Chemical composition of Late Cenozoic volcanic and volcaniclastic deposits from the western Woodlark Basin area, SW Pacific

Tephra fallout layers and volcaniclastic deposits, derived from volcanic sources around and on the Papuan Peninsula, form a substantial part of the Woodlark Basin marine sedimentary succession. Sampling by the Ocean Drilling Program Leg 180 in the western Woodlark Basin provides the opportunity to document the distribution of the volcanically-derived components as well as to evaluate their chronology, chemistry, and isotope compositions in order to gain information on the volcanic sources and original magmatic systems. Glass shards selected from 57 volcanogenic layers within the sampled Pliocene-Pleistocene sedimentary sequence show predominantly rhyolitic compositions, with subordinate basaltic andesites, basaltic trachy-andesites, andesites, trachy-andesites, dacites, and phonolites. It was possible to correlate only a few of the volcanogenic layers between sites using geochemical and age information apparently because of the formation of strongly compartmentalised sedimentary realms on this actively rifting margin. In many cases it was possible to correlate Leg 180 volcanic components with their eruption source areas based on chemical and isotope compositions. Likely sources for a considerable number of the volcanogenic deposits are Moresby and Dawson Strait volcanoes (D'Entrecasteaux Islands region) for high-K calc-alkaline glasses. The Dawson Strait volcanoes appear to represent the source for five peralkaline tephra layers. One basaltic andesitic volcaniclastic layer shows affinities to basaltic andesites from the Woodlark spreading tip and Cheshire Seamount. For other layers, a clear identification of the sources proved impossible, although their isotope and chemical signatures suggest similarities to south-west Pacific subduction volcanism, e.g. New Britain and Tonga- Kermadec island arcs. Volcanic islands in the Trobriand Arc (for example, Woodlark Island Amphlett Islands and/or Egum Atoll) are probable sources for several volcaniclastic layers with ages between 1.5 to 3 Ma. The Lusancay Islands can be excluded as a source for the volcanogenic layers found during Leg 180. Generally, the volcanogenic layers indicate much calc-alkaline rhyolitic volcanism in eastern Papua since 3.8 Ma. Starting at 135 ka, however, peralkaline tephra layers appear. This geochemical change in source characteristics might reflect the onset of a change in geotectonic regime, from crustal subduction to spreading, affecting the D'Entrecasteaux Islands region. Initial 143Nd/144Nd ratios as low as 0.5121 and 0.5127 for two of the tephra layers are interpreted as indicating that D'Entrecasteaux Islands volcanism younger than 2.9 Ma occasionally interacted with the Late Archean basement, possibly reflecting the mobilisation of the deep continental crust during active rift propagation.

Beryllium, neodymium and metal composition of ODP Leg 194 sites and survey sites crusts

Be and Nd isotope compositions and metal concentrations (Mn, Fe, Co, Ni, and Cu) of surface and subsurface ferromanganese hardground crusts from Ocean Drilling Program Leg 194 Marion Plateau Sites 1194 and 1196 provide new insights into the crusts' genesis, growth rates, and ages. Metal compositions indicate that the hardgrounds, which have grown on erosional surfaces in water depths of <400 m because of strong bottom currents, are not pure hydrogenetic precipitates. Nevertheless, the ratios between cosmogenic 10Be and stable 9Be in hardgrounds from the present-day seafloor at Site 1196 between 1 x 10**-7 and 1.5 x 10**-7 are within the range of values expected for Pacific seawater, which shows that the hardgrounds recorded the isotope composition of ambient seawater. This is also confirmed by their Nd isotope composition (epsilon Nd between -3 and 0). The 10Be/9Be ratios in the up to 30-mm-thick and partly laminated hardgrounds do not show a decrease with depth, which suggests high growth rates on the present-day seafloor. The subsurface crust at Site 1194 (117 m below the seafloor) grew during a sedimentation hiatus, when bottom currents in the late Miocene prevented sediment accumulation on the carbonate platform during a sea level lowstand. The age of 8.65 ± 0.50 Ma for this crust obtained from 10Be-based dating agrees well with the combined seismostratigraphic and biostratigraphic evidence, which suggests an age for the hiatus between 7.7 and 11.8 Ma.

