comparable to the Heinrich events of the mid and late Pleistocene. Glacial MIS 34, on the other hand, was a relative warm glacial period off southern Portugal. Overall, surface water and MOW conditions at Site U1387 show strong congruence with Mediterranean climate, whereas millennial-scale variations are closely linked to North Atlantic circulation changes.