Geochemistry of sediments from the Eastern Cape Basin

Sediment cores retrieved in the Benguela coastal upwelling system off Namibia show very distinct enrichments of solid phase barium at the sulfate/methane transition (SMT). These barium peaks represent diagenetic barite (BaSO4) fronts which form by the reaction of upwardly diffusing barium with interstitial sulfate. Calculated times needed to produce these barium enrichments indicate a formation time of about 14,000 yr. Barium spikes a few meters below the SMT were observed at one of the investigated sites (GeoB 8455). Although this sulfate-depleted zone is undersaturated with respect to barite, the dominant mineral phase of these buried barium enrichments was identified as barite by scanning electron microscopy (SEM). This is the first study which reports the occurrence/preservation of pronounced barite enrichments in sulfate-depleted sediments buried a few meters below the SMT. At site GeoB 8455 high concentrations of dissolved barium in pore water as well as barium in the solid phase were observed. Modeling the measured barium concentrations at site GeoB 8455 applying the numerical model CoTReM reveals that the dissolution rate of barite directly below the SMT is about one order of magnitude higher than at the barium enrichments deeper in the sediment core. This indicates that the dissolution of barite at these deeper buried fronts must be retarded. Thus, the occurrence of the enrichments in solid phase barium at site GeoB 8455 could be explained by decreased dissolution rates of barite due to the changes in the concentration of barite in the sediment, as well as changes in the saturation state of fluids. Furthermore, the alteration of barite into witherite (BaCO3) via the transient phase barium sulfide could lead to the preservation of a former barite front as BaCO3. The calculations and modeling indicate that a relocation of the barite front to a shallower depth occurred between the last glacial maxium (LGM) and the Pleistocene/Holocene transition. We suggest that an upward shift of the SMT occurred at that time, most likely as a result of an increase in the methanogenesis rates due to the burial of high amounts of organic matter below the SMT.

Geochemical records of sediment cores from the Sea of Japan

Intervals of organic C- and carbonate-rich laminated sediments occur in the Sea of Japan with roughly the same frequency as temperature changes observed in Greenland ice cores, providing clear evidence of rapid oceanographic change during the past 36 kyr. Planktonic foraminiferal d18O data suggest that only the laminated sediments deposited during the Last Glacial Maximum (LGM), and perhaps one other interval formed during a period of increased water column stratification. Sedimentary Re and Mo data are consistent with bottom waters that were sulfidic during the LGM and suboxic during other laminated intervals. Results of a numerical model of Corg and Re burial are consistent with a mechanism whereby an increased Corg flux to the seafloor drove oxygen concentrations toward depletion during times of deposition of the suboxic laminated intervals. Such a process could have resulted from increased upwelling driven either by increased deep water formation due to colder and/or more saline surface waters or by stronger northeasterly monsoonal winds.

Sea ice diatoms from Late Quaternary sediments in the Scotia Sea

Sea-ice growth and decay in Antarctica is one of the biggest seasonal changes on Earth, expanding ice cover from 4x10**6 km**2 to a maximum of 19x10**6 km**2 during the austral winter. Analyses of six marine sediment cores from the Scotia Sea, SW Atlantic, yield records of sea-ice migration across the basin since the Lateglacial. The cores span nearly ten degrees of latitude from the modern seasonal sea-ice zone to the modern Polar Front. Surface sediments in the cores comprise predominantly diatomaceous oozes and muddy diatom oozes that reflect Holocene conditions. The cores exhibit similar down-core stratigraphies with decreasing diatom concentrations and increasing magnetic susceptibility from modern through to the Last Glacial Maximum (LGM). Sediments in all cores contain sea-ice diatoms that preserve a signal of changing sea-ice cover and permit reconstruction of past sea-ice dynamics. The sea-ice records presented here are the first to document the position of both the summer and winter sea-ice cover at the Last Glacial Maximum (LGM) in the Scotia Sea. Comparison of the LGM and Holocene sea-ice conditions shows that the average winter sea-ice extent was at least 5° further north at the LGM. Average summer sea-ice extent was south of the most southerly core site at the LGM, and suggests that sea-ice expanded from approximately 61°S to 52°S each season. Our data also suggest that the average summer sea-ice position at the LGM was not the maximum extent of summer sea-ice during the last glacial. Instead, the sediments contain evidence of a pre-LGM maximum extent of summer sea-ice between ab. 30 ka and 22 ka that extended to ab. 59°S, close to the modern average winter sea-ice limit. Based on our reconstruction we propose that the timing of the maximum extent of summer sea-ice and subsequent retreat by 22 ka, could be insolation controlled and that the strong links between sea-ice and bottom water formation provide a potential mechanism by which Southern Hemisphere regional sea-ice dynamics at the LGM could have a global impact and promote deglaciation.

