Organic geochemistry of ODP Sites 128-798 and 128-799

Miocene to Quaternary sediments from the Oki Ridge (Site 798) and the Kita-Yamato Trough (Site 799) in the Japan Sea contain organic carbon ranging from about 0.6% in light-colored layers to almost 6% in dark layers. The organic matter consists of a variable mixture of marine and terrigenous contributions, the ratio of which is not correlated to the total organic carbon content. Marine organic particles clearly dominate in the deeper section of Hole 799B. The extractable bitumen is strongly dominated by long-chain alkenones from microalgae in the shallower sediments, whereas bishomohopanoic acid (C32) of eubacterial origin is the single most abundant compound in deeper samples. Normal alkanes and straight-chain carboxylic acids, both of which show a bimodal distribution with odd and even carbon-number predominance, respectively, are two other groups of compounds which are important constituents of the extracts. The deepest samples at Site 799 contain a considerable amount of short-chain components, which probably migrated upward from thermally more altered deeper sediments.

Messinian and pre-Messinian sediments of ODP Holes 107-652A and 107-654A

Sedimentology, mineralogy, and petrology of the pre-Pliocene sediments drilled at ODP Sites 652 and 654 in the Tyrrhenian Sea (Leg 107) have been studied with emphasis on the lower Messinian to pre-Messinian intervals. Messinian at Site 652 is essentially turbiditic and basinal in character; it was deposited during the syn-rift phase in a strongly subsiding half-graben and is correlatable with emerged coeval sequences; in part with the Laga Formation of the foredeep of Apennines, and in part with the filling of grabens dissecting that chain in the Tyrrhenian portion of Tuscany. The sequence found in Site 654 indicates an upper Tortonian to Messinian transgression accompanying crustal stretching in the western Tyrrhenian Sea and is perfectly correlatable with the so-called "Sahelian cycle" and with "postorogenic" cycles recognized in peninsular Italy and in Sicily.

The effect of elevated CO2 and increased temperature on in vitro fertilization success and initial embryonic development of single male:female crosses of broad-cast spawning corals at mid- and high-latitude locations

The impact of global climate change on coral reefs is expected to be most profound at the sea surface, where fertilization and embryonic development of broadcast-spawning corals takes place. We examined the effect of increased temperature and elevated CO2 levels on the in vitro fertilization success and initial embryonic development of broadcast-spawning corals using a single male:female cross of three different species from mid- and high-latitude locations: Lyudao, Taiwan (22° N) and Kochi, Japan (32° N). Eggs were fertilized under ambient conditions (27 °C and 500 µatm CO2) and under conditions predicted for 2100 (IPCC worst case scenario, 31 °C and 1000 µatm CO2). Fertilization success, abnormal development and early developmental success were determined for each sample. Increased temperature had a more profound influence than elevated CO2. In most cases, near-future warming caused a significant drop in early developmental success as a result of decreased fertilization success and/or increased abnormal development. The embryonic development of the male:female cross of A. hyacinthus from the high-latitude location was more sensitive to the increased temperature (+4 °C) than the male:female cross of A. hyacinthus from the mid-latitude location. The response to the elevated CO2 level was small and highly variable, ranging from positive to negative responses. These results suggest that global warming is a more significant and universal stressor than ocean acidification on the early embryonic development of corals from mid- and high-latitude locations.

(Table 1) CPI17-23, hopanoic acid, and n-C35 + lycopane/n-C31 ratios as well as 17beta(H), 21beta(H) homohopane, long-chain alkanes, and alkenones concentrations in IODP Exp302

During Integrated Ocean Drilling Program Expedition 302 (Arctic Coring Expedition (ACEX)) a more than 200 m thick sequence of Paleogene organic carbon (OC)-rich (black shale type) sediments was drilled. Here we present new biomarker data determined in ACEX sediment samples to decipher processes controlling OC accumulation and their paleoenvironmental significance during periods of Paleogene global warmth and proposed increased freshwater discharge in the early Cenozoic. Specific source-related biomarkers including n-alkanes, fatty acids, isoprenoids, carotenoids, hopanes/hopenes, hopanoic acids, aromatic terpenoids, and long-chain alkenones show a high variability of components, derived from marine and terrestrial origin. The distribution of hopanoic acid isomers is dominated by compounds with the biological 17beta(H), 21beta(H) configuration indicating a low level of maturity. On the basis of the biomarker data the terrestrial OC supply was significantly enriched during the late Paleocene and part of the earliest Eocene, whereas increased aquatic contributions and euxinic conditions of variable intensity were determined for the Paleocene-Eocene thermal maximum and Eocene thermal maximum 2 events as well as the middle Eocene time interval. Furthermore, samples from the middle Eocene are characterized by the occurrence of long-chain alkenones, high proportions of lycopane, and high ratios (>0.6) of (n-C35 + lycopane)/n-C31. The occurrence of C37-alkenenones, which were first determined toward the end of the Azolla freshwater event, indicates that the OC becomes more marine in origin during the middle Eocene. Preliminary UK'37- based sea surface temperature (SST) values display a longterm temperature decrease of about 15C during the time interval 49-44.5 Ma (25° to 10°C), coinciding with the global benthic d18O cooling trend after the early Eocene climatic optimum. At about 46 Ma, parallel with onset of ice-rafted debris, SST (interpreted as summer temperatures) decreased to values <15°C. For the late early Miocene a SST of 11°-15°C was determined. Most of the middle Eocene ACEX sediments are characterized by a smooth short-chain n-alkane distribution, which may point to natural oil-type hydrocarbons from leakage of petroleum reservoirs or erosion of related source rocks and redeposition.