(Table 1) Sample locations, Hf and Nd isotopic compositions and concentrations of Atlantic seawater samples with hydrographic details

The first full water column hafnium isotopic compositions of Atlantic seawater have been obtained at seven locations from the Labrador Sea to the Drake Passage. Despite subpicomolar concentrations in seawater, a precision of the Hf isotopic measurements of <0.7 epsilon-Hf units was achieved. An overall epsilon-Hf range between -3.1 in the Labrador Sea and +4.4 in Antarctic bottom water was determined, the distribution of which broadly reflects continental weathering inputs. Within particular water column profiles, significant differences of up to 4 epsilon-Hf units occur. Combined with Nd isotope data of the same samples, it is evident that the Hf isotopic composition of seawater is too radiogenic for a given Nd isotopic composition and that the largest difference between expected and measured Hf isotopic compositions in seawater occurs near the oldest continental crust in the Labrador Sea. This corroborates the previous proposition, which was mainly based on ferromanganese crust data, that the Hf isotopic composition of seawater is controlled by incongruent weathering of continental crust and possibly, to some extent, by hydrothermal contributions. Hafnium concentrations in the ocean do not increase along the deep ocean conveyer indicating an oceanic residence time of only a few hundred years, which is significantly shorter than previously assumed. The Hf isotopic composition of past seawater can therefore serve as a proxy for short distance, basin scale mixing processes and the regime and intensity of nearby continental weathering processes.

Radiogenic neodymium, strontium and lead isotopes of authigenic and detrital sedimentary phases and stable oxygen and carbon isotopes of benthic foraminifera from gravity cores SO213-59-2 and SO213-60-1 (central South Pacific).

The South Pacific is a sensitive location for the variability of the global oceanic thermohaline circulation given that deep waters from the Atlantic Ocean, the Southern Ocean, and the Pacific Basin are exchanged. Here we reconstruct the deep water circulation of the central South Pacific for the last two glacial cycles (from 240,000 years ago to the Holocene) based on radiogenic neodymium (Nd) and lead (Pb) isotope records complemented by benthic stable carbon data obtained from two sediment cores located on the flanks of the East Pacific Rise. The records show small but consistent glacial/interglacial changes in all three isotopic systems with interglacial average values of -5.8 and 18.757 for epsilon Nd and 206Pb/204Pb, respectively, whereas glacial averages are -5.3 and 18.744. Comparison of this variability of Circumpolar Deep Water (CDW) to previously published records along the pathway of the global thermohaline circulation is consistent with reduced admixture of North Atlantic Deep Water to CDW during cold stages. The absolute values and amplitudes of the benthic delta13C variations are essentially indistinguishable from other records of the Southern Hemisphere and confirm that the low central South Pacific sedimentation rates did not result in a significant reduction of the amplitude of any of the measured proxies. In addition, the combined detrital Nd and strontium (87Sr/86Sr) isotope signatures imply that Australian and New Zealand dust has remained the principal contributor of lithogenic material to the central South Pacific.

