Geochemistry of minerals in CRP sediment cores from the Ross Sea, Antarctica

Sixty-four volcanic chists, sandstones and tephras between 5.95 and 618.19 meters below sea floor (mbsf) in the Cape Roberts Project cores 2 and 2A cores (CRP-2/2A) were examined for Cenozoic and Mesozoic volcanic components, using optical and Scanning Electron Microscopy. Minerals and glass shards in a selection of samples were analysed by electron microprobe fined with an EDAX detector. Laser-Ablation ICP-Mass-Spectrometry (ICP-MS) was used to determine rare earth elements and 14 additional trace elements in glass shards, pyroxenes and feldspars in order to pin-point the onset of McMurdo Volcanic Group (MVG) activity in the stratigraphic column. Pumices in tephra layers of peralkaline phonolite composition in Unit 7.2 -between 108 and 114 mbsf - were also analysed for trace elements by ICP-MS. This tephra unit is not reworked and its isotopic age (21.44 ± 0.05 Ma) is the age of deposition. The height of the eruptive column responsible for the deposition of the tephra was probably less than 8 km; the source was local, probably within 30 km from the drill site. Phonolite of unit 7.2 of CRP-2/2A has no direct petrogenetic relation with the peralkaline trachyte in the tephra-enriched layer of CRP-1 at 116.55 mbsf. Volcanic clasts and sand grains (glass shards, aegirine-augite, anorthoclase) related to Cenozoic activity of MVG were observed only starting from Unit 9.8, where they are dated at 24.22 ± 0.06 Ma at c. 280 mbsf. In this unit the lowest- occurring basaltic glass shard is found at 297.54 mbsf. Sampled McMurdo volcanics are generally vesicular and vary in composition from alkali basalt to trachyte and peralkaline phonolite. By contrast, below 320 mbsf, aphyric or slightly-porphyritic volcanic clasts become more abundant but they are all non-vesiculated, pigeconite and ilmenite-bearing basalts and dolerite of tholeiitic affinity. These rocks are considered to be related to lava flows and associated intrusions of Jurassic age (Kirkpatrick basalts and Ferrar dolerite). As in CRP-1, McMurdo volcanics appear to derive from a variety of lithologics. Besides glaciers, a dominant role of wind transportation from exposed volcanic rocks may be inferred from the contemporary occurrence of glass shards of different compositions at depths above 297.54 mbsf. These data confirm that the onset of magmatic activity in southern Victoria Land is considerably delayed (by about 24 Ma) with respect to northern Victoria Land.

Age models of sediment cores from the Southern Ocean

Recent geochemical models invoke ocean alkalinity changes, particularly in the surface Southern Ocean, to explain glacial age pCO2 reduction. In such models, alkalinity increases in glacial periods are driven by reductions in North Atlantic Deep Water (NADW) supply, which lead to increases in deep-water nutrients and dissolution of carbonate sediments, and to increased alkalinity of Circumpolar Deep Water upwelling in the surface Southern Ocean. We use cores from the Southeast Indian Ridge and from the deep Cape Basin in the South Atlantic to show that carbonate dissolution was enhanced during glacial stages in areas now bathed by Circumpolar Deep Water. This suggests that deep Southern Ocean carbonate ion concentrations were lower in glacial stages than in interglacials, rather than higher as suggested by the polar alkalinity model [Broecker and Peng, 1989, doi:10.1029/GB001i001p00015]. Our observations show that changes in Southern Ocean CaCO3 preservation are coherent with changes in the relative flux of NADW, suggesting that Southern Ocean carbonate chemistry is closely linked to changes in deepwater circulation. The pattern of enhanced dissolution in glacials is consistent with a reduction in the supply of nutrient-depleted water (NADW) to the Southern Ocean and with an increase of nutrients in deep water masses. Carbonate mass accumulation rates on the Southeast Indian Ridge (3200-3800 m), and in relatively shallow cores (<3000 m) from the Kerguelen Plateau and the South Pacific were significantly reduced during glacial stages, by about 50%. The reduced carbonate mass accumulation rates and enhanced dissolution during glacials may be partly due to decreases in CaCO3:Corg flux ratios, acting as another mechanism which would raise the alkalinity of Southern Ocean surface waters. The polar alkalinity model assumes that the ratio of organic carbon to carbonate production on surface alkalinity is constant. Even if overall productivity in the Southern Ocean were held constant, a decrease in the CaCO3:Corg ratio would result in increased alkalinity and reduced pCO2 in Southern Ocean surface waters during glacials. This ecologically driven surface alkalinity change may enhance deepwater-mediated changes in alkalinity, and amplify rapid changes in pCO2.

