Age determinations and sedimentology on cores GIK17940 and 184-1144

Sedimentological, geochemical and paleomagnetic records were employed to reconstruct the history of East Asian Monsoon variability in the South China Sea (SCS) on orbital- and millennial-to-sub-decadal time scales. A detailed magnetostratigraphy for the southern central SCS was established as well as a stable isotope stratigraphy for ODP Site 1144 for the last 1.2 million years in the northern South China Sea. Furthermore a volcanic tephra layer from the southern central SCS could be identified as the Youngest Toba Ash, which thus re-presents an important age marker and was used to reconstruct paleo wind directions during the eruption 74 ka. Special attention was paid to the high- and ultrahigh-frequency variability in the last glacial-interglacial cycle and the Holocene, and to a precise age control of climate changes in general.

Stable carbon isotope record of Bahama Bank sediments

The carbon-isotopic composition (d13C) of bulk carbonates, obtained from a transect of sites drilled through platform and periplatform sediments of Holocene to Early Miocene age, has been compared to ascertain whether changes in the d13C can be correlated between sediments of equivalent ages and whether such changes can be related to global changes in the d13C of the dissolved inorganic carbon in the oceans over this time period. Five of the sites were drilled during Leg 166 of the Ocean Drilling Project (1003-1007) in a transect ranging from five km to 25 km away from the platform margin and penetrating sediments of Holocene to Oligocene age that are contained in 17 depositional sequences (A-Q). Two shallow-water sites, Clino and Unda were situated on a extension of the same transect on Great Bahama Bank in a water depth of 10-15 m. With the exception of Unda and Clino, the d13C of the carbonates ranges from +5 per mil in the younger sequences to +1 per mil in the Early Miocene. In each of the sites, the d13C is strongly positively correlated with the percentage of aragonite. As a consequence, the d13C of sequences A through F is strongly correlated, reflecting the decreasing amount of aragonite with increasing depth. In the two platform sites, the d13C is significantly lower in the younger portions of the cores as a result of the influences of meteoric diagenesis during repeated exposure during the Pleistocene. Although the d13C of the individual sequences can be correlated in most instances between the ODP holes, the changes are not related to global changes in the d13C of the oceans which in contrast to the d13C of the platform sediments become isotopically lower towards the present day. Instead variations in the d13C appear to be related to varying mixtures of d13C-rich banktop sediments and pelagic material.

Benthic foraminiferal fauna and isotope record in Holocene sediments of the northwest Indian Ocean

Historically, the Holocene has been considered an interval of relatively stable climate. However, recent studies from the northern Arabian Sea (Netherlands Indian Ocean Program 905) suggested high-amplitude climate shifts in the early and middle Holocene based on faunal and benthic isotopic proxy records. We examined benthic foraminiferal faunal and stable isotopic data from Ocean Drilling Program (ODP) Site 723 and total organic carbon data from ODP Site 724, Oman Margin (808 and 593 m water depths, respectively). At Site 723 the mid-Holocene shift in d18O values of infaunal benthic species Uvigerina peregrina (1.4 per mil) is 3 times larger than that of epifaunal benthic species Cibicides kullenbergi recorded at Site NIOP 905 off Somalia. However, none of the five other benthic species we measured at Hole 723A exhibits such a shift in d18O. We speculate that the late Holocene d18O decrease in U. peregrina represents species-specific changes in ecological habitat or food preference in response to changes in surface and deep ocean circulation. While the stable isotopic data do not appear to indicate a middle Holocene climatic shift, our total organic carbon and benthic faunal assemblage data do indicate that the early Holocene deep Arabian Sea was influenced by increased ventilation perhaps by North Atlantic Deep Water and/or Circumpolar Deep Water incursions into the Indian Ocean, leading to remineralization of organic matter and a relatively weak early Holocene oxygen minimum zone in the northwest Arabian Sea in spite of strong summer monsoon circulation.

