Seasonal changes in the D/H ratio of fatty acids of pelagic microorganisms

Culture studies of microorganisms have shown that the hydrogen isotopic composition of fatty acids depends on their metabolism, but there are only few environmental studies available to confirm this observation. Here we studied the seasonal variability of the deuterium/hydrogen (D/H) ratio of fatty acids in the coastal Dutch North Sea and compared this with the diversity of the phyto- and bacterioplankton. Over the year, the stable hydrogen isotopic fractionation factor epsilon between fatty acids and water ranged between -172 per mil and -237 per mil, the algal-derived polyunsaturated fatty acid nC20:5 being the most D-depleted and nC18:0 the least D-depleted fatty acid. The D-depleted nC20:5 is in agreement with culture studies, which indicates that photoautotrophic microorganisms produce fatty acids which are significantly depleted in D relative to water. The epsilon-lipid/water of all fatty acids showed a transient shift towards increased fractionation during the spring phytoplankton bloom, indicated by increasing chlorophyll a concentrations and relative abundance of the nC20:5 PUFA, suggesting increased contributions of photoautotrophy. Time periods with decreased fractionation (less negative epsilon-lipid/water values) can be explained by an increased contribution by heterotrophy to the fatty acid pool. Our results show that the hydrogen isotopic composition of fatty acids is a useful tool to assess the community metabolism of coastal plankton.

Grain counts and XRD mineralogy of turbidite sand and hemipelagic mud from ODP Leg 168 sites

Sequences of late Pliocene to Holocene sediment lap onto juvenile igneous crust within 20 km of the Juan de Fuca Ridge in northwestern Cascadia Basin, Pacific Ocean. The detrital modes of turbidite sands do not vary significantly within or among sites drilled during Leg 168 of the Ocean Drilling Program. Average values of total quartz, total feldspar, and unstable lithic fragments are Q = 35, F = 35, and L = 30. Average values of monocrystalline quartz, plagioclase, and K-feldspar are Qm = 46, P = 49, and K = 5, and the average detrital modes of polycrystalline quartz, volcanic-rock fragments, and sedimentary-rock plus metamorphic-rock fragments are Qp = 16, Lv = 43, and Lsm = 41. Likely source areas include the Olympic Peninsula and Vancouver Island; sediment transport was focused primarily through the Strait of Juan de Fuca, Juan de Fuca Channel, Vancouver Valley, and Nitinat Valley. Relative abundance of clay minerals (<2-µm-size fraction) fluctuate erratically with depth, stratigraphic age, and sediment type (mud vs. turbidite matrix). Mineral abundance in mud samples are 0%-35% smectite (mean = 8%), 18%-59% illite (mean = 40%), and 29%-78% chlorite + kaolinite (mean = 52%). We attribute the relatively low content of smectite to rapid mechanical weathering of polymictic source terrains, with little or no input of volcanic detritus from the Columbia River. The scatter in clay mineralogy probably was caused by converging of surface currents, turbidity currents, and near-bottom nepheloid clouds from several directions, as well as subtle changes in glacial vs. interglacial weathering products.

Mineralogical and stable isotope analyses of carbonates from the eastern Black Sea

Authigenic carbonates associated with cold seeps provide valuable archives of changes in the long-term seepage activity. To investigate the role of shallow-buried hydrates on the seepage strength and fluid composition we analysed methane-derived carbonate precipitates from a high-flux hydrocarbon seepage area ("Batumi seep area") located on the south-eastern Black Sea slope in ca. 850 m. In a novel approach, we combined computerized X-ray tomography (CT) with mineralogical and isotope geochemical methods to get additional insights into the three-dimensional internal structure of the carbonate build-ups. X-ray diffractometry revealed the presence of two different authigenic carbonate phases, i.e. pure aragonitic rims associated with vital microbial mats and high-Mg calcite cementing the hemipelagic sediment. As indicated by the CT images, the initial sediment has been strongly deformed, first plastic then brittle, leading to brecciation of the progressively cemented sediment. The aragonitic rims on the other hand, represent a presumably recent carbonate growth phase since they cover the already deformed sediment. The stable oxygen isotope signature indicates that the high-Mg calcite cement incorporated pore water mixed with substantial hydrate water amounts. This points at a dominant role of high gas/fluid flux from decomposing gas hydrates leading to the deformation and cementation of the overlying sediment. In contrast, the aragonitic rims do not show an influence of 18O-enriched hydrate water. The differences in d18O between the presumably recent aragonite precipitates and the older high-Mg cements suggest that periods of hydrate dissociation and vigorous fluid discharge alternated with times of hydrate stability and moderate fluid flow. These results indicate that shallow-buried gas hydrates are prone to episodic decomposition with associated vigorous fluid flow. This might have a profound impact on the seafloor morphology resulting e.g. in the formation of carbonate pavements and pockmark-like structures but might also affect the local carbon cycle.