Late Glacial and Holocene data from sediment cores MD99-2236 and MD99-2256

The Laurentide Ice Sheet (LIS) was a large, dynamic ice sheet in the early Holocene. The glacial events through Hudson Strait leading to its eventual demise are recorded in the well-dated Labrador shelf core, MD99-2236 from the Cartwright Saddle. We develop a detailed history of the timing of ice-sheet discharge events from the Hudson Strait outlet of the LIS during the Holocene using high-resolution detrital carbonate, ice rafted detritus (IRD), d18O, and sediment color data. Eight detrital carbonate peaks (DCPs) associated with IRD peaks and light oxygen isotope events punctuate the MD99-2236 record between 11.5 and 8.0 ka. We use the stratigraphy of the DCPs developed from MD99-2236 to select the appropriate DeltaR to calibrate the ages of recorded glacial events in Hudson Bay and Hudson Strait such that they match the DCPs in MD99-2236. We associate the eight DCPs with H0, Gold Cove advance, Noble Inlet advance, initial retreat of the Hudson Strait ice stream (HSIS) from Hudson Strait, opening of the Tyrrell Sea, and drainage of glacial lakes Agassiz and Ojibway. The opening of Foxe Channel and retreat of glacial ice from Foxe Basin are represented by a shoulder in the carbonate data. DeltaR of 350 years applied to the radiocarbon ages constraining glacial events H0 through the opening of the Tyrell Sea provided the best match with the MD99-2236 DCPs; DeltaR values and ages from the literature are used for the younger events. A very close age match was achieved between the 8.2 ka cold event in the Greenland ice cores, DCP7 (8.15 ka BP), and the drainage of glacial lakes Agassiz and Ojibway. Our stratigraphic comparison between the DCPs in MD99-2236 and the calibrated ages of Hudson Strait/Bay deglacial events shows that the retreat of the HSIS, the opening of the Tyrell Sea, and the catastrophic drainage of glacial lakes Agassiz and Ojibway at 8.2 ka are separate events that have been combined in previous estimates of the timing of the 8.2 ka event from marine records. SW Iceland shelf core MD99-2256 documents freshwater entrainment into the subpolar gyre from the Hudson Strait outlet via the Labrador, North Atlantic, and Irminger currents. The timing of freshwater release from the LIS Hudson Strait outlet in MD99-2236 matches evidence for freshwater forcing and LIS icebergs carrying foreign minerals to the SW Iceland shelf between 11.5 and 8.2 ka. The congruency of these records supports the conclusion of the entrainment of freshwater from the retreat of the LIS through Hudson Strait into the subpolar gyre and provides specific time periods when pulses of LIS freshwater were present to influence climate.

Radiocarbon ages, grain sizes, paleomagentic properties and XRF data of Lake Nam Co sediments, Tibetan Plateau

In September 2008 several cores (68 cm-115 cm length) (water depth: 93 m) were retrieved from Lake Nam Co (southern-central Tibetan Plateau; 4718 m a.s.l.). This study focuses on the interpretation of high-resolution (partly 0.2 cm) data from three gravity cores and the upper part of a 10.4 m long piston core, i.e., the past 4000 cal BP in terms of lake level changes, hydrological variations in the catchment area and consequently variations in monsoon strength. A wide spectrum of sedimentological, geochemical and mineralogical investigations was carried out. Results are presented for XRF core-scans, grain size distribution, XRD-measurements and SEM-image analyses. These data are complemented by an age-depth model using 210Pb and 137Cs analyses as well as eleven AMS-14C-ages. This model is supported by excellent agreement between secular variations determined on one of the gravity cores to geomagnetic field models. This is a significant improvement of the chronology as most catchments of lacustrine systems on the Tibetan Plateau contain carbonates resulting in an unknown reservoir effect for radiocarbon dates. The good correlation of our record to the geomagnetic field models confirms our age-depth model and indicates only insignificant changes in the reservoir effect throughout the last 4 ka. High (summer-) monsoonal activity, i.e. moist environmental conditions, was detected in our record between approximately 4000 and 1950 cal BP as well as between 1480 and 1200 cal BP. Accordingly, lower monsoon activity prevails in periods between the two intervals and thereafter. This pattern shows a good correlation to the variability of the Indian Ocean Summer Monsoon (IOSM) as recorded in a peat bog ~1000 km in NE direction from Lake Nam Co. This is the first time that such a supra regional homogenous monsoon activity is shown on the Tibetan Plateau and beyond. Finally our data show a significant lake level rise after the Little Ice Age (LIA) in Lake Nam Co which is suggested to be linked to glacier melting in consequence of rising temperatures occurring on the whole Tibetan Plateau during this time.

