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.

Benthic foraminifera groups of ODP Site 162-982

The pulsed decline and eventual extinction of 51 species of elongate, cylindrical deep-sea benthic foraminifera (Stilostomellidae, Pleurostomellidae, and some Nodosariidae) occurred at intermediate water depths (1145-2168 m, Sites 980 and 982) in the northern North Atlantic during the mid-Pleistocene transition (MPT, 1.2-0.6 Ma). In the early Pleistocene, prior to their disappearance, these species comprised up to 20% of the total abundance of the benthic foraminiferal assemblage at 2168 m, but up to only 2% at 1145 m. The MPT extinction of 51 species represents ?20% of the total benthic foraminiferal diversity at bathyal depths in the North Atlantic (excluding the myriad of small unilocular forms). The extinction rate during the MPT was approximately 10 species per 0.1 myr, being one or two orders of magnitude greater than normal background turnover rates of deep-sea benthic foraminifera. Comparison of the precise timings of declines and disappearances (= highest occurrences) of each species shows that they were often diachronous between the two depths. The last of these species to disappear in the North Atlantic was Pleurostomella alternans at ~0.679 and ~0.694 Ma in Sites 980 and 982, respectively, which is in good agreement with the previously documented global "Stilostomella extinction" datum within the period 0.7-0.58 Ma. Comparison with similar studies in intermediate depth waters in the Southwest Pacific Gateway indicates that ~61% of the extinct species were common to both regions, and that although the pattern of pulsed decline was similar, the precise order and timing of the extinction of individual species were mostly different on opposite sides of the world. Previous studies have indicated that this extinct group of elongate, cylindrical foraminifera lived infaunally and had their greatest abundances in poorly ventilated, lower oxygen environments. This is supported by our study where there is a strong positive correlation (r = ~+ 0.8) between the flux of the extinction group and low-oxygen/high organic input species (such as Uvigerina, Bulimina and Bolivina) during the MPT, suggesting a close relationship with lower oxygen levels and high food supply to the sea floor. The absolute abundance, flux, and number of the extinction group of species show a progressive withdrawal pattern with major decreases occurring in cold periods with high d13C values. This might be related to increasing chemical ventilation of glacial intermediate water.

Sedimentology on core MSM05/05_723-2

Two high-resolution sediment cores from eastern Fram Strait have been investigated for sea subsurface and surface temperature variability during the Holocene (the past ca 12,000 years). The transfer function developed by Husum and Hald (2012) has been applied to sediment cores in order to reconstruct fluctuations of sea subsurface temperatures throughout the period. Additional biomarker and foraminiferal proxy data are used to elucidate variability between surface and subsurface water mass conditions, and to conclude on the Holocene climate and oceanographic variability on the West Spitsbergen continental margin. Results consistently reveal warm sea surface to subsurface temperatures of up to 6 °C until ca 5 cal ka BP, with maximum seawater temperatures around 10 cal ka BP, likely related to maximum July insolation occurring at that time. Maximum Atlantic Water (AW) advection occurred at surface and subsurface between 10.6 and 8.5 cal ka BP based on both foraminiferal and dinocyst temperature reconstructions. Probably, a less-stratified, ice-free, nutrient-rich surface ocean with strong AW advection prevailed in the eastern Fram Strait between 10 and 9 cal ka BP. Weakened AW contribution is found after ca 5 cal ka BP when subsurface temperatures strongly decrease with minimum values between ca 4 and 3 cal ka BP. Cold late Holocene conditions are furthermore supported by high planktic foraminifer shell fragmentation and high d18O values of the subpolar planktic foraminifer species Turborotalita quinqueloba. While IP25-associated indices as well as dinocyst data suggest a sustained cooling due to a decrease in early summer insolation and consequently sea-ice increase since about 7 cal ka BP in surface waters, planktic foraminiferal data including stable isotopes indicate a slight return of stronger subsurface AW influx since ca 3 cal ka BP. The observed decoupling of surface and subsurface waters during the later Holocene is most likely attributed to a strong pycnocline layer separating cold sea-ice fed surface waters from enhanced subsurface AW advection. This may be related to changes in North Atlantic subpolar versus subtropical gyre activity.

