Environmental magnetism, geochemical measurements and colour reflectance of two sediment cores: GeoB4905-4 off Cameroon and GeoB4906-3 off Gabon

We combine environmental magnetism, geochemical measurements and colour reflectance to study two late Quaternary sediment cores: GeoB 4905-4 at 2° 30 N off Cameroon and GeoB 4906-3 at 0° 44 N off Gabon. This area is suitable for investigating precipitation changes over Central and West Africa because of its potential to record input of aeolian and fluvial sediments. Three magnetozones representing low and high degree of alteration of the primary rock magnetic signals were identified. The magnetic signature is dominated by fine-grained magnetite, while residual haematite prevails in the reduced intervals, showing increase in concentration and fine grain size at wet intervals. Our records also show millennial-scale changes in climate during the last glacial and interglacial cycles. At the northern location, the past 5.5 ka are marked by high-frequency oscillations of Ti and colour reflectance, which suggests aeolian input and hence aridity. The southern location remains under the influence of the Intertropical Convergence Zone and thus did not register aeolian signals. The millennial-scale climatic signals indicate that drier and/or colder conditions persisted during the late Holocene and are synchronous with the 900 a climatic cycles observed in Northern Hemisphere ice core records.

Stable isotope and Cd/Ca ratios of Neogloboquadrina pachyderma in high-latitude sediments

Recent studies have stressed the role of high latitude nutrient levels and productivity in controlling the carbon isotopic composition of the deep sea and the CO2 content of the atmosphere. We undertook a study of the chemical composition of the polar planktonic foraminifer Neogloboquadrina pachyderma (s., sinistral coiling) from 30 late Holocene samples and 49 down core records from the high-latitude North and South Atlantic Oceans to evaluate the history of sea surface chemical change from glacial to interglacial time. Stable isotopic analysis of coretop samples from the Atlantic, Pacific and Southern Oceans shows no significant correlation between the delta13C of N. pachyderma and either delta13C or PO4 in seawater. Conversely, Cd/Ca ratios in planktonic foraminifera are consistent with the PO4 content of surface waters. The level of maximum glaciation (18,000 yr B.P.), identified by CLIMAP and delta18O, was chosen for mapping. Isopleths of delta18O on N. pachyderma (s.) in the North Atlantic reveal a pattern largely influenced by sea surface temperature (S.S.T.) and generally support the S.S.T. reconstruction of CLIMAP. Differences between the two suggest significantly lower salinity in North Atlantic surface waters at high latitudes than in lower latitudes. Down core delta13C records of N. pachyderma confirm that low delta13C values occurred in the northeast Atlantic during the latest glacial maximum (Labeyrie and Duplessy, 1985, doi:10.1016/0031-0182(85)90069-0). However, a map of delta13C for the 18,000 yr B.P. level for a much larger region in the North Atlantic shows that minimum N. pachyderma delta13C occurred in temperate waters. N. pachyderma delta13C decreased toward the southwest, reaching a minimum of -1 per mil at 37°N. Despite the variability seen in delta13C records of N. pachyderma, none of our cores show significant temporal variability in Cd/Ca. From the combined Cd/Ca and delta13C data we can see no evidence for an upwelling gyre in the eastern North Atlantic during the latest glacial maximum, nor evidence that the southern and northern oceans had significantly different levels of preformed nutrients than today.

Description and chemical composition of ferromanganese encrustations and deposits in the Atlantic Ocean from R/V Atlantis II cruises 20, 42, 60, 85; R/V Chain cruise 35; R/V Knorr cruise 61 and RRS Shackleton cruise 75/1 stations

Chemical and mineralogical compositions of ferromanganese oxide coatings on rocks dredged from the New England Seamounts, the Sierra Leone Rise and the Mid-Atlantic Ridge near the Equator have been determined in an investigation of regional differences in Atlantic ferromanganese deposits. Most encrustations are clearly of hydrogenous origin, consisting mainly of todorokite and delta MnO2, but several recovered from the equatorial fracture zones may be hydrothermal accumulations. Differences in the chemistry of the water column and in growth rates of the ferromanganese coatings may be important in producing this regional contrast in composition. Fine-scale changes in element abundances within the encrustations indicate that the nature of the substrate has little influence on compositional variations.

