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.

Multi-proxy analyses of sediment cores from the Pakistan continental margin

Late Holocene laminated sediments from a core transect centred in the oxygen minimum zone (OMZ) impinging at the continental slope off Pakistan indicate stable oxygen minimum conditions for the past 7000 calendar years. High SW-monsoon-controlled biological productivity and enhanced organic matter preservation during this period is reflected in high contents of total organic carbon (TOC) and redox-sensitive elements (Ni, V), as well as by a low-diversity, high-abundance benthic foraminiferal Buliminacea association and high abundance of the planktonic species Globigerina bulloides indicative of upwelling conditions. Surface-water productivity was strongest during SW monsoon maxima. Stable OMZ conditions (reflected by laminated sediments) were found also during warm interstadial events (Preboreal, Bølling-Allerød, and Dansgaard-Oeschger events), as well as during peak glacial times (17-22.5 ka, all ages in calendar years). Sediment mass accumulation rates were at a maximum during the Preboreal and Younger Dryas periods due to strong riverine input and mobilisation of fine-grained sediment coinciding with rapid deglacial sea-level rise, whereas eolian input generally decreased from glacial to interglacial times. In contrast, the occurrence of bioturbated intervals from 7 to 10.5 ka (early Holocene), in the Younger Dryas (11.7-13 ka), from 15 to 17 ka (Heinrich event 1) and from 22.5 to 25 ka (Heinrich event 2) suggests completely different conditions of oxygen-rich bottom waters, extremely low mass and organic carbon accumulation rates, a high-diversity benthic fauna, all indicating lowered surface-water productivity. During these intervals the OMZ was very poorly developed or absent and a sharp fall of the aragonite compensation depth favoured the preservation of pteropods. The abundance of lithogenic proxies suggests aridity and wind transport by northwesterly or northeasterly winds during these periods coinciding with the North Atlantic Heinrich events and dust peaks in the Tibetan Loess records. The correlation of the monsoon-driven OMZ variability in the Arabian Sea with the rapid climatic fluctuations in the high northern latitudes suggests a close coupling between the climates of the high and low latitudes at a global scale.

Organic matter composition of Cretaceous sediments of the central Pacific Ocean

Complete records of organic-carbon-rich Cretaceous strata were continuouslycored on the flanks of the Mid-Pacific Mountains and southern Hess Rise in the central North Pacific Ocean during DSDP Leg 62. Organic-carbon-rich laminated silicified limestones were deposited in the western Mid-Pacific Mountains during the early Aptian, a time when that region was south of the equator and considerably shallower than at present. Organic-carbon-rich, laminated limestone on southern Hess Rise overlies volcanic basement and includes 136 m of stratigraphic section of late Albian to early Cenomanian age. This limestone unit was deposited rapidly as Hess Rise was passing under the equatorial high-productivity zone and was subsiding from shallow to intermediate depths. The association of volcanogenic components with organic-carbon-rich strata on Hess Rise in the Mid-Pacific Mountains is striking and suggests that there was a coincidence of mid-plate volcanic activity and the production and accumulation of organic matter at intermediate water depths in the tropical Pacific Ocean during the middle Cretaceous. Pyrolysis assays and analyses of extractable hydrocarbons indicate that the organic matter in the limestone on Hess Rise is composed mainly of lipid-rich kerogen derived from aquatic marine organisms and bacteria. Limestones from the Mid-Pacific Mountains generally contain low ratios of pyrolytic hydrocarbons to organic carbon and low hydrogen indices, suggesting that the organic matter may contain a significant proportion of land-derived material, possibly derived from numerous volcanic islands that must have existed before the area subsided. The organic carbon in all samples analyzed is isotopically light (d13C -24 to -29 per mil) relative to most modern rine organic carbon, and the lightest carbon is also the most lipid-rich. There is a positive linear correlation between sulfur and organic carbon in samples from Hess Rise and from the Mid-Pacific Mountains. The slopes and intercepts of C-S regression lines however, are different for each site and all are different from regression lines for samples from modern anoxic marine sediments and from Black Sea cores. The organic-carbon-rich limestones on Hess Rise, the Mid-Pacific Mountains, and other plateaus and seamounts in the Pacific Ocean are not synchronous but do occur within the same general middle Cretaceous time period as organic-carbon-rich lithofacies elsewhere in the world ocean, particularly in the Atlantic Ocean. Strata of equivalent age in the deep basins of the Pacific Ocean are not rich in organic carbon, and were deposited in oxygenated environments. This observation, together with the evidence that the plateau sites were considerably shallower and closse to the equator during the middle Creataceous suggests that local tectonic and hydrographic conditions may have resulted in high surface-water productivity and the preservation of organic matter in an oxygen-deficient environment where an expanded mid-water oxygen minimum developed and impinged on elevated platforms and seamounts.