Isotope characterisation of Villars Cave stalagmites

We present a new mid-latitude speleothem record of millennial-scale climatic variability during OIS3 from the Villars Cave that, combined with former published contemporaneous samples from the same cave, gives a coherent image of the climate variability in SW-France between ~55 ka and ~30 ka. The 0.82 m long stalagmite Vil-stm27 was dated with 26 TIMS U-Th analyses and its growth curve displays variations that are linked with the stable isotopes, both controlled by the climatic conditions. It consists in a higher resolved replicate of the previously published Vil-stm9 and Vil-stm14 stalagmites where Dansgaard-Oeschger (DO) events have been observed. The good consistency between these three stalagmites and the comparison with other palaoeclimatic reconstructions, especially high resolution pollen records (ODP 976 from the Alboran Sea, Monticchio Lake record from southern Italy) and the nearby MD04-2845 Atlantic Ocean record, permits to draw a specific climatic pattern in SW-France during the OIS3 and to see regional differences between these sites. Main features of this period are: 1) warm events corresponding to Greenland Interstadials (GIS) that are characterized by low speleothem d13C, high temperate pollen percentages, warm temperatures and high humidity; among these events, GIS#12 is the most pronounced one at Villars characterized by an abrupt onset at ~46.6 ka and a duration of about 2.5 ka. The other well individualized warm event coincides with GIS#8 which is however much less pronounced and occurred during a cooler period as shown by a lower growth rate and a higher d13C; 2) cold events corresponding to Greenland Stadials (GS) that are clearly characterized by high speleothem d13C, low temperate pollen abundance, low temperature and enhanced dryness, particularly well expressed during GS coinciding with Heinrich events H5 and H4. The main feature of the Villars record is a general cooling trend between the DO#12 event ~45.5 ka and the synchronous stop of the three stalagmites at ~30 ka ±1, with a first well marked climatic threshold at ~41 ka after which the growth rate and the diameter of all stalagmites slows down significantly. This climatic evolution differs from that shown at southern Mediterranean sites where this trend is not observed. The ~30 ka age marks the second climatic threshold after which low temperatures and low rainfalls prevent speleothem growth in the Villars area until the Lateglacial warming that occurred at ~16.5 ± 0.5 ka. This 15 ka long hiatus, as the older Villars growth hiatus that occurred between 67.4 and 61 ka, are linked to low sea levels, reduced ocean circulation and a southward shift of the Polar Front that likely provoked local permafrost formation. These cold periods coincide with both low summer 65°N insolation, low atmospheric CO2 concentration and large ice sheets development (especially the Fennoscandian).

Pollen record and dating of a sediment profile from Ahlequellmoor in Germany

A pollen diagram from the Ahlequellmoor in the Solling area shows the history of vegetation and settlement over the last 7,800 years. In the early Atlantic period mixed deciduous forest with mainly Tilia together with Ulmus and Quercus grew in the area. In the late Atlantic period Quercus became most abundant. Fagus spread in the Sub-boreal period at about 2700 B.C. Since ca. 900 B.C. the Solling was covered by beech forests with some oak. In prehistoric times woodland grazing is indicated. Only in Medieval times are two settlements in the vicinity of the Ahlequellmoor reflected in the pollen diagram. The earlier one is dated to about A.D. 750-1020, and may be connected with the former Monastery of Hethis, which is thought to have existed close to the fen from A.D. 815 to 822. The second Medieval settlement dates to the 11th-12th century. The large-scale woodland destruction of late Medieval and modern times is not clearly visible. The silvicultural measures of the last 200 years are reflected by increasing values of spruce and grassland taxa.

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.