Water temperature reconstruction for Terminations I and II of sediment core MD01-2378

We present centennial records of sea surface and upper thermocline temperatures in Core MD01-2378 from the Timor Sea, which provide new insights into the variability of the Indonesian outflow across the last two glacial terminations. Mg/Ca in Globigerinoides ruber (white s. s.) indicates an overall increase of 3.2 °C in sea surface temperature (SST) over Termination I. Following an early Holocene plateau at 11.3-6.4 ka, SSTs cooled by 0.6 °C during the middle to late Holocene (6.4-0.7 ka). The early Holocene warming occurred in phase with increasing northern hemisphere summer insolation, coinciding with northward displacement of the Intertropical Convergence Zone, enhanced boreal summer monsoon and expansion of the Indo-Pacific Warm Pool. Thermocline temperatures (Pulleniatina obliquiloculata Mg/Ca) gradually decreased from 24.5 to 21.5 °C since 10.3 ka, reflecting intensification of a cool thermocline throughflow. The vertical structure of the upper ocean in the Timor Sea evolved in similar fashion during the Holocene and MIS5e, although the duration of SST plateaux differed (11.3 to 6.4 ka in Termination I and from 129 to 119 ka in Termination II), which was probably due to the more intense northern hemisphere summer insolation during MIS 5e. During both terminations, SST increased simultaneously in the southern high latitudes and the tropical eastern Indian Ocean, suggesting virtually instantaneous atmospheric climate feedbacks between the high and low latitudes.

Plio-Pleistocene Mg/Ca and TEX86 sea surface temperature records of ODP Sites 184-1143 and 165-999,

The western warm pools of the Atlantic and Pacific oceans are a critical source of heat and moisture for the tropical climate system. Over the past five million years, global mean temperatures have cooled by 3-4 °C. Yet, current reconstructions of sea surface temperatures indicate that temperature in the warm pools has remained stable during this time. This stability has been used to suggest that tropical sea-surface temperatures are controlled by some sort of thermostat-like regulation. Here we reconstruct sea surface temperatures in the South China Sea, Caribbean Sea and western equatorial Pacific Ocean for the past five million years, using a combination of the Mg/Ca, TEXH86-and Uk'37 surface temperature proxies. Our data indicate that during the period of Pliocene warmth from about 5 to 2.6 million years ago, the western Pacific and western Atlantic warm pools were about 2 °C warmer than today. We suggest that the apparent lack of warming seen in the previous reconstructions was an artefact of low seawater Mg/Ca ratios in the Pliocene oceans. Taking this bias into account, our data indicate that tropical sea surface temperatures did change in conjunction with global mean temperatures. We therefore conclude that the temperature of the warm pools of the equatorial oceans during the Pliocene was not limited by a thermostat-like mechanism.

X-ray fluorescence (XRF) Ca intensity of sediment cores MD04-2760 and MD04-2788

Accelerator mass spectrometry (AMS) radiocarbon dating of ostracod and gastropod shells from the southwestern Black Sea cores combined with tephrochronology provides the basis for studying reservoir age changes in the lateglacial Black Sea. The comparison of our data with records from the northwestern Black Sea shows that an apparent reservoir age of ~1450 14C yr found in the glacial is characteristic of a homogenized water column. This apparent reservoir age is most likely due to the hardwater effect. Though data indicate that a reservoir age of ~1450 14C yr may have persisted until the Bølling-Allerød warm period, a comparison with the GISP2 ice-core record suggests a gradual reduction of the reservoir age to ~1000 14C yr, which might have been caused by dilution effects of inflowing meltwater. During the Bølling-Allerød warm period, soil development and increased vegetation cover in the catchment area of the Black Sea could have hampered erosion of carbonate bedrock, and hence diminished contamination by "old" carbon brought to the Black Sea basin by rivers. A further reduction of the reservoir age most probably occurred contemporary to the precipitation of inorganic carbonates triggered by increased phytoplankton activity, and was confined to the upper water column. Intensified deep water formation subsequently enhanced the mixing/convection and renewal of intermediate water. During the Younger Dryas, the age of the upper water column was close to 0 yr, while the intermediate water was ~900 14C yr older. The first inflow of saline Mediterranean water, at ~8300 14C yr BP, shifted the surface water age towards the recent value of ~400 14C yr.