Chemistry of upper Eocene microtektites

Late Eocene microtektites and crystal-bearing microkrystites extracted from DSDP and ODP cores from the Atlantic, Pacific, and Indian oceans have been analyzed to address their provenance. A new analysis of Nd and Sr isotopic compositions confirms previous work and the assignment of the uppermost microtektite layer to the North American tektites, which are associated with the 35.5 Ma, 85 km diameter Chesapeake impact structure of Virginia, USA. Extensive major element and Nd and Sr isotopic analyses of the microkrystites from the lowermost layer were obtained. The melanocratic microkrystites from Sites 216 and 462 in the Indian and Pacific oceans possess major element chemistries, Sr and Nd isotopic signatures and Sm-Nd, T CHUR, model ages similar to those of tagamite melt rocks in the Popigai impact structure. They also possess Rb-Sr, T UR, model ages that are younger than the tagamite TCHUR ages by up to ~1 Ga, which require a process, as yet undefined, of Rb/Sr enrichment. These melanocratic microkrystites are consistent with a provenance from the 35.7 Ma, 100 km diameter Popigai impact structure of Siberia, Russia, while ruling out other contemporaneous structures as a source. Melanocratic microkrystites from other sites and leucocratic microkrystites from all sites possess a wide range of isotopic compositions (epsilon (143Nd) values of -16 to -27.7 and epsilon (87Sr) values of 4.1-354.0), making the association with Popigai tagamites less clear. These microkrystites may have been derived by the melting of target rocks of mixed composition, which were ejected without homogenization. Dark glass and felsic inclusions extracted from Popigai tagamites possess epsilon (143Nd) and epsilon (87Sr) values of -26.7 to -27.8 and 374.7 and 432.4, respectively, and T CHUR and T UR model ages of 1640-1870 Ma and 240-1830 Ma, respectively, which require the preservation of initially present heterogeneity in the source materials. The leucocratic microkrystites possess diverse isotopic compositions that may reflect the melting of supra-basement sedimentary rocks from Popigai, or early basement melts that were ejected prior to homogenization of the Popigai tagamites. The ejection of melt rocks with chemistries consistent with a basement provenance, rather than the surface ~1 km of sedimentary cover rocks, atypically indicates a non-surficial source to some of the ejecta. Microkrystites from two adjacent biozones possess statistically indistinguishable major element compositions, suggesting they have a single source. The occurrence of microkrystites derived from a single impact event, but in different biozones, can be explained by: (1) diachronous biozone boundaries; (2) post-accumulation sedimentary reworking; or (3) erroneous biozonation.