Planktic foraminifera of sediment core GeoB1710-3

In this study, we test various parameters in deep-sea sediments (bulk sediment parameters and changes in microfossil abundances and preservation character) which are generally accepted as indicators of calcium carbonate dissolution. We investigate sediment material from station GeoB 1710-3 in the northern Cape Basin (eastern South Atlantic), 280 km away from the Namibian coast, well outside today's coastal upwelling. As northern Benguela upwelling cells were displaced westward and periodically preceded the core location during the past 245 kyr (Volbers et al., submitted), GeoB 1710-3 sediments reflect these changes in upwelling productivity. Results of the most commonly used calcium carbonate dissolution proxies do not only monitor dissolution within these calcareous sediments but also reflect changes in upwelling intensity. Accordingly, these conventional proxy parameters misrepresent, to some extent, the extent of calcium carbonate dissolution. These results were verified by an independent dissolution proxy, the Globigerina bulloides dissolution index (BDX') (Volbers and Henrich, 2002, doi:10.1016/S0025-3227(02)00333-X). The BDX' is based on scanning electronic microscope ultrastructural investigation of planktonic foraminiferal tests and indicates persistent good carbonate preservation throughout the past 245 kyr, with the exception of one pronounced dissolution event at early oxygen isotopic stage (OIS) 6. The early OIS 6 is characterized by calcium carbonate contents, sand contents, and planktonic foraminiferal concentrations all at their lowest levels for the last 245 kyr. At the same time, the ratio of radiolarian to planktonic foraminiferal abundances and the ratio of benthic to planktonic foraminiferal tests are strongly increased, as are the rain ratio, the fragmentation index, and the BDX'. The sedimentary calcite lysocline rose above the core position and GeoB 1710-3 sediments were heavily altered, as attested to by the unusual accumulation of pellets, aggregates, sponge spicules, radiolaria, benthic foraminifera, and planktonic foraminiferal assemblages. Solely the early OIS 6 dissolution event altered the coarse fraction intensely, and is therefore reflected by all conventional calcium carbonate preservation proxies and the BDX'. We attribute the more than 1000 m rise of the sedimentary calcite lysocline to the combination of two processes: (a) a prominent change in the deep-water mass distribution within the South Atlantic and (b) intense degradation of organic material within the sediment (preserved as maximum total organic carbon content) creating microenvironments favorable for calcium carbonate dissolution.

Sea surface temperature reconstruction based on planktonic foraminifera of surface sediments and sediment cores off Iberia

Quantitative and qualitative analyses of planktonic foraminiferal assemblages from 134 core-top sediment samples collected along the western Iberian margin were used to assess the latitudinal and longitudinal changes in surface water conditions and to calibrate a Sea Surface Temperature (SST) transfer function for this seasonal coastal upwelling region. Q-mode factor analysis performed on relative abundances yielded three factors that explain 96% of the total variance: factor 1 (50%) is exclusively defined by Globigerina bulloides, the most abundant and widespread species, and reflects the modern seasonal (May to September) coastal upwelling areas; factor 2 (32%) is dominated by Neogloboquadrina pachyderma (dextral) and Globorotalia inflata and seems to be associated with the Portugal Current, the descending branch of the North Atlantic Drift; factor 3 (14%) is defined by the tropical-sub-tropical species Globigerinoides ruber (white), Globigerinoides trilobus trilobus, and G. inflata and mirrors the influence of the winter-time eastern branch of the Azores Current. In conjunction with satellite-derived SST for summer and winter seasons integrated over an 18 year period the regional foraminiferal data set is used to calibrate a SST transfer function using Imbrie & Kipp, MAT and SIMMAX(ndw) techniques. Similar predicted errors (RMSEP), correlation coefficients, and residuals' deviation from SST estimated for both techniques were observed for both seasons. All techniques appear to underestimate SST off the southern Iberia margin, an area mainly occupied by warm waters where upwelling occurs only occasionally, and overestimate SST on the northern part of the west coast of the Iberia margin, where cold waters are present nearly all year round. The comparison of these regional calibrations with former Atlantic and North Atlantic calibrations for two cores, one of which is influenced by upwelling, reveals that the regional one attests more robust paleo-SSTs than for the other approaches.

Planktonic foraminifera abundances and isotopes of Late Quaternary sediments off New Zealand

A series of cores from east of New Zealand have been examined to determine the paleoceanographic history of the late Quaternary in the SW Pacific using planktonic foraminiferal data. Distinct shifts of species can be seen between glacial and interglacial times especially south of Chatham Rise east of South Island. Foraminiferal fragmentation ratios and benthic/planktonic foraminiferal ratios both show increased dissolution during glacials, especially isotope stage 2 to the south of Chatham Rise. The present-day Subtropical Convergence appears to be tied to the Chatham Rise at 44°S, but during glacial times this rise separated cold water to the south from much warmer water to the north, with an associated strong thermal gradient across the rise. We estimate that this gradient could have presented as much as an 8°C temperature change across 4° of latitude during the maximum of the last ice age. There is only weak evidence of the Younger Dryas cool event, but there is a clear climatic optimum between 8 and 6.4 ka with temperatures 1°-2°C higher than the present day. The marine changes compare well with vegetational changes on both South and North Island.