Distribution and stable isotopic compositions of hydrogen and carbon of plant-wax derived n-C29 and -C31 alkanes in terrestrial, coastal and offshore surface sediments

Reconstructing terrestrial water budgets is of prime importance for understanding past climate and environment. To shed more light on how plant-wax derived n-alkanes may be used for this purpose we investigated the distribution and stable isotopic compositions of hydrogen (dD) and carbon (d13C) of plant-wax derived n-C29 and -C31 alkanes in terrestrial, coastal and offshore surface sediments in relation to hydrology along a NW-SE transect east of the Italian Apennines from the Po River to the Eastern Gulf of Taranto. The plant wax average chain length increases southward and may relate to increasing temperature and/or aridity. The plant wax dD of the terrestrial and coastal samples also increases southward and mainly reflects changes in the dD of precipitation. The d13C of plant waxes is primarily interpreted in terms of C3 vegetation changes rather than varying contributions by C4 plants. The plant wax d13C-dD composition of the Po River and Apennine rivers differs considerably from that in southern Italy, and suggests a mainly southern source for plant waxes in marine sediments of the Gulf of Taranto. This calibration provides a basis for the reconstruction of past changes in the Italian water balance and n-alkane source areas.

(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.

dD values of C31 n-alkane (dD wax) from sediment core GeoB9501-4 offshore the Northwest African Sahel

Various studies have demonstrated that the stable hydrogen isotopic composition (dD) of terrestrial leaf waxes tracks that of precipitation (dDprecip) both spatially across climate gradients and over a range of different timescales. Yet, reconstructed estimates of dDprecip and corresponding rainfall typically remain largely qualitative, due mainly to uncertainties in plant ecosystem net fractionation, relative humidity, and the stability of the amount effect through time. Here we present dD values of the C31n-alkane (dDwax) from a marine sediment core offshore the Northwest (NW) African Sahel covering the past 100 years and overlapping with the instrumental record of rainfall. We use this record to investigate whether accurate, quantitative estimates of past rainfall can be derived from our dDwax time series. We infer the composition of vegetation (C3/C4) within the continental catchment area by analysis of the stable carbon isotopic composition of the same compounds (d13Cwax), calculated a net ecosystem fractionation factor, and corrected the dDwax time series accordingly to derive dDprecip. Using the present-day relationship between dDprecip and the amount of precipitation in the tropics, we derive quantitative estimates of past precipitation amounts. Our data show that (a) vegetation composition can be inferred from d13Cwax, (b) the calculated net ecosystem fractionation represents a reasonable estimate, and (c) estimated total amounts of rainfall based on dDwax correspond to instrumental records of rainfall. Our study has important implications for future studies aiming to reconstruct rainfall based on dDwax; the combined data presented here demonstrate that it is feasible to infer absolute rainfall amounts from sedimentary dDwax in tandem with d13Cwax in specific depositional settings.

The mechanism of ϕC31 integrase directionality : experimental analysis and computational modelling

Acknowledgments We thank Sally Rowland for helpful comments on the manuscript. © The Author(s) 2016. Published by Oxford University Press on behalf of Nucleic Acids Research.