Abundance of organic-walled dinoflagellate cysts and geochemical analysis of sediment core GeoB5546-2

NW African climate shows orbital and millenial-scale variations, which are tightly connected to changes in marine productivity. We present an organic-walled dinoflagellate cyst (dinocyst) record from a sediment core off Cape Yubi at about 27°N in the Canary Basin covering the time period from 47 to 3ka before present (BP). The dinocyst record reflects differences in upwelling intensity and seasonality as well as the influence of fluvial input. Sea-level changes play an important role for the upwelling pattern and productivity signals at the core site. Within the studied time interval, four main phases were distinguished. (1) From 45 to 24ka BP, when sea-level was mostly about 75m lower than today, high relative abundances of cysts of heterotrophic taxa point to enhanced upwelling activity, especially during Heinrich Events, while relatively low dinocyst accumulation rates indicate that filament activity at the core location was strongly reduced. (2) At sea-level lowstand during the LGM to H1, dinocyst accumulation rates suggest that local filament formation was even more inhibited. (3) From the early Holocene to about 8ka BP, extraordinary high accumulation rates of most dinocyst species, especially of Lingulodinium machaerophorum, suggest that nutrient supply via fluvial input increased and rising sea-level promoted filament formation. At the same time, the upwelling season prolongated. (4) A relative increase in cysts of photoautotrophic taxa from about 8ka BP on indicates more stratified conditions while fluvial input decreased. Our study shows that productivity records can be very sensitive to regional features. From the dinocyst data we infer that marine surface productivity off Cape Yubi during glacial times was within the scale of modern times but extremely enhanced during deglaciation.

Stable isotope record of planktonic foraminifera from the western Iberian margin during marine isotope stage 2

The surface water hydrography along the western Iberian margin, as part of the North Atlantic's eastern boundary upwelling system, consists of a complex, seasonally variable system of equatorward and poleward surface and subsurface currents and seasonal upwelling. Not much information exists to ascertain if the modern current and productivity patterns subsisted under glacial climate conditions, such as during marine isotope stage (MIS) 2, and how North Atlantic meltwater events, especially Heinrich events, affected them. To help answer these questions we are combining stable isotope records of surface to subsurface dwelling planktonic foraminifer species with sea surface temperature and export productivity data for four cores distributed along the western and southwestern Iberian margin (MD95-2040, MD95-2041, MD99-2336, and MD99-2339). The records reveals that with the exception of the Heinrich events and Greenland Stadial (GS) 4 hydrographic conditions along the western Iberian margin were not much different from the present. During the Last Glacial Maximum (LGM), subtropical surface and subsurface waters penetrated poleward to at least 40.6°N (site MD95-2040). Export productivity was, in general, high on the western margin during the LGM and low in the central Gulf of Cadiz, in agreement with the modern situation. During the Heinrich events and GS 4, on the other hand, productivity was high in the Gulf of Cadiz and suppressed in the upwelling regions along the western margin where a strong halocline inhibited upwelling. Heinrich event 1 had the strongest impact on the hydrography and productivity off Iberia and was the only period when subarctic surface waters were recorded in the central Gulf of Cadiz. South of Lisbon (39°N), the impact of the other Heinrich events was diminished, and not all of them led to a significant cooling in the surface waters. Thus, climatic impacts of Heinrich events highly varied with latitude and the prevailing hydrographic conditions in this region.

Age models, sedimentology and geochemistry from sediment cores in Drake Passage throughflow

The Drake Passage (DP) is the major geographic constriction for the Antarctic Circumpolar Current (ACC) and exerts a strong control on the exchange of physical, chemical, and biological properties between the Atlantic, Pacific, and Indian Ocean basins. Resolving changes in the flow of circumpolar water masses through this gateway is, therefore, crucial for advancing our understanding of the Southern Ocean's role in global ocean and climate variability. Here, we reconstruct changes in DP throughflow dynamics over the past 65,000 y based on grain size and geochemical properties of sediment records from the southernmost continental margin of South America. Combined with published sediment records from the Scotia Sea, we argue for a considerable total reduction of DP transport and reveal an up to ~40% decrease in flow speed along the northernmost ACC pathway entering the DP during glacial times. Superimposed on this long-term decrease are high-amplitude, millennial-scale variations, which parallel Southern Ocean and Antarctic temperature patterns. The glacial intervals of strong weakening of the ACC entering the DP imply an enhanced export of northern ACC surface and intermediate waters into the South Pacific Gyre and reduced Pacific-Atlantic exchange through the DP ("cold water route"). We conclude that changes in DP throughflow play a critical role for the global meridional overturning circulation and interbasin exchange in the Southern Ocean, most likely regulated by variations in the westerly wind field and changes in Antarctic sea ice extent.