Stable oxygen isotope record of Globigerinoides sacculifer and age determination of sediment cores from teh Somali Basin

This study documents the biological signatures impressed upon the sedimentary record underlying both the 5°N upwelling system of the Somali Current and the equatorial area of the Somali Basin out of the upwelling influence. The evolution of these two distinct hydrographic systems is compared for the last 160 kyr. Correspondence and cluster analyses are performed on combined radiolarian and planktonic foraminiferal quantitative data in order to study the changes of the planktonic assemblages through time and space. The Upwelling Radiolarian Index (URI) is used as a productivity proxy. The water temperature and hydrographic structure of the upper water masses appear to be the major factors controlling the distribution patterns of the fauna. The relative abundances of three groups of foraminifera, cold water form (dextral N. pachyderma), mixed layer dwellers (G. trilobus, G. ruber, G. sacculifer, G. conglobatus, and G. glutinata), and thermocline dwellers (G. menardii, G. tumida, N. dutertrei, G. crassaformis, and P. obliquiloculata), follow distinct evolutionary patterns at the two sites during the last 160 kyr. At the equatorial site (core MD 85668), downcore fluctuations in the relative abundances of the three groups are closely related to the glacial/interglacial cyclicity and provide some insights into the interpretation of hydrographic changes. The dominance of the mixed layer foraminifera at the transition intervals between isotope stages 6/5 and 2/1, combined with weak URI values, is thought to reflect the reorganization of the oceanographic circulation. These short-term events (with a duration of < 5000 year) could be related to the rapid inflow of oxygen-depleted water through the Indonesian straits as a result of sea level rise during deglaciation. Underneath the 5°N gyre (core MD 85674), the response to global climatic changes is overprinted by the regional effect of the Somalian upwelling, which has been persistent over the last 160 kyr.

Granulometry of two sediment cores from Maxwell Bay, South Shetland Islands, West Antarctica

The climate evolution of the South Shetland Islands during the last c. 2000 years is inferred from the multiproxy analyses of a long (928 cm) sediment core retrieved from Maxwell Bay off King George Island. The vertical sediment flux at the core location is controlled by summer melting processes that cause sediment-laden meltwater plumes to form. These leave a characteristic signature in the sediments of NE Maxwell Bay. We use this signature to distinguish summer and winter-dominated periods. During the Medieval Warm Period, sediments are generally finer which indicates summer-type conditions. In contrast, during the Little Ice Age (LIA) sediments are generally coarser and are indicative of winter-dominated conditions. Comparison with Northern and Southern Hemisphere, Antarctic, and global temperature reconstructions reveals that the mean grain-size curve from Maxwell Bay closely resembles the curve of the global temperature reconstruction. We show that the medieval warming occurred earlier in the Southern than in the Northern Hemisphere, which might indicate that the warming was driven by processes occurring in the south. The beginning of the LIA appears to be almost synchronous in both hemispheres. The warming after the LIA closely resembles the Northern Hemisphere record which might indicate this phase of cooling was driven by processes occurring in the north. Although the recent rapid regional warming is clearly visible, the Maxwell Bay record does not show the dominance of summer-type sediments until the 1970s. Continued warming in this area will likely affect the marine ecosystem through meltwater induced turbidity of the surface waters as well as an extension of the vegetation period due to the predicted decrease of sea ice in this area.

