Description: The West Antarctic Ice Sheet (WAIS) is one of the largest potential sources of future sea-level rise, with glaciers draining the WAIS thinning at an accelerating rate over the past 40 years. Due to complexities in calibrating palaeoceanographic proxies for the Southern Ocean, it remains difficult to assess whether similar changes have occurred earlier during the Holocene or whether there is underlying centennial- to millennial-scale forcing in oceanic variability. Archaeal lipid-based proxies, specifically glycerol dialkyl glycerol tetraether (GDGT; e.g. TEX86 and TEXL86), are powerful tools for reconstructing ocean temperature, but these proxies have been shown previously to be difficult to apply to the Southern Ocean. A greater understanding of the parameters that control Southern Ocean GDGT distributions would improve the application of these biomarker proxies and thus help provide a longer-term perspective on ocean forcing of Antarctic ice sheet changes. In this study, we characterised intact polar lipid (IPL)-GDGTs, representing (recently) living archaeal populations in suspended particulate matter (SPM) from the Amundsen Sea and the Scotia Sea. SPM samples from the Amundsen Sea were collected from up to four water column depths representing the surface waters through to Circumpolar Deep Water (CDW), whereas the Scotia Sea samples were collected along a transect encompassing the sub-Antarctic front through to the southern boundary of the Antarctic Circumpolar Current. IPL-GDGTs with low cyclic diversity were detected throughout the water column with high relative abundances of hydroxylated IPL-GDGTs identified in both the Amundsen and Scotia seas. Results from the Scotia Sea show shifts in IPL-GDGT signatures across well-defined fronts of the Southern Ocean. Indicating that the physicochemical parameters of these water masses determine changes in IPL-GDGT distributions. The Amundsen Sea results identified GDGTs with hexose-phosphohexose head groups in the CDW, suggesting active GDGT synthesis at these depths. These results suggest that GDGTs synthesised at CDW depths may be a significant source of GDGTs exported to the sedimentary record and that temperature reconstructions based on TEX86 or TEXL86 proxies may be significantly influenced by the warmer waters of the CDW.

Description: The intensification of the Northern Hemisphere Glaciation (INHG) was a major event in the development of the current climate state, and as one of the most productive regions in the world's oceans, the behaviour of the Benguela Upwelling System (BUS) following the INHG is of wide interest. To investigate post-INHG changes in productivity and organic matter accumulation, total organic carbon and biomarker accumulation rates were determined for sediments from COP Site 1083 and compared to alkenone-derived sea surface temperatures and nitrogen isotopic compositions. These data indicate that the interval between 2.6 and 2.4 Ma was characterized by dramatic changes in upwelling intensity and organic carbon export on the northern edge of the modern BUS. The upwelling is reflected by significant changes in alkenone-derived SST estimates between glacial and interglacial intervals, with a total variability of 16 degrees C. The studied interval is also characterized by large changes in organic matter export as reflected by changes in TOC and biomarker accumulation rates, which show maxima during OIS 98 and during the transition from OIS 97 to 96. Intervals of elevated TOC are also characterized by elevated concentrations of sedimentary microbial biomarkers and lower %CaCO(3), suggesting that enhanced delivery of labile organic matter to the seafloor resulted in enhanced remineralisation with released CO(2) being consumed by CaCO(3) dissolution. However, in apparent contrast to recent Pleistocene sediments at the same site, organic matter export after the INHG was not solely driven by upwelling intensity. Of the three Pliocene glacial-interglacial cycles examined (OIS 101 to 96). each is unique with respect to the timing and magnitude of changes in organic matter accumulation. Each is also characterized by different algal assemblages as inferred from biomarker distributions, with OIS 97 and 96 particularly dominated by diatoms. We suggest that these differences reflect the important but evolving role of Southern Ocean waters in the Pliocene BUS: nutrient depletion of SO waters occurred during parts of Pliocene glacial intervals such that even intense upwelling did not persistently result in enhanced organic matter accumulation rates. (C) 2009 Elsevier B.V. All rights reserved.