Documentation of sediment cores from the Great Meteor Seamount, North Atlantic

Sedimentological and biostratigraphic investigations of 15 cores (total length: 88 m) from the vicinity of Great Meteor seamount (about 30° N, 28° W) showed that the calcareous ooze are asymmetrically distributed around the seamount and vertically differentiated into two intervals. East and west of the seampunt, the upper "A"-interval is characterized by yellowish-brown sediment colors and bioturbation; ash layers and diatoms are restricted to the eastern cores. On both seamount flanks, the sediment of the lower "B"-interval are white and very rich in CaCO3 with a major fine silt (2-16 µ) mode (mainly coccoliths). Lamination, manganese micronodules, Tertiary foraminifera and discoasters, and small limestone and basalt fragments are typical of the "B"-interval of the eastern cores only. The sediments contain abundant displaced material which was reworked from the upper parts of the seamount. The sedimentation around the seamount is strongly influenced by the kind of displaced material and the intensity of its differentiated dispersal: the sedimentation rates are generally higher on the east than on the west flank /e.g. in "B": 0.9 cm/1000 y in the W; 3.1 cm/1000 y in the E), and lower for the "A" than for the "B"-interval. The lamination is explained by the combination of increased sedimentation rates with a strong input of material poor in organic carbon producing a hostile environment for benthic life. The CaCO3 content of the core is highly influenced by the proportion of displaced bigenous carbonate material (mainly coccoliths). The genuine in-situ conditions of the dissolution facies are only reflected by the minimum CaCO3 values of the cores (CCD = about 5,500 m; first bend in dissolution curve = 4,000 m; ACD = about 3,400 m). The preservation of the total foraminiferal association depends on the proportions of in-situ versus displaced specimens. In greater water depths (stronger dissolution), for example, the preservation can be improved by the admixture of relatively well preserved displaced foraminifera. Carbonate cementation and the formation of manganese micronodules are restricted to microenvironments with locally increased organic carbon contents (e.g. pellets; foraminifera). The ash layers consist of redeposited, silicic volcanic glass of trachytic composition and Mio-Pliocene age; possibly, they can be derived from the upper part of the seamount. Siliceous organisms, especially diatoms, are frequent close to the ash layers and probably also redeposited. Their preservation was favoured by the increase of the SiO2 content in the pore water caused by the silicic volcanic glass. The cores were biostraftsraphically subdivided with the aid of planktonic foraminifera and partly alsococcoliths. In most cases, the biostratigraphically determined cold- and warm sections could be correlated from core to core. Almost all cores do not penetrate the Late Pleistocene. All Tertiary fossils are reworked. In general, the warm/cold boundary W2/C2 corresponds with the lithostratigraphic A/B boundray. Benthonic foraminifera indicate the original site deposition of the displaced material (summit plateau or flanks of the seamount). The asymmetric distribution of the sediments around the seamount east and west of the NE-directed antarctic bottom current (AABW) is explained by the distortion of the streamlines by the Coriolis force; by this process the current velocity is increased west of the seamount and decreased east of it. The different proportion of displaced material within the "A" and "B" interval is explained by changes of the intensity of the oceanic circulation. At the time of "B" the flow of the AABW around the seamount was stronger than during "A"; this can be inferred from the presence of characteristic benthonic foraminifera. The increased oceanic circulation implies an enhanced differentiation of the current velocities, and by that, also of the sedimentation rates, and intensifies the winnowed sediment material was transported downslope by turbid layers into the deep-sea, incorporated into the current system of the AABW, and asymmetrically deposited around the seamount.

Aragonite distribution and preservation of sediment cores from the Brazilian Continental Slope

We present late Quaternary records of aragonite preservation determined for sediment cores recovered on the Brazilian Continental Slope (1790-2585 m water depth) where North Atlantic Deep Water (NADW) dominates at present. We have used various indirect dissolution proxies (carbonate content, aragonite/calcite contents, and sand percentages) as well as gastropodal abundances and fragmentation of Limacina inflata to determine the state of aragonite preservation. In addition, microscopic investigations of the dissolution susceptibility of three Limacina species yielded the Limacina Dissolution Index which correlates well with most of the other proxies. Excellent preservation of aragonite was found in the Holocene section, whereas aragonite dissolution gradually increases downcore. This general pattern is attributed to an overall increase in aragonite corrosiveness of pore waters. Overprinted on this early diagenetic trend are high-frequency fluctuations of aragonite preservation, which may be related to climatically induced variations of intermediate water masses.