Stable isotopic ratios, shell lengths and organochlorine compounds in four bivalve species collected in July 2009 around Svalbard

Organochlorine compounds (OC) were determined in Arctic bivalves (Mya truncata, Serripes groenlan-dicus, Hiatella arctica and Chlamys islandica) from Svalbard with regard to differences in geographic location, species and variations related to their size and age. Higher chlorinated polychlorinated biphenyls (PCB 101-PCB 194), chlordanes and alpha-hexachlorocyclohexane (alpha-HCH) were consistently detected in the bivalves and PCBs dominated the OC load in the organisms. OC concentrations were highest in Mya truncata and the lowest in Serripes groenlandicus. Species-specific OC levels were likely related to differences in the species' food source, as indicated by the d13C results, rather than size and age. Higher OC concentrations were observed in bivalves from Kongsfjorden compared to the northern sampling locations Liefdefjorden and Sjuoyane. The spatial differences might be related to different water masses influencing Kongsfjorden (Atlantic) and the northern locations (Arctic), with differing phytoplankton bloom situations.

Isotope ratios, trace elements and ultrastructure results of Mytilus galloprovincialis shells and experimental site data off Ischia (Italy)

Bivalve shells can provide excellent archives of past environmental change but have not been used to interpret ocean acidification events. We investigated carbon, oxygen and trace element records from different shell layers in the mussels Mytilus galloprovincialis combined with detailed investigations of the shell ultrastructure. Mussels from the harbour of Ischia (Mediterranean, Italy) were transplanted and grown in water with mean pHT 7.3 and mean pHT 8.1 near CO2 vents on the east coast of the island. Most prominently, the shells recorded the shock of transplantation, both in their shell ultrastructure, textural and geochemical record. Shell calcite, precipitated subsequently under acidified seawater responded to the pH gradient by an in part disturbed ultrastructure. Geochemical data from all test sites show a strong metabolic effect that exceeds the influence of the low-pH environment. These field experiments showed that care is needed when interpreting potential ocean acidification signals because various parameters affect shell chemistry and ultrastructure. Besides metabolic processes, seawater pH, factors such as salinity, water temperature, food availability and population density all affect the biogenic carbonate shell archive.

Geochemistry and mineralogy of selected carbonaceous claystones at DSDP Hole 76-534

Four dominant depositions of carbonaceous claystones are recognized to have occurred during the early Aptian to middle Albian at Site 534. There are correlations of stable isotope ratios with organic carbon content and of clay content with clay mineralogy of the samples. Almost all organic carbon in these sequences has very negative terrestrial isotope ratios, and the clay of that age indicates predominance of aluminous montmorillonite, which is thought to be of terrigenous origin. It is suggested that development of coastal vegetation belts and deltaic outbuilding with consequent outpouring of land-plant detritus and terrigenous elastics into the deep basins probably led to formation of the "black shale" facies.

Displaced diatom, discoasters and benthic foraminifers at DSDP Hole 72-515A

Late Pliocene to Recent sediments from the southern Brazil Basin (DSDP Hole 515A, hydraulic piston core) were analyzed for evidence of episodic flow of Antarctic Bottom Water (AABW) through the Vema Channel. Carbonate-enriched layers punctuate the post-Pliocene section, otherwise composed predominantly of terrigenous silt and clay. Carbonate enrichment is thought to result from rapid deposition of fine-grained calcareous turbidites, originating in canyons incised on the northern margin of the Rio Grande Rise. The composition of benthic foraminiferal assemblages and the presence of stratigraphically displaced discoasters is consistent with a turbidite origin. Based on the presence of displaced Antarctic diatoms, AABW flow through the Vema Channel apparently has had a major influence on this site for only four periods during the last 2.7 Ma (about 45 to 250; 375 to 430; 700 to 780; 1320 to 1345 thousand yr. ago).