Description: We investigated the occurrence and activity of anaerobic ammonia oxidation (anammox) bacteria in sandy and muddy sand sediments of the southern North Sea. The presence of anammox bacteria was established through the detection of specific phosphocholine-monoether ladderane lipids, 16S rRNA gene, and hydrazine synthase (hzsA) genes. Anammox activity was measured in intact sediment cores (in situ rate) and in sediment slurries (potential rate) as the rate of N2 evolution from 15N-labeled substrates and compared to the transcriptional activity of genes of anammox bacteria. The contribution of anammox to N2 production ranged between 0% and 29%. The potential rate of anammox agreed well with the abundance of anammox bacteria 16S rRNA and hzsA gene copies and the transcriptional activity of the anammox bacteria 16S rRNA gene. We found a higher abundance and activity of anammox bacteria in sediments with higher organic carbon content and also higher activity in summer than in winter. The abundance of anammox bacteria and their potential anammox rates were similar to those reported for other marine coastal sediments, suggesting that potentially they are important contributors to the nitrogen cycle in sandy sediments of shallow continental shelf areas.

Description: We have examined the spatial and seasonal distribution of Thaumarchaeota in the water column and sediment of the southern North Sea using the specific intact polar lipid (IPL) hexose, phosphohexose (HPH) crenarchaeol, as well as thaumarchaeotal 16S rRNA gene abundances and expression. In the water column, a higher abundance of Thaumarchaeota was observed in the winter season than in the summer, which is in agreement with previous studies, but this was not the case in the sediment where Thaumarchaeota were most abundant in spring and summer. This observation corresponds well with the idea that ammonia availability is a key factor in thaumarchaeotal niche determination. In the surface waters of the southern North Sea, we observed a spatial variability in HPH crenarchaeol, thaumarchaeotal 16S rRNA gene abundance and transcriptional activity that corresponded well with the different water masses present. In bottom waters, a clear differentiation based on water masses was not observed; instead, we suggest that observed differences in thaumarchaeotal abundance with depth may be related to resuspension from the sediment. This could be due to suspension of benthic Thaumarchaeota to the water column or due to delivery of e.g. resuspended sediment or ammonium to the water column, which could be utilized by pelagic Thaumarchaeota. This study has shown that the seasonality of Thaumarchaeota in water and sediment is different and highlights the importance of water masses, currents and sedimentary processes in determining the spatial abundance of Thaumarchaeota in the southern North Sea.

Description: 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-to-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 (epsilon lipid/water) ranged between -172 and -237 per mil, the algal-derived polyunsaturated fatty acid nC20:5 generally being the most D-depleted (-177 to -235 per mil) and nC18:0 the least D-depleted fatty acid (-172 to -210 per mil). The in general highly 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 polyunsaturated fatty acids, suggesting increased contributions of photoautotrophy. Time periods with decreased fractionation (less negative epsilon lipid/water values) can potentially be explained by an increased contribution of heterotrophy to the fatty acid pool. Our results show that the hydrogen isotopic composition of fatty acids is a promising tool to assess the community metabolism of coastal plankton potentially in combination with the isotopic analysis of more specific biomarker lipids.

Description: Marine endosymbiotic heterocystous cyanobacteria make unique heterocyst glycolipids (HGs) containing pentose (C5) moieties. Functionally similar HGs with hexose (C6) moieties found in free-living cyanobacteria occur in the sedimentary record, but C5 HGs have not been documented in the natural environment. Here we developed a high performance liquid chromatography multiple reaction monitoring (MRM) mass spectrometry (HPLC-MS2) method specific for trace analysis of long chain C5HGs and applied it to cultures of Rhizosolenia clevei Ostenfeld and its symbiont Richelia intracellularis which were found to contain C5 HGs and no C6 HGs. The method was then applied to suspended particulate matter (SPM) and surface sediment from the Amazon plume region known to harbor marine diatoms carrying heterocystous cyanobacteria as endosymbionts. C5 HGs were detected in both marine SPM and surface sediments, but not in SPM or surface sediment from freshwater settings in the Amazon basin. Rather, the latter contained C6 HGs, established biomarkers for free-living heterocystous cyanobacteria. Our results indicate that the C5 HGs may be potential biomarkers for marine endosymbiotic heterocystous cyanobacteria.