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.

Planktic foraminifers, oxygen- and carbon isotopic compositions, and radiocarbon age in bottom sediments from Core AMK4-316GC

In a sediment core AMK4-316 (460 cm long) on the basis of radiocarbon, oxygen isotope, and lithological data climatostratigraphy is established for time interval about 145 ka. The method of factor analysis and spline interpolation applied to data on distribution of planktic foraminifera species has allowed to reconstruct average annual and seasonal temperatures and salinity at the surface and at depth 100 m. The optimum of the Last Interglaciation (5e) is characterized by maximal temperatures, low amplitudes of seasonal fluctuations, and by increased thickness of the upper homogeneous layer. The glacial hydrological mode has arisen here 115 ka ago. Coolings outstripped appropriate events of the global continental glaciation. Minimal average annual temperatures (4-4.5°C) are reconstructed for 47-45, 42, 36, 29-30, and 10 ka. For 50-30 ka interval numerous strong temperature fluctuations that reflect migrations of the polar front are established. Maximal differences of salinity at the surface and depth 100 m showing influence of melting waters were in the beginning of deglaciations (135 and 20 ka) and repeatedly arose in 50-30 ka interval. The Last Glacial Maximum (18 ka) is characterized by the lowest salinity but not by a peak of low temperatures at the surface. Surface temperature was lowered up to 10 ka. Average annual surface temperature of the Holocene optimum was 2°C above the modern one and 2°C below temperature in the Interglaciation optimum (5e), thickness of the upper homogeneous layer exceeded 100 m.

Accumulation rates of plant-wax-derived long-chain C25 to C35 odd-numbered n-alkanes and d13C values of the n-C31 alkane of ODP Hole 175-1077B

The dominant forcing factors for past large-scale changes in vegetation are widely debated. Changes in the distribution of C4 plants-adapted to warm, dry conditions and low atmospheric CO2 concentrations (Collatz et al., 1998, doi:10.1007/s004420050468) -have been attributed to marked changes in environmental conditions, but the relative impacts of changes in aridity, temperature (Pagani et al., 1999, doi:10.1126/science.285.5429.876; Huang et al., 2001, doi:10.1126/science.1060143) and CO2 concentration (Cerling et al., 1993, doi:10.1038/361344a0; Kuypers et al., 1999, doi:10.1038/20659) are not well understood. Here, we present a record of African C4 plant abundance between 1.2 and 0.45 million years ago, derived from compound-specific carbon isotope analyses of wind-transported terrigenous plant waxes. We find that large-scale changes in African vegetation are linked closely to sea surface temperatures in the tropical Atlantic Ocean. We conclude that, in the mid-Pleistocene, changes in atmospheric moisture content - driven by tropical sea surface temperature changes and the strength of the African monsoon - controlled aridity on the African continent, and hence large-scale vegetation changes.

Paleotemperature and productivity reconstruction of sediment core D11957P on the Iberian Margin

Foraminifera counts and climatic assemblages from the Tore Seamount are used to approach the glacial and interglacial changes in temperature and productivity on the Iberian Margin over the last 225 kyr. Chronostratigraphy is based on Globigerinoides ruber and Globigerina bulloides oxygen isotopes and supported by foraminifera and carbonate stadial fluctuations. Foraminifera indicate cooling from late interglacial stage 5 to the beginning of Termination I (TI). Neogloboquadnna pachyderma-s reflects cold conditions during glacial stages 4-2. In contrast, glacial stage 6 is dominated by warmer N. pachyderma-d and dutertrei and a restricted arctic assemblage. Past sea surface temperatures confirm the general cooling, reaching 4.3°C (SIMMAX.28) during stage 2. Multiple productivity proxies such as organic carbon, productivity-related foraminifera, and delta13C constrain the changes observed. A productivity increase occurs after interglacial stage 5, enhanced from late glacial stage 3 to TI Present-day satellite-detected phytoplankton plumes off Portugal would have accounted in the past glacial stages for the general productivity increase over the Tore. On top of this, welldefined peaks of organic carbon and productivity-related foraminifera correspond with Heinrich events 1-4.

Seawater carbonate chemistry and impacts of calcium and carbonate ion concentration on Mg and Sr incorporation in cultured benthic foraminifera (Ammonia tepida and Heterostegina depressa), 2011

Laboratory culture experiments were conducted to determine effects of seawater carbonate ion concentration ([CO32-]), and thereby calcite saturation state, on Mg and Sr incorporation into calcite of two species of shallow-water benthic foraminifera: Ammonia tepida and Heterostegina depressa. Impact on Mg and Sr incorporation by increased seawater [CO32-] and thereby higher calcite saturation state, is absent in either species. Comparison to results from a similar culturing experiment, in which calcite saturation state was varied as a function of [Ca2+], reveals that saturation state affects incorporation of Mg and Sr through calcium- rather than carbonate availability. The similarity in response by both species is surprising since the average Mg/Ca ratio is ~ 70 times higher in H. depressa than in A. tepida. Furthermore, these results suggest that the ions involved in biomineralization (i.e. Ca2+ and DIC) are processed by separate cellular transport mechanisms. The similar response of Mg and Sr incorporation in this study suggests that only differences in the Ca2+ transport mechanism affect divalent cation partitioning.