Mineralogical and geochemical data from five lake sediment cores of Lake Donggi Cona

Sediments of Lake Donggi Cona on the northeastern Tibetan Plateau were studied to infer changes in the lacustrine depositional environment, related to climatic and non-climatic changes during the last 19 kyr. The lake today fills a 30 X 8 km big and 95 m deep tectonic basin, associated with the Kunlun Fault. The study was conducted on a sediment-core transect through the lake basin, in order to gain a complete picture of spatiotemporal environmental change. The recovered sediments are partly finely laminated and are composed of calcareous muds with variable amounts of carbonate micrite, organic matter, detrital silt and clay. On the basis of sedimentological, geochemical, and mineralogical data up to five lithological units (LU) can be distinguished that document distinct stages in the development of the lake system. The onset of the lowermost LU with lacustrine muds above basal sands indicates that lake level was at least 39 m below the present level and started to rise after 19 ka, possibly in response to regional deglaciation. At this time, the lacustrine environment was characterized by detrital sediment influx and the deposition of siliciclastic sediment. In two sediment cores, upward grain-size coarsening documents a lake-level fall after 13 cal ka BP, possibly associated with the late-glacial Younger Dryas stadial. From 11.5 to 4.3 cal ka BP, grainsize fining in sediment cores from the profundal coring sites and the onset of lacustrine deposition at a litoral core site (2m water depth) in a recent marginal bay of Donggi Cona document lake-level rise during the early tomid-Holocene to at least modern level. In addition, high biological productivity and pronounced precipitation of carbonate micrites are consistent with warm and moist climate conditions related to an enhanced influence of summer monsoon. At 4.3 cal ka BP the lake system shifted from an aragonite- to a calcite-dominated system, indicating a change towards a fully open hydrological lake system. The younger clay-rich sediments are moreover non-laminated and lack any diagenetic sulphides, pointing to fully ventilated conditions, and the prevailing absence of lake stratification. This turning point in lake history could imply either a threshold response to insolation-forced climate cooling or a response to a non-climatic trigger, such as an erosional event or a tectonic pulse that induced a strong earthquake, which is difficult to decide from our data base.

Planktonic foraminifera and sea surface temperture reconstruction for Red Sea sediment cores

In order to assess how insolation-driven climate change superimposed on sea level rise and millennial events influenced the Red Sea during the Holocene, we present new paleoceanographic records from two sediment cores to develop a comprehensive reconstruction of Holocene circulation dynamics in the basin. We show that the recovery of the planktonic foraminiferal fauna after the Younger Dryas was completed earlier in the northern than in the central Red Sea, implying significant changes in the hydrological balance of the northern Red Sea region during the deglaciation. In the early part of the Holocene, the environment of the Red Sea closely followed the development of the Indian summer monsoon and was dominated by a circulation mode similar to the current summer circulation, with low productivity throughout the central and northern Red Sea. The climatic signal during the late Holocene is dominated by a faunal transient event centered around 2.4 ka BP. Its timing corresponds to that of North Atlantic Bond event 2 and to a widespread regionally recorded dry period. This faunal transient is characterized by a more productive foraminiferal fauna and can be explained by an intensification of the winter circulation mode and high evaporation. The modern distribution pattern of planktonic foraminifera, reflecting the prevailing circulation system, was established after 1.7 ka BP.

Sedimentation rate calculations and isotopic analysis on sediment cores along the IODP Expedition 311 transect