Chemical and isotopic analysis of bulk organic matter and hydrocarbon biomarkers from IODP Holes 311-U1327C, 311-U1328B and 311-U1328C

The chemical and isotopic compositions of sedimentary organic matter (SOM) from two mid-slope sites of the northern Cascadia margin were investigated during Integrated Ocean Drilling Program (IODP) Expedition 311 to elucidate the organic matter origins and identify potential microbial contributions to SOM. Gas hydrate is present at both locations (IODP Sites U1327 and U1328), with distinct patterns of near-seafloor structural accumulations at the cold seep Site U1328 and deeper stratigraphic accumulations at the slope-basin Site U1327. Source characterization and evidence that some components of the organic matter have been diagenetically altered are determined from the concentrations and isotopic compositions of hydrocarbon biomarkers, total organic carbon (TOC), total nitrogen (TN) and total sulfur (TS). The carbon isotopic compositions of TOC (d13C TOC = -26 to -22 per mil) and long-chain n-alkanes (C27, C29 and C31, d13C = -34 to -29 per mil) suggest the organic matter at both sites is a mixture of 1) terrestrial plants that employ the C3 photosynthetic pathway and 2) marine algae. In contrast, the d15N TN values of the bulk sediment (+4 to +8 per mil) are consistent with a predominantly marine source, but these values most likely have been modified during microbial organic matter degradation. The d13C values of archaeal biomarker pentamethylicosane (PMI) (-46.4 per mil) and bacterial-sourced hopenes, diploptene and hop-21-ene (-40.9 to -34.7 per mil) indicate a partial contribution from methane carbon or a chemoautotrophic pathway. Our multi-isotope and biomarker-based conclusions are consistent with previous studies, based only on the elemental composition of bulk sediments, that suggested a mixed marine-terrestrial organic matter origin for these mid-slope sites of the northern Cascadia margin.

Stable isotope record of the Okhotsk Sea

Stable isotope data on benthic foraminifera from more than 30 cores on the northern Emperor Seamounts and in the Okhotsk Sea are synthesized in paleohydrographic profiles spanning the depth range 1000-4000 m. Holocene (core-top) benthic foraminiferal d18O and d13C data are calibrated to modern hydrographic properties through measurements of d13C of SumCO2 and d18O of seawater. Cibicidoides stable isotope ratios are close to the d13C and equilibrium d18O of seawater, whereas Uvigerina d18O and d13C are variably offset from Cibicidoides. Glacial maximum d13C of Cibicidoides displays a different vertical profile than that of the Holocene. When results are adjusted by +0.32 per mil to account for the secular change in d13C during the last glacial maximum, the data coincide with the modern seawater and foraminiferal curves deeper than ~2 km. However, at shallower depths d13C gradually increases by as much as 1 per mil above the modern value. Furthermore, above 2 km the benthic d18O decreases by ~0.5 per mil. These results are consistent with a benthic front at ~2 km in the North Pacific (see Herguera et al., 1992), but they differ from interpretations based on trace metal data which indicate a source of nutrient-depleted deep water during glaciation. The isotopic data suggest that during glaciation there was a better ventilated watermass at intermediate depths in the far northwestern Pacific, it was relatively fresher than deep waters there, and deep waters were as nutrient-rich as today.

Pollen analysis of a sediment profile from Gabelsee in Germany

The article shows that pollen analysis plays an important role in the prediction of potential settlement areas and, furthermore, can offer a crude determination of settlement duration. Especially when the archaeological data fails to offer a possibility of dating, pollen analysis in connection with 14C can importantly broaden the knowledge base. As in the present case, the results of the Archaeo-Prognosis mapping and the pollen analysis of the Gabelsee are compared and, within this vicinity, confirmend. = Der Beitrag zeigt, dass die Pollenanalyse eine wichtige Rolle für die Vorhersage von potenziellen Siedlungsflächen spielen und darüber hinaus eine grobe Berechnung der Siedlungsdauer bieten kann. Insbesondere wenn die archäologische Datenbasis keine genaue Datierung zulässt, ermöglicht die Pollenanalyse in Verbindung mit der 14C-Datierung eine wichtige Erweiterung der Kenntnisse. Im vorliegenden Fall konnten die Ergebnisse der Archäoprognosekarte mit denjenigen der Pollenanalyse des Gabelsees verglichen und für diesen lokalen Raum bestätigt werden.