Stable carbon and oxygen isotope ratios of foraminifera from Holocene sediments of the North Atlantic

The Denmark Strait Overflow (DSO) today compensates for the northward flowing Norwegian and Irminger branches of the North Atlantic Current that drive the Nordic heat pump. During the Last Glacial Maximum (LGM), ice sheets constricted the Denmark Strait aperture in addition to ice eustatic/isostatic effects which reduced its depth (today ~630 m) by ~130 m. These factors, combined with a reduced north-south density gradient of the water-masses, are expected to have restricted or even reversed the LGM DSO intensity. To better constrain these boundary conditions, we present a first reconstruction of the glacial DSO, using four new and four published epibenthic and planktic stable-isotope records from sites to the north and south of the Denmark Strait. The spatial and temporal distribution of epibenthic delta18O and delta13C maxima reveals a north-south density gradient at intermediate water depths from sigma0 ~28.7 to 28.4/28.1 and suggests that dense and highly ventilated water was convected in the Nordic Seas during the LGM. However, extremely high epibenthic delta13C values on top of the Mid-Atlantic Ridge document a further convection cell of Glacial North Atlantic Intermediate Water to the south of Iceland, which, however, was marked by much lower density (sigma0 ~28.1). The north-south gradient of water density possibly implied that the glacial DSO was directed to the south like today and fed Glacial North Atlantic Deep Water that has underthrusted the Glacial North Atlantic Intermediate Water in the Irminger Basin.

Planktic and benthic 14C reservoir ages, calibrated by a suite of 14C plateaus in the glacial-to-deglacial Suigetsu atmospheric 14C record

We here present a compilation of planktic and benthic 14C reservoir ages for the Last Glacial Maximum (LGM) and early deglacial from 11 key sites of global ocean circulation in the Atlantic and Indo-Pacific Ocean. The ages were obtained by 14C plateau tuning, a robust technique to derive both an absolute chronology for marine sediment records and a high-resolution record of changing reservoir/ventilation ages (Delta14C values) for surface and deep waters by comparing the suite of planktic 14C plateaus of a sediment record with that of the atmospheric 14C record (Sarnthein et al., 2007, doi:10.1029/173GM13). Results published thus far used as atmospheric 14C reference U/Th-dated corals, the Cariaco planktic record, and speleothems (Fairbanks et al., 2005, doi:10.1016/j.quascirev.2005.04.007; Hughen et al., 2006, doi:10.1016/j.quascirev.2006.03.014; Beck et al., 2001, doi:10.1023/A:1008175728826). We have now used the varve-counted atmospheric 14C record of Lake Suigetsu terrestrial macrofossils (Ramsey et al., 2012, doi:10.1126/science.1226660) to recalibrate the boundary ages and reservoir ages of the seven published records directly to an atmospheric 14C record. In addition, the results for four new cores and further planktic results for four published records are given. Main conclusions from the new compilation are: (1) The Suigetsu atmospheric 14C record on its varve counted time scale reflects all 14C plateaus, their internal structures and relative length previously identified, but implies a rise in the average 14C plateau age by 200-700 14C yr during LGM and early deglacial times. (2) Based on different 14C ages of coeval atmospheric and planktic 14C plateaus, marine surface water Delta14C may have temporarily dropped to an equivalent of ~0 yr in low-latitude lagoon waters, but reached >2500 14C yr both in stratified subpolar waters and in upwelled waters such as in the South China Sea. These values differ significantly from a widely assumed constant global planktic Delta14C value of 400 yr. (3) Suites of deglacial planktic Delta14C values are closely reproducible in 14C records measured at neighboring core sites. (4) Apparent deep-water 14C ventilation ages (equivalents of benthic Delta14C), deduced from the sum of planktic Delta14C and coeval benthic-planktic 14C differences, vary from 500 up to >5000 yr in LGM and deglacial ocean basins.

