Carbonate preservation of sediment cores from the Great Bahama Bank

The oceanic carbon cycle mainly comprises the production and dissolution/ preservation of carbonate particles in the water column or within the sediment. Carbon dioxide is one of the major controlling factors for the production and dissolution of carbonate. There is a steady exchange between the ocean and atmosphere in order to achieve an equilibrium of CO2; an anthropogenic rise of CO2 in the atmosphere would therefore also increase the amount of CO2 in the ocean. The increased amount of CO2 in the ocean, due to increasing CO2-emissions into the atmosphere since the industrial revolution, has been interpreted as "ocean acidification" (Caldeira and Wickett, 2003). Its alarming effects, such as dissolution and reduced CaCO3 formation, on reefs and other carbonate shell producing organisms form the topic of current discussions (Kolbert, 2006). Decreasing temperatures and increasing pressure and CO2 enhance the dissolution of carbonate particles at the sediment-water interface in the deep sea. Moreover, dissolution processes are dependent of the saturation state of the surrounding water with respect to calcite or aragonite. Significantly increased dissolution has been observed below the aragonite or calcite chemical lysocline; below the aragonite compensation depth (ACD), or calcite compensation depth (CCD), all aragonite or calcite particles, respectively, are dissolved. Aragonite, which is more prone to dissolution than calcite, features a shallower lysocline and compensation depth than calcite. In the 1980's it was suggested that significant dissolution also occurs in the water column or at the sediment-water interface above the lysocline. Unknown quantities of carbonate produced at the sea surface, would be dissolved due to this process. This would affect the calculation of the carbonate production and the entire carbonate budget of the world's ocean. Following this assumption, a number of studies have been carried out to monitor supralysoclinal dissolution at various locations: at Ceara Rise in the western equatorial Atlantic (Martin and Sayles, 1996), in the Arabian Sea (Milliman et al., 1999), in the equatorial Indian Ocean (Peterson and Prell, 1985; Schulte and Bard, 2003), and in the equatorial Pacific (Kimoto et al., 2003). Despite the evidence for supralysoclinal dissolution in some areas of the world's ocean, the question still exists whether dissolution occurs above the lysocline in the entire ocean. The first part of this thesis seeks answers to this question, based on the global budget model of Milliman et al. (1999). As study area the Bahamas and Florida Straits are most suitable because of the high production of carbonate, and because there the depth of the lysocline is the deepest worldwide. To monitor the occurrence of supralysoclinal dissolution, the preservation of aragonitic pteropod shells was determined, using the Limacina inflata Dissolution Index (LDX; Gerhardt and Henrich, 2001). Analyses of the grain-size distribution, the mineralogy, and the foraminifera assemblage revealed further aspects concerning the preservation state of the sediment. All samples located at the Bahamian platform are well preserved. In contrast, the samples from the Florida Straits show dissolution in 800 to 1000 m and below 1500 m water depth. Degradation of organic material and the subsequent release of CO2 probably causes supralysoclinal dissolution. A northward extension of the corrosive Antarctic Intermediate Water (AAIW) flows through the Caribbean Sea into the Gulf of Mexico and might enhance dissolution processes at around 1000 m water depth. The second part of this study deals with the preservation of Pliocene to Holocene carbonate sediments from both the windward and leeward basins adjacent to Great Bahama Bank (Ocean Drilling Program Sites 632, 633, and 1006). Detailed census counts of the sand fraction (250-500 µm) show the general composition of the coarse grained sediment. Further methods used to examine the preservation state of carbonates include the amount of organic carbon and various dissolution indices, such as the LDX and the Fragmentation Index. Carbonate concretions (nodules) have been observed in the sand fraction. They are similar to the concretions or aggregates previously mentioned by Mullins et al. (1980a) and Droxler et al. (1988a), respectively. Nonetheless, a detailed study of such grains has not been made to date, although they form an important part of periplatform sediments. Stable isotopemeasurements of the nodules' matrix confirm previous suggestions that the nodules have formed in situ as a result of early diagenetic processes (Mullins et al., 1980a). The two cores, which are located in Exuma Sound (Sites 632 and 633), at the eastern margin of Great Bahama Bank (GBB), show an increasing amount of nodules with increasing core depth. In Pliocene sediments, the amount of nodules might rise up to 100%. In contrast, nodules only occur within glacial stages in the deeper part of the studied core interval (between 30 and 70 mbsf) at Site 1006 on the western margin of GBB. Above this level the sediment is constantly being flushed by bottom water, that might also contain corrosive AAIW, which would hinder cementation. Fine carbonate particles (<63 µm) form the matrix of the nodules and do therefore not contribute to the fine fraction. At the same time, the amount of the coarse fraction (>63 µm) increases due to the nodule formation. The formation of nodules might therefore significantly alter the grain-size distribution of the sediment. A direct comparison of the amount of nodules with the grain-size distribution shows that core intervals with high amounts of nodules are indeed coarser than the intervals with low amounts of nodules. On the other hand, an initially coarser sediment might facilitate the formation of nodules, as a high porosity and permeability enhances early diagenetic processes (Westphal et al., 1999). This suggestion was also confirmed: the glacial intervals at Site 1006 are interpreted to have already been rather coarse prior to the formation of nodules. This assumption is based on the grain-size distribution in the upper part of the core, which is not yet affected by diagenesis, but also shows coarser sediment during the glacial stages. As expected, the coarser, glacial deposits in the lower part of the core show the highest amounts of nodules. The same effect was observed at Site 632, where turbidites cause distinct coarse layers and reveal higher amounts of nodules than non-turbiditic sequences. Site 633 shows a different pattern: both the amount of nodules and the coarseness of the sediment steadily increase with increasing core depth. Based on these sedimentological findings, the following model has been developed: a grain-size pattern characterised by prominent coarse peaks (as observed at Sites 632 and 1006) is barely altered. The greatest coarsening effect due to the nodule formation will occur in those layers, which have initially been coarser than the adjacent sediment intervals. In this case, the overall trend of the grain-size pattern before and after formation of the nodules is similar to each other. Although the sediment is altered due to diagenetic processes, grain size could be used as a proxy for e.g. changes in the bottom-water current. The other case described in the model is based on a consistent initial grain-size distribution, as observed at Site 633. In this case, the nodule reflects the increasing diagenetic alteration with increasing core depth rather than the initial grain-size pattern. In the latter scenario, the overall grain-size trend is significantly changed which makes grain size unreliable as a proxy for any palaeoenvironmental changes. The results of this study contribute to the understanding of general sedimentation processes in the periplatform realm: the preservation state of surface samples shows the influence of supralysoclinal dissolution due to the degradation of organic matter and due to the presence of corrosive water masses; the composition of the sand fraction shows the alteration of the carbonate sediment due to early diagenetic processes. However, open questions are how and when the alteration processes occur and how geochemical parameters, such as the rise in alkalinity or the amount of strontium, are linked to them. These geochemical parameters might reveal more information about the depth in the sediment column, where dissolution and cementation processes occur.