Stable isotope ratios of foraminifera and sea surface temperature estimation of sediment core W2804A-14

Carbon isotopically based estimates of CO2 levels have been generated from a record of the photosynthetic fractionation of 13C (epsilon p) in a central equatorial Pacific sediment core that spans the last ~255 ka. Contents of 13C in phytoplanktonic biomass were determined by analysis of C37 alkadienones. These compounds are exclusive products of Prymnesiophyte algae which at present grow most abundantly at depths of 70-90 m in the central equatorial Pacific. A record of the isotopic compostion of dissolved CO2 was constructed from isotopic analyses of the planktonic foraminifera Neogloboquadrina dutertrei, which calcifies at 70-90 m in the same region. Values of epsilon p, derived by comparison of the organic and inorganic delta values, were transformed to yield concentrations of dissolved CO2 (c e) based on a new, site-specific calibration of the relationship between epsilon p and c e. The calibration was based on reassessment of existing epsilon p versus c e data, which support a physiologically based model in which epsilon p is inversely related to c e. Values of PCO2, the partial pressure of CO2 that would be in equilibrium with the estimated concentrations of dissolved CO2, were calculated using Henry's law and the temperature determined from the alkenone-unsaturation index UK 37. Uncertainties in these values arise mainly from uncertainties about the appropriateness (particularly over time) of the site-specific relationship between epsilon p and 1/c e. These are discussed in detail and it is concluded that the observed record of epsilon p most probably reflects significant variations in Delta pCO2, the ocean-atmosphere disequilibrium, which appears to have ranged from ~110 µatm during glacial intervals (ocean > atmosphere) to ~60 µatm during interglacials. Fluxes of CO2 to the atmosphere would thus have been significantly larger during glacial intervals. If this were characteristic of large areas of the equatorial Pacific, then greater glacial sinks for the equatorially evaded CO2 must have existed elsewhere. Statistical analysis of air-sea pCO2 differences and other parameters revealed significant (p < 0.01) inverse correlations of Delta pCO2 with sea surface temperature and with the mass accumulation rate of opal. The former suggests response to the strength of upwelling, the latter may indicate either drawdown of CO2 by siliceous phytoplankton or variation of [CO2]/[Si(OH)4] ratios in upwelling waters.

Geochemistry and morphometry on planktonic foraminifera

About one third of the anthropogenic carbon dioxide (CO2) released into the atmosphere in the past two centuries has been taken up by the ocean. As CO2 invades the surface ocean, carbonate ion concentrations and pH are lowered. Laboratory studies indicate that this reduces the calcification rates of marine calcifying organisms, including planktic foraminifera. Such a reduction in calcification resulting from anthropogenic CO2 emissions has not been observed, or quantified in the field yet. Here we present the findings of a study in the Western Arabian Sea that uses shells of the surface water dwelling planktic foraminifer Globigerinoides ruber in order to test the hypothesis that anthropogenically induced acidification has reduced shell calcification of this species. We found that light, thin-walled shells from the surface sediment are younger (based on 14C and d13C measurements) than the heavier, thicker-walled shells. Shells in the upper, bioturbated, sediment layer were significantly lighter compared to shells found below this layer. These observations are consistent with a scenario where anthropogenically induced ocean acidification reduced the rate at which foraminifera calcify, resulting in lighter shells. On the other hand, we show that seasonal upwelling in the area also influences their calcification and the stable isotope (d13C and d18O) signatures recorded by the foraminifera shells. Plankton tow and sediment trap data show that lighter shells were produced during upwelling and heavier ones during non-upwelling periods. Seasonality alone, however, cannot explain the 14C results, or the increase in shell weight below the bioturbated sediment layer. We therefore must conclude that probably both the processes of acidification and seasonal upwelling are responsible for the presence of light shells in the top of the sediment and the age difference between thick and thin specimens.