Mineralogical (bulk rock and clay fraction) and stable isotope composition (d13C, d18O) of Aptian deposits of the Bir Oum Ali succession, central Tunisia

Alternations between siliciclastic, carbonate and evaporitic sedimentary systems, as recorded in the Aptian mixed succession of southern Tunisia, reflect profound palaeoceanographic and palaeoclimatic changes in this area of the southern Tethyan margin. The evolution from Urgonian-type carbonates (Berrani Formation, lower Aptian) at the base of the series, to intervals dominated by gypsum or detrital deposits in the remainder of the Aptian is thought to result from the interplay between climate change and tectonic activity that affected North Africa. Based on the evolution of clay mineral assemblages, the early Aptian is interpreted as having been dominated by slightly humid conditions, since smectitic minerals are observed. Near the early to late Aptian boundary, the onset of a gypsiferous sedimentation is associated with the appearance of palygorskite and sepiolite, which supports the installation of arid conditions in this area of the southern Tethyan margin. The evaporitic sedimentation may have also been promoted by the peculiar tectonic setting of the Bir Oum Ali area during the Aptian, where local subsidence may have been tectonically enhanced linked to the opening of northern and central Atlantic. Stress associated with the west and central African rift systems may have triggered the development of NW-SE, hemi-graben structures. Uplifted areas may have constituted potential new sources for clastic material that has been subsequently deposited during the late Aptian. Chemostratigraphic (d13C) correlation of the Bir Oum Ali succession with other peri-Tethyan regions complements biostratigraphic findings, and indicates that a potential expression of the Oceanic Anoxic Event (OAE) 1a may be preserved in this area of Tunisia. Although the characteristic negative spike at the base of this event is not recognized in the present study, a subsequent, large positive excursion with d13C values is of similar amplitude and absolute values to that reported from other peri-Tethyan regions, thus supporting the identification of isotopic segments C4-C7 of the OAE1a. The absence of the negative spike may be linked to either non preservation or non deposition: the OAE1a occurred in a global transgressive context, and since the Bir Oum Ali region was located in the innermost part of the southern Tethyan margin during most of the Aptian, stratigraphic hiatuses may have been longer than in other regions of the Tethys. This emphasizes the importance of integrating several stratigraphic disciplines (bio-, chemo- and sequence stratigraphy) when performing long-distance correlation.

Stable isotope record of foraminifera from the Barents Sea

We measured the oxygen isotopic composition of planktonic and benthic foraminifera in three cores collected at key positions to reconstruct the paleoceanography of the Barents Sea: core ASV 880 on the path of the northern branch of Atlantic water inflowing from the Arctic Ocean, core ASV 1200 in the central basin near the polar front, and core ASV 1157 in the main area of brine formation. Modern seawater d18O measurements show that far from the coast, d18O variations are linearly linked to the salinity changes associated with sea ice melting. The foraminifer d18O records are dated by 14C measurements performed on mollusk shells, and they provide a detailed reconstruction of the paleoceanographic evolution of the Barents Sea during the Holocene. Four main steps were recognized: the terminal phase of the deglaciation with melting of the main glaciers, which were located on the surrounding continent and islands, the short thermal optimum from 7.8 ka B.P. to 6.8 ka B.P., a cold mid-Holocene phase with a large reduction of the inflow of Atlantic water, and the inception of the modern hydrological pattern by 4.7 ka B.P. Brine water formation was active during the whole Holocene. The paleoclimatic evolution of the Barents Sea was driven by both high-latitude summer insolation and the intensity of the Atlantic water inflow.

Benthic (C. wuellerstorfi) d18O, d13C and Cd/Ca in sediment core NEAP 4K across the last deglaciation

We present evidence that the characteristic chemical signature (based on coupled benthic foraminiferal Cd/Ca and d13C) of Antarctic Intermediate waters (AAIW) penetrated throughout the intermediate depths of the Atlantic basin to the high-latitude North Atlantic during the abrupt cooling events of the last deglaciation: Heinrich 1 and the Younger Dryas. AAIW may play the dynamic counterpart to the "bipolar seesaw" when near-freezing salty bottom waters from the Antarctic (AABW) sluggishly ventilate the deep ocean. Our data reinforce the concept that interglacial circulation is stabilized by salinity feedbacks between salty northern sourced deep waters (NADW) and fresh southern sourced waters (AABW and AAIW). Further, the glacial ocean may be susceptible to the more finely balanced relative densities of NADW and AAIW, due to either freshwater input or a reversal of the salinity gradient, such that the ocean is poised for NADW collapse via a negative salinity feedback. The unstable climate of the glacial period and its termination may arise from the closer competition for ubiquity at intermediate depths between northern and southern sourced intermediate waters.