Lipid analytic of environmental and cultural samples

Membrane lipids of marine planktonic archaea have provided unique insights into archaeal ecology and paleoceanography. However, past studies of archaeal lipids in suspended particulate matter (SPM) and sediments mainly focused on a small class of fully saturated glycerol dibiphytanyl glycerol tetraether (GDGT) homologues identified decades ago. The apparent low structural diversity of GDGTs is in strong contrast to the high diversity of metabolism and taxonomy among planktonic archaea. Furthermore, adaptation of archaeal lipids in the deep ocean remains poorly constrained. We report the archaeal lipidome in SPM from diverse oceanic regimes. We extend the known inventory of planktonic archaeal lipids to include numerous unsaturated archaeal ether lipids (uns-AELs). We further reveal i) different thermal regulations and polar headgroup compositions of membrane lipids between the epipelagic (<= 100 m) and deep (> 100 m) populations of archaea; ii) stratification of unsaturated GDGTs with varying redox conditions; and iii) enrichment of tetra-unsaturated archaeol and fully saturated GDGTs in epipelagic and deep oxygenated waters, respectively. Such stratified lipid patterns are consistent with the typical distribution of archaeal phylotypes in marine environments. We thus provide an ecological context for GDGT-based paleoclimatology and bring about the potential use of uns-AELs as biomarkers for planktonic Euryarchaeota. This article is protected by copyright. All rights reserved.