Global compilation of last glacial maximum oxygen isotopic ratios for planktonic and benthic foraminifera

We use the fully coupled atmosphere-ocean three-dimensional model of intermediate complexity iLOVECLIM to simulate the climate and oxygen stable isotopic signal during the Last Glacial Maximum (LGM, 21 000 yr). By using a model that is able to explicitly simulate the sensor (d18O), results can be directly compared with data from climatic archives in the different realms. Our results indicate that iLOVECLIM reproduces well the main feature of the LGM climate in the atmospheric and oceanic components. The annual mean d18O in precipitation shows more depleted values in the northern and southern high latitudes during the LGM. The model reproduces very well the spatial gradient observed in ice core records over the Greenland ice-sheet. We observe a general pattern toward more enriched values for continental calcite d18O in the model at the LGM, in agreement with speleothem data. This can be explained by both a general atmospheric cooling in the tropical and subtropical regions and a reduction in precipitation as confirmed by reconstruction derived from pollens and plant macrofossils. Data-model comparison for sea surface temperature indicates that iLOVECLIM is capable to satisfyingly simulate the change in oceanic surface conditions between the LGM and present. Our data-model comparison for calcite d18O allows investigating the large discrepancies with respect to glacial temperatures recorded by different microfossil proxies in the North Atlantic region. The results argue for a trong mean annual cooling between the LGM and present (>6°C), supporting the foraminifera transfer function reconstruction but in disagreement with alkenones and dinocyst reconstructions. The data-model comparison also reveals that large positive calcite d18O anomaly in the Southern Ocean may be explained by an important cooling, although the driver of this pattern is unclear. We deduce a large positive d18Osw anomaly for the north Indian Ocean that contrasts with a large negative d18Osw anomaly in the China Sea between the LGM and present. This pattern may be linked to changes in the hydrological cycle over these regions. Our simulation of the deep ocean suggests that changes in d18Osw between the LGM and present are not spatially homogenous. This is supported by reconstructions derived from pore fluids in deep-sea sediments. The model underestimates the deep ocean cooling thus biasing the comparison with benthic calcite d18O data. Nonetheless, our data-model comparison support a heterogeneous cooling of few degrees (2-4°C) in the LGM Ocean.

Late Pleistocene oxygen isotope record of biognic silica

We determined the isotopic composition of oxygen in marine diatoms in eight deep-sea cores recovered from the Atlantic sector of the Southern Ocean. The analytical reproducibility and core-to-core consistency of the isotopic signal suggests that diatom delta18O can be used as a new paleocenographic tool to reconstruct past variations in surface water characteristics and to generate 18O -isotope-based stratigraphy for the Southern Ocean. The data indicate that diatom delta18O reflects sea surface temperature and seawater isotopic composition and that diatoms retain their isotopic signal on timescales of a least 430 ka. The delta18O analyses of different diatom assemblages reveal that the isotopic signal is free of species effects and that the common Antarctic species have the same water-opal fractionation. The transition from the last glacial maximum (LGM) to the Holocene is fully recorded in high sedimentation rate cores. An 18O enrichment during the LGM, a post-LGM meltwater spike and an input of meltwater during the late Holocene are the main isotopic features observed in down core records. The origin of this meltwater was very likely melting icebergs and/or continental ice or by melting sea ice that had accumulated snow. The most pronounced meltwater effects are recorded in cores that are associated with the Weddel gyre. Our results provide the basis for extending isotope studies to oceanic regions devoid of carbonate; further, isotopic stratigraphies may be constructed for records and regions where they were previously not possible.

Micropaleontological and geochemical proxy studies of sediment core GeoB7926-2

[1] The low-latitude upwelling regime off the Mauritanian coast in the subtropical NE Atlantic accounts for a significant part of global export production. Although productivity variations in coastal upwelling areas are usually attributed to changes in wind stress and upwelling intensity, productivity dynamics off Mauritania are less straightforward because of the complex atmospheric and hydrographic setting. Here we integrate micropaleontological (diatoms) and geochemical (bulk biogenic sediment components, X-ray fluorescence, and alkenones) proxies to examine on submillennial-to-millennial changes in diatom production that occurred off Mauritania, NW Africa, for the last 25 ka. During the Last Glacial Maximum (LGM, 19.0-23.0 ka B.P.), moderate silicate content of upwelled waters coupled with weakened NE trade winds determined moderate diatom productivity. No significant cooling is observed during the LGM, suggesting that our alkenone-based SST reconstruction represents a local, upwelling-related signal rather than a global insolation related one. Extraordinary increases in diatom and opal concentrations during Heinrich event 1 (H1, 15.5-18.0 ka B.P.) and the Younger Dryas (YD, 13.5-11.5 ka B.P.) are attributed to enhanced upwelling of silica-rich waters and an enlarged upwelling filament, due to more intense NE trade winds. The synchronous increase of CaCO3 and K intensity and the decreased opal and diatoms values mark the occurrence of the Bølling/Allerød (BA, 13.5-15.5 ka B.P.) due to weakened eolian input and more humid conditions on land. Although the high export of diatoms is inextricably linked to upwelling intensity off Mauritania, variability in the nutrient content of the thermocline also plays a decisive role.