Effects of increasing seawater carbon dioxide concentrations on chain formation of the diatom Asterionellopsis glacialis

Diatoms can occur as single cells or as chain-forming aggregates. These two strategies affect buoyancy, predator evasion, light absorption and nutrient uptake. Adjacent cells in chains establish connections through various processes that determine strength and flexibility of the bonds, and at distinct cellular locations defining colony structure. Chain length has been found to vary with temperature and nutrient availability as well as being positively correlated with growth rate. However, the potential effect of enhanced carbon dioxide (CO2) concentrations and consequent changes in seawater carbonate chemistry on chain formation is virtually unknown. Here we report on experiments with semi-continuous cultures of the freshly isolated diatom Asterionellopsis glacialis grown under increasing CO2 levels ranging from 320 to 3400 µatm. We show that the number of cells comprising a chain, and therefore chain length, increases with rising CO2 concentrations. We also demonstrate that while cell division rate changes with CO2 concentrations, carbon, nitrogen and phosphorus cellular quotas vary proportionally, evident by unchanged organic matter ratios. Finally, beyond the optimum CO2 concentration for growth, carbon allocation changes from cellular storage to increased exudation of dissolved organic carbon. The observed structural adjustment in colony size could enable growth at high CO2 levels, since longer, spiral-shaped chains are likely to create microclimates with higher pH during the light period. Moreover increased chain length of Asterionellopsis glacialis may influence buoyancy and, consequently, affect competitive fitness as well as sinking rates. This would potentially impact the delicate balance between the microbial loop and export of organic matter, with consequences for atmospheric carbon dioxide.

Stable hydrogen and carbon isotope records and concentration data for four long chain n-alkanes from core GIK16160-3 derived from the Zambezi delta in the Mozambique Channel during the last 37,000 years

Hydrogen isotope values (dD) of sedimentary terrestrial leaf wax such as n-alkanes or n-acids have been used to map and understand past changes in rainfall amount in the tropics because dD of precipitation is commonly assumed as the first order controlling factor of leaf wax dD. Plant functional types and their photosynthetic pathways can also affect leaf wax dD but these biological effects are rarely taken into account in paleo studies relying on this rainfall proxy. To investigate how biological effects may influence dD values we here present a 37,000-year old record of dD and stable carbon isotopes (d13C) measured on four n-alkanes (n-C27, n-C29, n-C31, n-C33) from a marine sediment core collected off the Zambezi River mouth. Our paleo d13C records suggest that each individual n-alkanes had different C3/C4 proportional contributions. n-C29 was mostly derived from a C3 dicots (trees, shrubs and forbs) dominant vegetation throughout the entire record. In contrast, the longer chain n-C33 and n-C31 were mostly contributed by C4 grasses during the Glacial period but shifted to a mixture of C4 grasses and C3 dicots during the Holocene. Strong correlations between dD and d13C values of n-C33 (correlation coefficient R2 = 0.75, n = 58) and n-C31 (R2 = 0.48, n = 58) suggest that their dD values were strongly influenced by changes in the relative contributions of C3/C4 plant types in contrast to n-C29 (R2 = 0.07, n = 58). Within regions with variable C3/C4 input, we conclude that dD values of n-C29 are the most reliable and unbiased indicator for past changes in rainfall, and that dD and d13C values of n-C31 and n-C33 are sensitive to C3/C4 vegetation changes. Our results demonstrate that a robust interpretation of palaeohydrological data using n-alkane dD requires additional knowledge of regional vegetation changes from which nalkanes are synthesized, and that the combination of dD and d13C values of multiple n-alkanes can help to differentiate biological effects from those related to the hydrological cycle.