Siliceous phytoplankton fluxes off northwest Africa

Four years of observations (1988-1991) of downward fluxes of diatoms and silicoflagellates at a trap site off Cape Blanc (ca. 20°N, 20°W), northwest Africa, are presented. Significant variations in flux and species composition were observed as well as a marked drop in the export of biogenic opal (and diatoms) from 1988 to 1989; fluxes remained low thereafter. We hypothesize that this diminution might be related to decreased coastal upwelling intensity and offshore spreading of the typical chlorophyll filament, and/or a lesser silicate content of upwelling waters off Cape Blanc. In addition, the more seaward positioning of the mooring may have influenced the fluxes. At all times, diatoms were the most prominent contributors to the biogenic opal flux, and diatom fluxes closely paralleled total mass flux fluctuations. Although species composition varied seasonally, no significant qualitative variations were observed from year to year. In general, the dominance of neritic diatoms, such as Thalassionema nitzschioides var. nitzschioides, resting spores of Chaetoceros and Cyclotella litoralis, reflected the continuous offshore influence of coastal upwelling at the Cape Blanc trap site, with stronger intensity in spring/summer. In contrast, the occurrence of pelagic diatoms (e.g. Nitzschia bicapitata, N. interruptestriata, T. nitzschioides var. parva and Fragilariopsis doliolus), and high silicoflagellate fluxes (mainly Dictyocha messanensis) were linked to inshore transport of oceanic waters, generally in winter. With the exception of some fragile, pelagic diatoms, dominant species found in the settled material also occurred in the underlying sediments, suggesting that diatom thanatocoenosis downcore (Organisms preserved from the top to the bottom in sediment core) can be used as a reliable indicator of the intensity and persistence of the offshore spreading of coastal upwelling.

Radiocarbon dating, oxygen isotopes, and sea-level reconstruction of sediment core GeoB5844-2 from the northern end of the Red Sea

Based on a radiocarbon and paleomagnetically dated sediment record from the northern Red Sea and the exceptional sensitivity of the regional changes in the oxygen isotope composition of sea water to the sea-level-dependent water exchange with the Indian Ocean, we provide a new global sea-level reconstruction spanning the last glacial period. The sea-level record has been extracted from the temperature-corrected benthic stable oxygen isotopes using coral-based sea-level data as constraints for the sea-level/oxygen isotope relationship. Although, the general features of this millennial-scale sea-level records have strong similarities to the rather symmetric and gradual Southern Hemisphere climate patterns, we observe, in constrast to previous findings, pronounced sea level rises of up to 25 m to generally correspond with Northern Hemisphere warmings as recorded in Greenland ice-core interstadial intervals whereas sea-level lowstands mostly occur during cold phases. Corroborated by CLIMBER-2 model results, the close connection of millennial-scale sea-level changes to Northern Hemisphere temperature variations indicates a primary climatic control on the mass balance of the major Northern Hemisphere ice sheets and does not require a considerable Antarctic contribution.

Organic-walled dinoflagellate cysts and environmental analysis of surface sediments from the Northwest African upwelling area

In order to examine the spatial distribution of organic-walled dinoflagellate cysts (dinocysts) in recent sediments related to environmental conditions in the water column, thirty-two surface sediment samples from the NW African upwelling region (20-32°N) were investigated. Relative abundances of the dinocyst species show distinct regional differences allowing the separation of four hydrographic regimes. (1) In the area off Cape Ghir, which is characterized by most seasonal upwelling and river discharge, Lingulodinium machaerophorum strongly dominates the associations which are additionally characterized by cysts of Gymnodinium nolleri, cysts of Polykrikos kofoidii and cysts of Polykrikos schwartzii. (2) Off Cape Yubi, a region with increasing perennial upwelling, L. machaerophorum, Brigantedinium spp., species of the genus Impagidinium and cysts of Protoperidinium stellatum occur in highest relative abundances. (3) In coastal samples between Cape Ghir and Cape Yubi, Gymnodinium catenatum, species of the genus Impagidinium, Nematosphaeropsis labyrinthus, Operculodinium centrocarpum, cysts of P. stellatum and Selenopemphix nephroides determine the species composition. (4) Off Cape Blanc, where upwelling prevails perennially, and at offshore sites, heterotrophic dinocyst species show highest relative abundances. A Redundancy Analysis reveals fluvial mud, sea surface temperature and the depth of the mixed layer in boreal spring (spring) as the most important parameters relating to the dinocyst species association. Dinocyst accumulation rates were calculated for a subset of samples using well-constrained sedimentation rates. Highest accumulation rates with up to almost 80.000 cysts cm**-2 ky**-1 were found off Cape Ghir and Cape Yubi reflecting their eutrophic upwelling filaments. A Redundancy Analysis gives evidence that primary productivity and the input of fluvial mud are mostly related to the dinocyst association. By means of accumulation rate data, quantitative cyst production of individual species can be considered independently from the rest of the association, allowing autecological interpretations. We show that a combined interpretation of relative abundances and accumulation rates of dinocysts can lead to a better understanding of the productivity conditions off NW Africa.