Organic carbon concentrations and Cd/Ca ratios of sediment core RC13-229

A comparison of cadmium/calcium (Cd/Ca) records of benthic foraminifera from a deep Cape Basin and a deep eastern equatorial Pacific core suggests that over the past 400,000 years, the nutrient concentration of Circumpolar Deep Water (CPDW) has always been lower than that of the deep Pacific. The data further suggest that at the 100,000- and 23,000-year orbital periods, the contribution of North Atlantic Deep Water to CPDW is at a maximum during periods of ice growth and at a minimum during periods of ice decay. These results are not in agreement with results based on carbon isotope records of benthic foraminifera, which suggest intervals of CPDW nutrient enrichment relative to the deep Pacific and an approximately in-phase relationship between CPDW nutrient concentration and ice volume. Resolution of the apparent conflict between delta13C and Cd/Ca data may provide important constraints on past deep-ocean circulation and nutrient variability.

Grain size analyses, Ca/Ti and other selected elemental ratios from XRF core scanning of sediment cores from the Apulian Margin

An extensive, high-resolution, sedimentological-geochemical survey was done using geo-acoustics, XRF-core scans, ICP-AES, AMS 14C-dating and grain size analyses of sediments in 11 cores from the Gulf of Taranto, the southern Adriatic Sea, and the central Ionian Sea spanning the last 16 cal. ka BP. Comparable results were obtained for cores from the Gallipoli Shelf (eastern Gulf of Taranto), and the southern Adriatic Sea suggesting that the dominant provenance of Gallipoli Shelf sediments is from the western Adriatic mud belt. The 210Pb and 14C-dated high-accumulation-rate sediments permit a detailed reconstruction of climate variability over the last 16 cal. ka BP. Although, the Glacial-Interglacial transition is generally dry and stable these conditions are interrupted by two phases of increased detrital input during the Bølling-Allerød and the late Younger Dryas. The event during the Younger Dryas period is characterized by increased sediment inputs from southern Italian sources. This suggests that run-off was higher in southern- compared to northern Italy. At approximately ~ 7 cal. ka BP, increased detrital input from the Adriatic mud belt, related to sea level rise and the onset of deep water formation in the Adriatic Sea, is observed and is coincident with the end of sapropel S1 formation in the southern Adriatic Sea. During the mid-to-late Holocene we observed millennial-scale events of increased detrital input, e.g. during the Roman Humid Period, and of decreased detrital input, e.g., Medieval Warm Period. These dry/wet spells are consistent with variability in the North Atlantic Oscillation (NAO). A negative state of the NAO and thus a more advanced penetration of the westerlies into the central Mediterranean, that result in wet conditions in the research area concord with events of high detrital input e.g., during the Roman Humid Period. In contrast, a positive state of the NAO, resulting in dry conditions in the Mediterranean, dominated during events of rapid climate change such as the Medieval Warm Period and the Bronze Age.

X-ray fluorescence scanning of discrete samples on the Schwalbenberg II loess-paleosol sequence, raw data, magnetic susceptibility, organic carbon and U-ratio as grainsize index

The Schwalbenberg II loess-paleosol sequence (LPS) denotes a key site for Marine Isotope Stage (MIS 3) in Western Europe owing to eight succeeding cambisols, which primarily constitute the Ahrgau Subformation. Therefore, this LPS qualifies as a test candidate for the potential of temporal high-resolution geochemical data obtained X-ray fluorescence (XRF) scanning of discrete samplesproviding a fast and non-destructive tool for determining the element composition. The geochemical data is first contextualized to existing proxy data such as magnetic susceptibility (MS) and organic carbon (Corg) and then aggregated to element log ratios characteristic for weathering intensity [LOG (Ca/Sr), LOG (Rb/Sr), LOG (Ba/Sr), LOG (Rb/K)] and dust provenance [LOG (Ti/Zr), LOG (Ti/Al), LOG (Si/Al)]. Generally, an interpretation of rock magnetic particles is challenged in western Europe, where not only magnetic enhancement but also depletion plays a role. Our data indicates leaching and top-soil erosion induced MS depletion at the Schwalbenberg II LPS. Besides weathering, LOG (Ca/Sr) is susceptible for secondary calcification. Thus, also LOG (Rb/Sr) and LOG (Ba/Sr) are shown to be influenced by calcification dynamics. Consequently, LOG (Rb/K) seems to be the most suitable weathering index identifying the Sinzig Soils S1 and S2 as the most pronounced paleosols for this site. Sinzig Soil S3 is enclosed by gelic gleysols and in contrast to S1 and S2 only initially weathered pointing to colder climate conditions. Also the Remagen Soils are characterized by subtle to moderate positive excursions in the weathering indices. Comparing the Schwalbenberg II LPS with the nearby Eifel Lake Sediment Archive (ELSA) and other more distant German, Austrian and Czech LPS while discussing time and climate as limiting factors for pedogenesis, we suggest that the lithologically determined paleosols are in-situ soil formations. The provenance indices document a Zr-enrichment at the transition from the Ahrgau to the Hesbaye Subformation. This is explained by a conceptual model incorporating multiple sediment recycling and sorting effects in eolian and fluvial domains.