The oceanographic and tectonic conditions of accretionary margins are well-suited for several potential processes governing methane generation, storage and release. To identify the relevant methane evolution pathways in the northern Cascadia accretionary margin, a four-site transect was drilled during Integrated Ocean Drilling Program Expedition 311. The d13C values of methane range from a minimum value of -82.2 per mil on an uplifted ridge of accreted sediment near the deformation front (Site U1326, 1829 mbsl, meters below sea level) to a maximum value of -39.5 per mil at the most landward location within an area of steep canyons near the shelf edge (Site U1329, 946 mbsl). An interpretation based solely on methane isotope values might conclude the 13C-enrichment of methane indicates a transition from microbially- to thermogenically-sourced methane. However, the co-existing CO2 exhibits a similar trend of 13C-enrichment along the transect with values ranging from -22.5 per mil to +25.7 per mil. The magnitude of the carbon isotope separation between methane and CO2 (Ec = 63.8 ± 5.8) is consistent with isotope fractionation during microbially mediated carbonate reduction. These results, in conjunction with a transect-wide gaseous hydrocarbon content composed of > 99.8% (by volume) methane and uniform dDCH4 values (-172 per mil ± 8) that are distinct from thermogenic methane at a seep located 60 km from the Expedition 311 transect, suggest microbial CO2 reduction is the predominant methane source at all investigated sites. The magnitude of the intra-site downhole 13C-enrichment of CO2 within the accreted ridge (Site U1326) and a slope basin nearest the deformation front (Site U1325, 2195 mbsl) is ~ 5 per mil. At the mid-slope site (Site U1327, 1304 mbsl) the downhole 13C-enrichment of the CO2 is ~ 25 per mil and increases to ~ 40 per mil at the near-shelf edge Site U1329. This isotope fractionation pattern is indicative of more extensive diagenetic alteration at sites with greater 13C-enrichment. The magnitude of the 13C-enrichment of CO2 correlates with decreasing sedimentation rates and a diminishing occurrence of stratigraphic gas hydrate. We suggest the decreasing sedimentation rates increase the exposure time of sedimentary organic matter to aerobic and anaerobic degradation, during burial, thereby reducing the availability of metabolizable organic matter available for methane production. This process is reflected in the occurrence and distribution of gas hydrate within the northern Cascadia margin accretionary prism. Our observations are relevant for evaluating methane production and the occurrence of stratigraphic gas hydrate within other convergent margins.

Methane concentration in sediment cores during METEOR cruise M92

We studied the concurrence of methanogenesis and sulfate reduction in surface sediments (0-25 cm below sea floor, cmbsf) at six stations (70, 145, 253, 407, 770 and 1024 m) along the Peruvian margin (12° S). This oceanographic region is characterized by high carbon export to the seafloor, creating an extensive oxygen minimum zone (OMZ) on the shelf, both factors that could favor surface methanogenesis. Sediments sampled along the depth transect traversed areas of anoxic and oxic conditions in the bottom-near water. Net methane production (batch incubations) and sulfate reduction (35S-sulfate radiotracer incubation) were determined in the upper 0-25 cmbsf of multicorer cores from all stations, while deep hydrogenotrophic methanogenesis (> 30 cmbsf, 14C-bicarbonate radiotracer incubation) was determined in two gravity cores at selected sites (78 and 407 m). Furthermore, stimulation (methanol addition) and inhibition (molybdate addition) experiments were carried out to investigate the relationship between sulfate reduction and methanogenesis. Highest rates of methanogenesis and sulfate reduction in the surface sediments, integrated over 0-25 cmbsf, were observed on the shelf (70-253 m, 0.06-0.1 and 0.5-4.7 mmol m-2 d-1, respectively), while lowest rates were discovered at the deepest site (1024 m, 0.03 and 0.2 mmol m-2 d-1, respectively). The addition of methanol resulted in significantly higher surface methanogenesis activity, suggesting that the process was mostly based on non-competitive substrates, i.e., substrates not used by sulfate reducers. In the deeper sediment horizons, where competition was probably relieved due to the decline of sulfate, the usage of competitive substrates was confirmed by the detection of hydrogenotrophic activity in the sulfate-depleted zone at the shallow shelf station (70 m). Surface methanogenesis appeared to be correlated to the availability of labile organic matter (C / N ratio) and organic carbon degradation (DIC production), both of which support the supply of methanogenic substrates. A negative correlation of methanogenesis rates with dissolved oxygen in the bottom-near water was not obvious, however, anoxic conditions within the OMZ might be advantageous for methanogenic organisms at the sediment-water interface. Our results revealed a high relevance of surface methanogenesis on the shelf, where the ratio between surface to deep (below sulfate penetration) methanogenic activity ranged between 0.13 and 105. In addition, methane concentration profiles indicate a partial release of surface methane into the water column as well as a partial consumption of methane by anaerobic methane oxidation (AOM) in the surface sediment. The present study suggests that surface methanogenesis might play a greater role in benthic methane budgeting than previously thought, especially for fueling AOM above the sulfate-methane transition zone.