Chemistry and grain-size distribution of terrigenous sediments deposited at Site GeoB9501

The Sahara Desert is the largest source of mineral dust in the world. Emissions of African dust increased sharply in the early 1970s, a change that has been attributed mainly to drought in the Sahara/Sahel region caused by changes in the global distribution of sea surface temperature. The human contribution to land degradation and dust mobilization in this region remains poorly understood, owing to the paucity of data that would allow the identification of long-term trends in desertification. Direct measurements of airborne African dust concentrations only became available in the mid-1960s from a station on Barbados and subsequently from satellite imagery since the late 1970s: they do not cover the onset of commercial agriculture in the Sahel region ~170 years ago. Here we construct a 3,200-year record of dust deposition off northwest Africa by investigating the chemistry and grain-size distribution of terrigenous sediments deposited at a marine site located directly under the West African dust plume. With the help of our dust record and a proxy record for West African precipitation we find that, on the century scale, dust deposition is related to precipitation in tropical West Africa until the seventeenth century. At the beginning of the nineteenth century, a sharp increase in dust deposition parallels the advent of commercial agriculture in the Sahel region. Our findings suggest that human-induced dust emissions from the Sahel region have contributed to the atmospheric dust load for about 200 years.

Nd isotopes an geochemistry of bulk deep sea sediments of the Atlantic Ocean

Nd isotopes preserved in fossil fish teeth and ferromanganese crusts have become a common tool for tracking variations in water mass composition and circulation through time. Studies of Nd isotopes extracted from Pleistocene to Holocene bulk sediments using hydroxylamine hydrochloride (HH) solution yield high resolution records of Nd isotopes that can be interpreted in terms of deep water circulation, but concerns about diagenesis and potential contamination of the seawater signal limit application of this technique to geologically young samples. In this study we demonstrate that Nd extracted from the > 63 µm, decarbonated fraction of older Ocean Drilling Program (ODP) sediments using a 0.02 M HH solution produces Nd isotopic ratios that are within error of values from cleaned fossil fish teeth collected from the same samples, indicating that the HH-extractions are robust recorders of deep sea Nd isotopes. This excellent correlation was achieved for 94 paired fish teeth and HH-extraction samples ranging in age from the Miocene to Cretaceous, distributed throughout the north, tropical and south Atlantic, and composed of a range of lithologies including carbonate-rich oozes/chalks and black shales. The strong Nd signal recovered from Cretaceous anoxic black shale sequences is unlikely to be associated with ferromanganese oxide coatings, but may be derived from abundant phosphatic fish teeth and debris or organic matter in these samples. In contrast to the deep water Nd isotopic signal, Sr isotopes from HH-extractions are often offset from seawater values, suggesting that evaluation of Sr isotopes is a conservative test for the integrity of Nd isotopes in the HH fraction. However, rare earth elements (REE) from the HH-extractions and fish teeth produce distinctive middle REE bulge patterns that may prove useful for evaluating whether the Nd isotopic signal represents uncontaminated seawater. Alternatively, a few paired HH-extraction and cleaned fish teeth samples from each site of interest can be used to verify the seawater composition of the HH-extractions. The similarity between isotopic values for the HH-extraction and fish teeth illustrates that the extensive cleaning protocol applied to fish teeth samples is not necessary in typical, carbonate-rich, deep sea sediments.

Biogeochemical, sedimentological and isotopic sediment record of Lake Dojran

A Late Glacial to Holocene sediment sequence (Co1260, 717 cm) from Lake Dojran, located at the boarder of the F.Y.R. of Macedonia and Greece, has been investigated to provide information on climate variability in the Balkan region. A robust age-model was established from 13 radiocarbon ages, and indicates that the base of the sequence was deposited at ca. 12 500 cal yr BP, when the lake-level was low. Variations in sedimentological (H2O, TOC, CaCO3, TS, TOC/TN, TOC/TS, grain-size, XRF, d18Ocarb, d13Ccarb, d13Corg) data were linked to hydro-acoustic data and indicate that warmer and more humid climate conditions characterised the remaining period of the Younger Dryas until the beginning of the Holocene. The Holocene exhibits significant environmental variations, including the 8.2 and 4.2 ka cooling events, the Medieval Warm Period and the Little Ice Age. Human induced erosion processes in the catchment of Lake Dojran intensified after 2800 cal yr BP.