Geochemistry and mineralogy of sediments from the Atlantis II Fracture Zone

Thirteen sediment samples, including calcareous ooze, sandy clay, volcanic sand, gravel, and volcanic breccia, from Ocean Drilling Program (ODP) Sites 732B, 734B, 734G and Conrad Cruise 27-9, Station 17, were examined. Contents of major and trace elements were determined using XRF or ICP (on samples <0.5 g). Determinations of rare earth elements (REE) were performed using ICP-MS. Mineralogy was determined using XRD. On the basis of the samples studied, the sediments accumulating in the Atlantis II Fracture Zone are characterized by generally high MgO, Cr, and Ni contents compared with other deep-sea sediments. A variety of sources are reflected in the mineralogy and geochemistry of these sediments. Serpentine, brucite, magnetite, and high MgO, Cr, and Ni contents indicate derivation from ultramafic basement. The occurrence of albite, analcime, primary mafic minerals, and smectite/chlorite in some samples, coupled with high SiO2, Al2O3, TiO2, Fe2O3, V, and Y indicate contribution from basaltic basement. A third major sediment source is characterized as biogenic material and is reflected primarily in the presence of carbonate minerals, and high CaO, Sr, Pb, and Zn in certain samples. Kaolinite, illite, quartz, and some chlorite are most likely derived from continental areas or other parts of the ocean by long-distance sediment transport in surface or other ocean currents. Proportions of source materials in the sediments reflect the thickness of the sediment cover, slope of the seafloor, and the nature of and proximity to basement lithologies. REE values are low compared to other deep-sea sediments and indicate no evidence of hydrothermal activity in the Atlantis II Fracture Zone sediments. This is supported by major- and trace-element data.

Sr/Ca ratios of Cenozoic benthic foraminifera

A Cenozoic multi-species record of benthic foraminiferal calcite Sr/Ca has been produced and is corrected for interspecific offsets (typically less than 0.3 mmol/mol) and for the linear relationship between decreasing benthic foraminiferal Sr/Ca and increasing water depth. The water depth correction, determined from Holocene, Late Glacial Maximum and Eocene paleowater-depth transects, is ~0.1 mmol/mol/km. The corrected Cenozoic benthic foraminiferal Sr/Ca record ranges from 1.2 to 2.0 mmol/mol, and has been interpreted in terms of long-term changes in seawater Sr/Ca, enabling issues related to higher-resolution variability in Sr/Ca to be ignored. We estimate that seawater Sr/Ca was ~1.5 times modern values in the late Cretaceous, but declined rapidly into the Paleogene. Following a minimum in the Eocene, seawater Sr/Ca increased gradually through to the present day with a minimum superimposed on this trend centered in the late Miocene. By assuming scenarios for changing seawater calcium concentration, and using published carbonate accumulation rate data combined with suitable values for Sr partition coefficients into carbonates, the seawater Sr/Ca record is used to estimate global average river Sr fluxes. These fluxes are used in conjunction with the seawater strontium isotope curve and estimates of hydrothermal activity/tectonic outgassing to calculate changes in global average river 87Sr/86Sr through the Cenozoic. The absolute magnitude of Sr fluxes and isotopic compositions calculated in this way are subject to relatively large uncertainties. Nevertheless, our results suggest that river Sr flux increased from 35 Ma to the present day (roughly two-fold) accompanied by an overall increase in 87Sr/86Sr (by ~0 to 0.001). Between 75 and 35 Ma, river 87Sr/86Sr also increased (by ~0.001 to 0.002) but was accompanied by a decrease (two- to three-fold) in river Sr flux.