Biomarker and x-ray diffraction data from Site U1313 (MIS 16 - 9)

A reconstruction of Milankovitch to millennial-scale variability of sea-surface temperature (SST) and sea-surface productivity in the Pleistocene mid-latitude North Atlantic Ocean (MIS 16-9) and its relationship to ice sheet instability was carried out on sediments from IODP Site U1313. This reconstruction is based on alkenone and n-alkane concentrations, Uk37' index, total organic carbon (TOC) and carbonate contents, X-Ray diffraction (XRD) data, magnetic susceptibility, and accumulation rates. Increased input of ice-rafted debris (IRD) occurred during MIS 16, 12, and 10, characterized by high concentrations of dolomite, quartz, and feldspars and elevated accumulation rates of terrigenous matter. Minimum input values of terrigenous matter, on the other hand, were determined for MIS 13 and 11. Peak values of dolomite, coinciding with quartz, plagioclase, and kalifeldspar peaks and maxima in long-chain n-alkanes indicative for land plants, are interpreted as Heinrich-like Events related to sudden instability of the Laurentide Ice Sheet during early and late (deglacial) phases of the glacials. The coincidence of increased TOC values with elevated absolute concentrations of alkenones suggest increased glacial productivity, probably due to a more southern position of the Polar Front. Alkenone-based SST reached absolute maxima of about 19°C during MIS 11.3 and absolute minima of <10°C during MIS 12 and 10. Within MIS 11, prominent cooling events (MIS 11.22 and 11.24) occurred. The absolute SST minima recorded directly before and after the glacial maxima MIS 10.2 and 12.2, are related to Heinrich-like Event meltwater pulses, as supported by the coincidence of SST minima and maxima in C37:4 alkenones and dolomite. These sudden meltwater pulses - especially during Terminations IV and V - probably caused a collapse of phytoplankton productivity as indicated by the distinct drop in alkenone concentrations. Ice-sheet disintegration and subsequent surges and outbursts of icebergs and meltwater discharge may have been triggered by increased insolation in the Northern High Latitudes.

Mineral composition of sediments from ODP Leg 190 sites and DSDP Hole 31-297

This data report documents the acquisition of two new sets of normalization factors for semiquantitative X-ray diffraction analyses. One set of factors is for bulk sediment powders, and the other applies to oriented aggregates of clay-sized fractions (<2 µm). We analyzed mixtures of standard minerals with known weight percentages of each component and solved for the normalization factors using matrix singular value decomposition. The components in bulk powders include total clay minerals (a mixture of smectite, illite, and chlorite), quartz, plagioclase, and calcite. For clay-sized fractions, the minerals are smectite, illite, chlorite, and quartz. We tested the utility of the method by analyzing natural mudstone specimens from Site 297 of the Deep Sea Drilling Project, which is located in the Shikoku Basin south of Site 1177 of the Ocean Drilling Program (Ashizuri transect).

XRF-scanned elemental concentrations from sediment cores off Peru

We present a high-resolution marine record of sediment input from the Guayas River, Ecuador, that reflects changes in precipitation along western equatorial South America during the last 18ka. We use log (Ti/Ca) derived from X-ray Fluorescence (XRF) to document terrigenous input from riverine runoff that integrates rainfall from the Guayas River catchment. We find that rainfall-induced riverine runoff has increased during the Holocene and decreased during the last deglaciation. Superimposed on those long-term trends, we find that rainfall was probably slightly increased during the Younger Dryas, while the Heinrich event 1 was marked by an extreme load of terrigenous input, probably reflecting one of the wettest period over the time interval studied. When we compare our results to other Deglacial to Holocene rainfall records located across the tropical South American continent, different modes of variability become apparent. The records of rainfall variability imply that changes in the hydrological cycle at orbital and sub-orbital timescales were different from western to eastern South America. Orbital forcing caused an antiphase behavior in rainfall trends between eastern and western equatorial South America. In contrast, millennial-scale rainfall changes, remotely connected to the North Atlantic climate variability, led to homogenously wetter conditions over eastern and western equatorial South America during North Atlantic cold spells. These results may provide helpful diagnostics for testing the regional rainfall sensitivity in climate models and help to refine rainfall projections in South America for the next century.