Delta 44/40 Ca, Mg/Ca and Sr/Ca record of Globigerinoides sacculifer and calculated temperatures and salinity changes of ODP Hole 165-999A

The delta18O values of planktonic foraminifera increased in the Caribbean by about 0.5? relative to the equatorial East Pacific values between 4.6 and 4.2 Ma as a consequence of the closure of the Central American Gateway (CAG). This increase in delta18O can be interpreted either as an increase in Caribbean sea surface (mixed layer) salinity (SSS) or as a decrease in sea surface temperatures (SST). This problem represents an ideal situation to apply the recently developed paleotemperature proxy delta44/40Ca together with Mg/Ca and d18O on the planktic foraminifer Globigerinoides sacculifer from ODP Site 999. Although differences in absolute temperature calibration of delta44/40Ca and Mg/Ca exist, the general pattern is similar indicating a SST decrease of about 2-3 8C between 4.4 and 4.3 Ma followed by an increase in the same order of magnitude between 4.3 and 4.0 Ma. Correcting the delta18O record for this temperature change and assuming that changes in global ice volume are negligible, the salinity-induced planktonic delta18O signal decreased by about 0.4? between 4.4 and 4.3 Ma and increased by about 0.9? between 4.3 and 4.0 Ma in the Caribbean. The observed temperature and salinity trends are interpreted to reflect the restricted exchange of surface water between the Caribbean and the Pacific in response to the shoaling of the Panamanian Seaway, possibly accompanied by a southward shift of the Intertropical Convergence Zone (ITCZ) between 4.4 and 4.3 Ma. Differences in Mg/Ca- and delta44/40Ca-derived temperatures can be reconciled by corrections for secular variations of the marine Mg/Ca[sw] and delta44/40Ca, a salinity effect on the Mg/Ca ratio and a constant temperature offset of ~2.5 °C between both SST proxy calibrations.

Isotope analysis and heat flow measurements of Maria S. Merian cruise MSM21/4 on the western Svalbard margin

Methane hydrate is an ice-like substance that is stable at high-pressure and low temperature in continental margin sediments. Since the discovery of a large number of gas flares at the landward termination of the gas hydrate stability zone off Svalbard, there has been concern that warming bottom waters have started to dissociate large amounts of gas hydrate and that the resulting methane release may possibly accelerate global warming. Here, we can corroborate that hydrates play a role in the observed seepage of gas, but we present evidence that seepage off Svalbard has been ongoing for at least three thousand years and that seasonal fluctuations of 1-2°C in the bottom-water temperature cause periodic gas hydrate formation and dissociation, which focus seepage at the observed sites.

(Table 1) Experimental details and results

Factor-of-safety analyses of submarine slope failure depend critically on the shear strength of the slope material, which is often evaluated with residual strength values and for normally consolidated sediments. Here, we report on direct measurements of both shear strength and cohesion for a quartz-clay mixture over a wide range of overconsolidation ratios (OCRs). For normally consolidated sediment at low stresses, cohesion is the dominant source of shear strength compared to friction. Significant increases in peak shear strength occur for OCR > 4, and the primary source of this strength increase is due to increased cohesion, rather than friction. The proportion of added shear strength due to cohesion depends log-linearly on the OCR. We show that at shallow depths where OCR values can be high, overconsolidated clays can be stronger than pure or nearly pure quartz sediments, which are cohesionless under near-surface conditions. Our data also suggest that areas which have experienced significant unroofing due to previous mass movements are less likely to experience subsequent failure at shallow depths due to increased peak strength, and if failure occurs it is expected to be deeper where the OCR is lower. In seismically active areas, this is one potential explanation for the general observation of lower slope failure recurrence compared to rates expected from triggering due to local earthquakes.