Geochemistry and stratigraphy on sediment cores from Leg198 and Leg 208

The first complete cyclic sedimentary successions for the early Paleogene from drilling multiple holes have been retrieved during two ODP expeditions: Leg 198 (Shatsky Rise, NW Pacific Ocean) and Leg 208 (Walvis Ridge, SE Atlantic Ocean). These new records allow us to construct a comprehensive astronomically calibrated stratigraphic framework with an unprecedented accuracy for both the Atlantic and the Pacific Oceans covering the entire Paleocene epoch based on the identification of the stable long-eccentricity cycle (405-kyr). High resolution X-ray fluorescence (XRF) core scanner and non-destructive core logging data from Sites 1209 through1211 (Leg 198) and Sites 1262, 1267 (Leg 208) are the basis for such a robust chronostratigraphy. Former investigated marine (ODP Sites 1001 and 1051) and land-based (e.g., Zumaia) sections have been integrated as well. The high-fidelity chronology is the prerequisite for deciphering mechanisms in relation to prominent transient climatic events as well as completely new insights into Greenhouse climate variability in the early Paleogene. We demonstrate that the Paleocene epoch covers 24 long eccentricity cycles. We also show that no definite absolute age datums for the K/Pg boundary or the Paleocene - Eocene Thermal Maximum (PETM) can be provided by now, because of still existing uncertainties in orbital solutions and radiometric dating. However, we provide two options for tuning of the Paleocene which are only offset by 405-kyr. Our orbitally calibrated integrated Leg 208 magnetostratigraphy is used to revise the Geomagnetic Polarity Time Scale (GPTS) for Chron C29 to C25. We established a high-resolution calcareous nannofossil biostratigraphy for the South Atlantic which allows a much more detailed relative scaling of stages with biozones. The re-evaluation of the South Atlantic spreading rate model features higher frequent oscillations in spreading rates for magnetochron C28r, C27n, and C26n.

Radiocarbon ages and 230Th data of five sediment cores from the Björn and Gardar Drift, North Atlantic

In locations of rapid sediment accumulation receiving substantial amounts of laterally transported material the timescales of transport and accurate quantification of the transported material are at the focus of intense research. Here we present radiocarbon data obtained on co-occurring planktic foraminifera, marine haptophyte biomarkers (alkenones) and total organic carbon (TOC) coupled with excess Thorium-230 (230Thxs) measurements on four sediment cores retrieved in 1649-2879 m water depth from two such high accumulation drift deposits in the Northeast Atlantic, Björn and Gardar Drifts. While 230Thxs inventories imply strong sediment focussing, no age offsets are observed between planktic foraminifera and alkenones, suggesting that redistribution of sediments is rapid and occurs soon after formation of marine organic matter, or that transported material contains negligible amounts of alkenones. An isotopic mass balance calculation based on radiocarbon concentrations of co-occurring sediment components leads us to estimate that transported sediment components contain up to 12% of fossil organic matter that is free of or very poor in alkenones, but nevertheless appears to consist of a mixture of fresh and eroded fossil material. Considering all available constraints to characterize transported material, our results show that although focussing factors calculated from bulk sediment 230Thxs inventories may allow useful approximations of bulk redeposition, they do not provide a unique estimate of the amount of each laterally transported sediment component. Furthermore, our findings provide evidence that the occurrence of lateral sediment redistribution alone does not always hinder the use of multiple proxies but that individual sediment fractions are affected to variable extents by sediment focussing.