Age model and palaeoclimate records over the past 22,000 years of sediment core GeoB10053-7

The Australian-Indonesian monsoon is an important component of the climate system in the tropical Indo-Pacific region. However, its past variability, relation with northern and southern high-latitude climate and connection to the other Asian monsoon systems are poorly understood. Here we present high-resolution records of monsoon-controlled austral winter upwelling during the past 22,000 years, based on planktic foraminiferal oxygen isotopes and faunal composition in a sedimentary archive collected offshore southern Java. We show that glacial-interglacial variations in the Australian-Indonesian winter monsoon were in phase with the Indian summer monsoon system, consistent with their modern linkage through cross-equatorial surface winds. Likewise, millennial-scale variability of upwelling shares similar sign and timing with upwelling variability in the Arabian Sea. On the basis of element composition and grain-size distribution as precipitation-sensitive proxies in the same archive, we infer that (austral) summer monsoon rainfall was highest during the Bølling-Allerød period and the past 2,500 years. Our results indicate drier conditions during Heinrich Stadial 1 due to a southward shift of summer rainfall and a relatively weak Hadley cell south of the Equator. We suggest that the Australian-Indonesian summer and winter monsoon variability were closely linked to summer insolation and abrupt climate changes in the northern hemisphere.

Sea-surface temperature reconstruction and calibration-function of sediment cores from the Southern Ocean

We provide a new multivariate calibration-function based on South Atlantic modern assemblages of planktonic foraminifera and atlas water column parameters from the Antarctic Circumpolar Current to the Subtropical Gyre and tropical warm waters (i.e., 60°S to 0°S). Therefore, we used a dataset with the abundance pattern of 35 taxonomic groups of planktonic foraminifera in 141 surface sediment samples. Five factors were taken into consideration for the analysis, which account for 93% of the total variance of the original data representing the regional main oceanographic fronts. The new calibration-function F141-35-5 enables the reconstruction of Late Quaternary summer and winter sea-surface temperatures with a statistical error of ~0.5°C. Our function was verified by its application to a sediment core extracted from the western South Atlantic. The downcore reconstruction shows negative anomalies in sea-surface temperatures during the early-mid Holocene and temperatures within the range of modern values during the late Holocene. This pattern is consistent with available reconstructions.

Strontium isotope and rare earth element geochemistry of basalts from DSDP Leg 37

87Sr/S6Sr ratios have been determined on eleven whole rock basalt samples from DSDP Leg 37. The 87Sr/S6Sr ratios range from 0.70305 +/- 4 to 0.70451 +/- 4 due to alteration and contamination with seawater Sr. Leaching with 5% HF has only a small effect on the 87Sr/86Sr of the samples. However, treatment with 6M HCl in acid digestion bombs at 130°C removes the contaminant more effectively. Altered plagioclase and olivine are dissolved during this process. The mean 87Sr/86Sr of four HCl-treated samples from hole 332A is 0.70299 and that for five samples from hole 332B is 0.70297. The 87Sr/86Sr ratios of treated samples from holes 333A and 335 are 0.70304 +/- 4 and 0.70316 +/- 4, respectively. These 87Sr/86Sr ratios are within the range observed for other basalts elsewhere along the Mid-Atlantic Ridge in the North Atlantic. REE distribution patterns have been determined for four samples, three from hole 332B and one from hole 335. CeN/YbN ratios range from 0.58 to 1.30 and do not correlate with 87Sr/86Sr ratios. The source regions of these basalts appear to have been variable in REE abundances.

Model - data comparison of western African rainfall evolutions during the Last Interglacial (130-115 ka)

This dataset characterizes the evolution of western African precipitation indicated by marine sediment geochemical records in comparison to transient simulations using CCSM3 global climate model throughout the Last Interglacial (130-115 ka). It contains (1) defined tie-points (age models), newly published stable isotopes of benthic foraminifera and Al/Si log-ratios of eight marine sediment cores from the western African margin and (2) annual and seasonal rainfall anomalies (relative to pre-industrial values) for six characteristic latitudinal bands in western Africa simulated by CCSM3 (two transient simulations: one non-accelerated and one accelerated experiment).