Planktonic foraminifera of sediment core MD01-2390

Sea-surface temperature (SST) estimates in the sediment core MD01-2390 based on planktonic foraminiferal species abundances using five different transfer function techniques suggest nearly unchanged or unusually higher temperatures in the tropical southern South China Sea (SCS) during the Last Glacial Maximum (LGM) relative to modern temperatures. These results are in contrast to substantial cooling of 2-5 °C inferred by geochemical (Uk'37, Mg/Ca ratios) and terrestrial proxies from the western tropical Pacific region. Using multivariate statistics we show that the glacial southern SCS harboured unique planktonic foraminiferal assemblages that have no modern analogs. Analyses of faunal variation through the core reveal that planktonic foraminiferal assemblages responded to temperature changes inferred from Mg/Ca data but that this signal is subdued by superimposed variations in the relative abundance of Pulleniatina obliquiloculata and Neogloboquadrina pachyderma (dextral). These species occur in glacial samples at proportions that are not observed in the calibration data set. The glacial high abundance of N. pachyderma (dextral) are interpreted to reflect a seasonal (winter) inflow of cold surface water from the northeast via the Bashi Strait due to the combined effects of an intensified winter monsoon, a southward shift of the polar front and the eastward migration of the Kuroshio Current. In contrast, processes controlling the high relative abundances of P. obliquiloculata during the LGM may be unique to the southern SCS. We propose a scenario involving a stronger (winter) mixing or enhanced upwelling due to an intensified winter monsoon that prevented shallow-dwelling, warm indicators to establish larger populations during the LGM. Our results indicate that a no-analog behaviour of planktonic foraminifera faunas is responsible for the warm glacial conditions in this part of the western Pacific warm pool as implied by foraminiferal transfer functions and that a more significant surface cooling in the region as implied by terrestrial and geochemical (Mg/Ca ratios; alkenone unsaturation index) marine proxies is a more likely scenario.

Dust fluxes and iron fertilization in Holocene and Last Glacial Maximum climates

Mineral dust aerosols play a major role in present and past climates. To date, we rely on climate models for estimates of dust fluxes to calculate the impact of airborne micronutrients on biogeochemical cycles. Here we provide a new global dust flux data set for Holocene and Last Glacial Maximum (LGM) conditions based on observational data. A comparison with dust flux simulations highlights regional differences between observations and models. By forcing a biogeochemical model with our new data set and using this model's results to guide a millennial-scale Earth System Model simulation, we calculate the impact of enhanced glacial oceanic iron deposition on the LGM-Holocene carbon cycle. On centennial timescales, the higher LGM dust deposition results in a weak reduction of <10?ppm in atmospheric CO2 due to enhanced efficiency of the biological pump. This is followed by a further ~10?ppm reduction over millennial timescales due to greater carbon burial and carbonate compensation.

Averages and ranges of paleoenvironmental proxy records of ODP Hole 108-658C (Table 1)

Several high-resolution proxy environmental records have been obtained for the last 35 kyr from ODP Hole 658C, a well-studied site ca. 200 km off Cap Blanc, NW Africa. The collective assessment based on the marine proxies (UK'37 SST, contents of TOC and chlorins, Upwelling Radiolarian Index and the percentage of Florisphaera profunda), surprisingly indicates that the last glacial maximum (LGM) was characterized by warmer sea surface temperature (SST), weaker upwelling, and lower marine productivity, compared with the preceding older glacial and subsequent deglaciation periods. Of the terrigenous proxies, the mean grain size of the non-carbonate fraction and the terrigenous alkane content indicate that wind strength and aridity were high. The weaker upwelling at the 658 site during the LGM may have resulted from changes in the strength and direction of the wind systems and/or shifts in the position and geometry of the upwelling cell.