Micro-facies and µXRF element scanning data of Dead Sea sediment cores DSEn and 5017-1

Laminated lake sediments from the Dead Sea basin provide high-resolution records of climatic variability in the eastern Mediterranean region, which is especially sensitive to changing climatic conditions. In this study, we aim on detailed reconstruction of climatic fluctuations and related changes in the frequency of flood and dust deposition events at ca. 3300 and especially at 2800 cal. yr BP from high-resolution sediment records of the Dead Sea basin. A ca. 4-m-thick, mostly varved sediment section from the western margin of the Dead Sea (DSEn - Ein Gedi profile) was analysed and correlated to the new International Continental Scientific Drilling Program (ICDP) Dead Sea Deep Drilling Project core 5017-1 from the deep basin. To detect even single event layers, we applied a multi-proxy approach of high-resolution microscopic thin section analyses, micro-X-ray fluorescence (µ-XRF) element scanning and magnetic susceptibility measurements, supported by grain size data and palynological analyses. Based on radiocarbon and varve dating, two pronounced dry periods were detected at ~3500-3300 and ~3000-2400 cal. yr BP which are differently expressed in the sediment records. In the shallow-water core (DSEn), the older dry period is characterised by a thick sand deposit, whereas the sedimentological change at 2800 cal. yr BP is less pronounced and characterised mainly by an enhanced frequency of coarse detrital layers interpreted as erosion events. In the 5017-1 deep-basin core, both dry periods are depicted by halite deposits. The onset of the younger dry period coincides with the Homeric Grand Solar Minimum at ca. 2800 cal. yr BP. Our results suggest that during this period, the Dead Sea region experienced an overall dry climate, superimposed by an increased occurrence of flash floods caused by a change in synoptic weather patterns.

(Data S1) Palynological analysis of IODP and ODP sediment cores around the Antarctic margin

The circum-Antarctic Southern Ocean is an important region for global marine food webs and carbon cycling because of sea-ice formation and its unique plankton ecosystem. However, the mechanisms underlying the installation of this distinct ecosystem and the geological timing of its development remain unknown. Here, we show, on the basis of fossil marine dinoflagellate cyst records, that a major restructuring of the Southern Ocean plankton ecosystem occurred abruptly and concomitant with the first major Antarctic glaciation in the earliest Oligocene (~33.6 million years ago). This turnover marks a regime shift in zooplankton-phytoplankton interactions and community structure, which indicates the appearance of eutrophic and seasonally productive environments on the Antarctic margin. We conclude that earliest Oligocene cooling, ice-sheet expansion, and subsequent sea-ice formation were important drivers of biotic evolution in the Southern Ocean.

Age tie points and geochemistry of sediment cores from the Antarctic continental margin

Few high-latitude terrestrial records document the timing and nature of the Cenozoic "Greenhouse" to "Icehouse" transition. Here we exploit the bulk geochemistry of marine siliciclastic sediments from drill cores on Antarctica's continental margin to extract a unique semiquantitative temperature and precipitation record for Eocene to mid-Miocene (~54-13 Ma). Alkaline elements are strongly enriched in the detrital mineral fraction in fine-grained siliciclastic marine sediments and only occur as trace metals in the biogenic fraction. Hence, terrestrial climofunctions similar to the chemical index of alteration (CIA) can be applied to the alkaline major element geochemistry of marine sediments on continental margins in order to reconstruct changes in precipitation and temperature. We validate this approach by comparison with published paleotemperature and precipitation records derived from fossil wood, leaves, and pollen and find remarkable agreement, despite uncertainties in the calibrations of the different proxies. A long-term cooling on the order of >=8°C is observed between the Early Eocene Climatic Optimum (~54-52 Ma) and the middle Miocene (~15-13 Ma) with the onset of transient cooling episodes in the middle Eocene at ~46-45 Ma. High-latitude stratigraphic records currently exhibit insufficient temporal resolution to reconstruct continental aridity and inferred ice-sheet development during the middle to late Eocene (~45-37 Ma). However, we find an abrupt aridification of East Antarctica near the Eocene-Oligocene transition (~34 Ma), which suggests that ice coverage influenced high-latitude atmospheric circulation patterns through albedo effects from the earliest Oligocene onward.