Hydrogeological investigations in the upper Ouémé catchment in Benin, West Africa

The scope of this PhD thesis was the hydrogeological conceptualisation of the Upper Ouémé river catchment in Benin. The study area exceeds 14,500 km**2 and is underlain by a crystalline basement. At this setting the typical sequence of aquifers - a regolith aquifer at the top and a fractured bedrock aquifer at the bottom - is encountered, which is found in basement areas all over Africa and elsewhere in the world. The chosen regional approach revealed important information about the hydrochemistry and hydrogeology of this catchment. Based on the regional conceptual model a numerical groundwater flow model was designed. The numerical model was used to estimate the impact of climate change on the regional groundwater resources. This study was realised within the framework of the German interdisciplinary research project IMPETUS (English translation: "Integrated approach to the efficient management of scarce water resources in West Africa"), which is jointly managed by the German universities of Bonn and Cologne. Since the year 2000 the Upper Ouémé catchment was the principal target for investigations into the relevant processes of the regional water cycle. A first study from 2000 to 2003 (Fass, 2004, http://nbn-resolving.de/urn:nbn:de:hbz:5n-03849) focused on the hydrogeology of a small local catchment (~30 km**2). In the course of this thesis five field campaigns were underdone from the year 2004 to 2006. In the beginning of 2004 a groundwater monitoring net was installed based on 12 automatic data loggers. Manual piezometric measurements and the sampling of groundwater and surface water were realised for each campaign throughout the whole study area. Water samples were analysed for major ions, for a choice of heavy metals and for their composition by deuterium, oxygen-18 and tritium. The numerical model was performed with FEFLOW. The hydraulic and hydrochemical characteristics were described for the regolith aquifer and the bedrock aquifer. The regolith aquifer plays the role of the groundwater stock with low conductivity while the fractures of the bedrock may conduct water relatively fast towards extraction points. Flow in fractures of the bedrock depends on the connectivity of the fracture network which might be of local to subregional importance. Stable isotopes in combination with hydrochemistry proved that recharge occurs on catchment scale and exclusively by precipitation. Influx of groundwater from distant areas along dominant structures like the Kandi fault or from the Atacora mountain chain is excluded. The analysis of tritium in groundwater from different depths revealed the interesting fact of the strongly rising groundwater ages. Bedrock groundwater may possibly be much older than 50 years. Equilibrium phases of the silicate weathering products kaolinite and montmorillonite showed that the deeper part of the regolith aquifer and the bedrock aquifer feature either stagnant or less mobile groundwater while the shallow aquifer level is influenced by seasonal groundwater table fluctuations. The hydrochemical data characterised this zone by the progressive change of the hydrochemical facies of recently infiltrated rainwater on its flow path into deeper parts of the aquifers. Surprisingly it was found out that seasonal influences on groundwater hydrochemistry are minor, mainly because they affect only the groundwater levels close to the surface. The transfer of the hydrogeological features of the Upper Ouémé catchment into a regional numerical model demanded a strong simplification. Groundwater tables are a reprint of the general surface morphology. Pumping or other types of groundwater extraction would have only very local impact on the available groundwater resources. It was possible to integrate IMPETUS scenario data into the groundwater model. As a result it was shown that the impact of climate change on the groundwater resources until the year 2025 under the given conditions will be negligible due to the little share of precipitation needed for recharge and the low water needs for domestic use. Reason for concern is the groundwater quality on water points in the vicinity of settlements because of contamination by human activities as shown for the village of Dogué. Nitrate concentrations achieved in many places already alerting levels. Health risks from fluoride or heavy metals were excluded for the Upper Ouémé area.

Radiocarbon dates of sediments from ODP Site 161-976

Multiproxy paleoenvironmental records (pollen and planktonic isotope) from Ocean Drilling Program Site 976 (Alboran Sea) document rapid ocean and climate variations during the last glacial that follow the Dansgaard-Oeschger climate oscillations seen in the Greenland ice core records, thus suggesting a close link of the Mediterranean climate swings with North Atlantic climates. Continental conditions rapidly oscillated through cold-arid and warm-wet conditions in the course of stadial-interstadial climate jumps. At the time of Heinrich events, i.e., maximum meltwater flux to the North Atlantic, western Mediterranean marine microflora and microfauna show rapid cooling correlated with increasing continental dryness. Enhanced aridity conceivably points to prolonged wintertime stability of atmospheric high-pressure systems over the southwestern Mediterranean in conjunction with cooling of the North Atlantic.