Model simulation output data (CCSM3) related to uplift of Africa and Himalaya/Tibet Plateau and the influence on tropical African vegetation

Hominid evolution in the late Miocene has long been hypothesized to be linked to the retreat of the tropical rainforest in Africa. One cause for the climatic and vegetation change often considered was uplift of Africa, but also uplift of the Himalaya and the Tibetan Plateau was suggested to have impacted rainfall distribution over Africa. Recent proxy data suggest that in East Africa open grassland habitats were available to the common ancestors of hominins and apes long before their divergence and do not find evidence for a closed rainforest in the late Miocene. We used the coupled global general circulation model CCSM3 including an interactively coupled dynamic vegetation module to investigate the impact of topography on African hydro-climate and vegetation. We performed sensitivity experiments altering elevations of the Himalaya and the Tibetan Plateau as well as of East and Southern Africa. The simulations confirm the dominant impact of African topography for climate and vegetation development of the African tropics. Only a weak influence of prescribed Asian uplift on African climate could be detected. The model simulations show that rainforest coverage of Central Africa is strongly determined by the presence of elevated African topography. In East Africa, despite wetter conditions with lowered African topography, the conditions were not favorable enough to maintain a closed rainforest. A discussion of the results with respect to other model studies indicates a minor importance of vegetation-atmosphere or ocean-atmosphere feedbacks and a large dependence of the simulated vegetation response on the land surface/vegetation model.

Al/Si record of sediment core GeoB6211-2

Detrending natural and anthropogenic components of climate variability is arguably an issue of utmost importance to society. To accomplish this issue, one must rely on a comprehensive understanding of the natural variability of the climate system on a regional level. Here we explore how different proxies (e.g., stalagmite oxygen isotopic composition, pollen percentages, bulk sediment elemental ratios) record Holocene precipitation variability over southeastern South America. We found a general good agreement between the different records both on orbital and centennial time-scales. Dry mid Holocene, and wet late Holocene, Younger Dryas and a period between ~9.4 and 8.12 cal kyr BP seem to be pervasive features. Moreover, we show that proxy-specific sensitivity can greatly improve past precipitation reconstructions.

Transient simulations for present and last interglacials using a comprehensive coupled climate model CCSM3 (Community Climate System Model 3.0), links to model result files in NetCDF format

Transient simulations are widely used in studying the past climate as they provide better comparison with any exisiting proxy data. However, multi-millennial transient simulations using coupled climate models are usually computationally very expensive. As a result several acceleration techniques are implemented when using numerical simulations to recreate past climate. In this study, we compare the results from transient simulations of the present and the last interglacial with and without acceleration of the orbital forcing, using the comprehensive coupled climate model CCSM3 (Community Climate System Model 3). Our study shows that in low-latitude regions, the simulation of long-term variations in interglacial surface climate is not significantly affected by the use of the acceleration technique (with an acceleration factor of 10) and hence, large-scale model-data comparison of surface variables is not hampered. However, in high-latitude regions where the surface climate has a direct connection to the deep ocean, e.g. in the Southern Ocean or the Nordic Seas, acceleration-induced biases in sea-surface temperature evolution may occur with potential influence on the dynamics of the overlying atmosphere. The data provided here are from both accelerated and non-accelerated runs as decadal mean values.

(Appendix A) Sedimentation rate, geochemical and environmental magnetic proxies of the samples of the Metochia section, on the island of Gavdos, south of Crete

The upper Tortonian Metochia marls on the island of Gavdos provide an ideal geological archive to trace variations in Aegean sediment supply as well as changes in the North African monsoon system. A fuzzy-cluster analysis on the multiproxy geochemical and rock magnetic dataset of the astronomically tuned sedimentary succession shows a dramatic shift in the dominance of 'Aegean tectonic' clusters to 'North African climate' clusters. The tectonic signature, traced by the starvation of the Cretan sediment, now enables to date the late Tortonian basin foundering on Crete, related to the tectonic break-up of the Aegean landmass, at c. 8.2 Ma. The synchronous decrease in the North African climate proxies is interpreted to indicate a change in the depositional conditions of the sink rather than a climatic change in the African source. This illustrates that interpretations of climate proxies require a multiproxy approach which also assesses possible contributions of regional tectonism.