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Rationale: The hydrogen isotopic composition of lipids (δ2Hlipid) is widely used in food science and as a proxy for past hydrological conditions. Determining the δ2H values of large, well‐preserved triacylglycerides and other microbial lipids, such as glycerol dialkyl glycerol tetraether (GDGT) lipids, is thus of widespread interest but has so far not been possible due to their low volatility which prohibits analysis by traditional gas chromatography/pyrolysis/isotope ratio mass spectrometry (GC/P/IRMS). Methods: We determined the δ2H values of large, polar molecules and applied high‐temperature gas chromatography (HTGC) methods on a modified GC/P/IRMS system. The system used a high‐temperature 7‐m GC column, and a glass Y‐splitter for low thermal mass. Methods were validated using authentic standards of large, functionalised molecules (triacylglycerides, TGs), purified standards of GDGTs. The results were compared with δ2H values determined by high‐temperature elemental analyser/pyrolysis/isotope ratio mass spectrometry (HTEA/P/IRMS), and subsequently applied to the analysis of GDGTs in a sample from a methane seep and a Welsh peat. Results: The δ2H values of TGs agreed within error between HTGC/P/IRMS and HTEA/IRMS, with HTGC/P/IRMS showing larger errors. Archaeal lipid GDGTs with up to three cyclisations could be analysed: the δ2H values were not significantly different between methods with standard deviations of 5 to 6 ‰. When environmental samples were analysed, the δ2H values of isoGDGTs were 50 ‰ more negative than those of terrestrial brGDGTs. Conclusions: Our results indicate that the HTGC/P/IRMS method developed here is appropriate to determine the δ2H values of TGs, GDGTs with up to two cyclisations, and potentially other high molecular weight compounds. The methodology will widen the current analytical window for biomarker and food light stable isotope analyses. Moreover, our initial measurements suggest that bacterial and archaeal GDGT δ2H values can record environmental and ecological conditions. [ABSTRACT FROM AUTHOR]

Many cold-water sponges harbour microorganisms of which the role in the sponge host remains enigmatic. Here, we show a transfer of fixed inorganic carbon by sponge-associated microbes to its host, the cold-water coral encrusting sponge Hymedesmia (Stylopus) coriacea. Sponge were collected at approx. 100 m depth and incubated for 1.5–2.5 days with 13C labelled dissolved inorganic carbon (DIC) as tracer. Total DIC fixation rates ranged from 0.03–0.11 mmol C × mmol Csponge × d−1. 13C-tracer was recovered in bacterial-specific (i.e. short and branched) and sponge-specific (very long-chained) phospholipid-derived fatty acids (PLFA's), but was not incorporated into archaeal lipids. 13C-incorporation in biomarkers such as C16:1w7c and C18:1w7c indicated that nitrifying and/or sulphur-oxidizing bacteria (chemoautotrophs) were likely active in the sponge. Trophic transfer of microbially-fixed carbon to the sponge host was confirmed by recovery of label in very long chain fatty acids (VLCFA's) including C26:2 and C26:3. Tracer accumulation into several VLCFA's continued after removal of 13C-DIC, while tracer in most bacteria-specific PLFA's declined, indicating a transfer and elongation of bacterial-specific PLFA's to sponge-specific PLFA's. This implies that PLFA precursors released from chemo- as well as heterotrophic microbes in sponges contributed to the synthesis of VLCFA's, identifying sponge-associated bacteria as symbionts of the sponge. [ABSTRACT FROM AUTHOR]

The biology and ecology of calcarean sponges are not as well understood as they are for demosponges. Here, in order to gain new insights, particularly about symbiotic relationships, the calcarean sponge Leucetta prolifera was sampled from south-western Australia and examined for its assumed photosymbionts. Pulse amplitude modulated fluorometry and extraction of photopigments established that the sponge was photosynthetic. Molecular analysis of the bacterial symbionts via sequencing of the V1–V3 region of the 16S rDNA gene confirmed that between 5 and 22% of all sequences belonged to the phylum Cyanobacteria, depending on the individual sample, with the most dominant strain aligning with Hormoscilla spongeliae, a widely distributed sponge symbiont. Analysis of fatty acids suggested that the sponge obtains nutrition through photosynthates from its symbionts. The relationship is assumed to be mutualistic, with the sponge receiving dietary support and the cyanobacteria sheltering in the sponge tissues. We list all Calcarea presently known to harbour photosymbionts. [ABSTRACT FROM PUBLISHER]

RATIONALE As a by-product of oil sands extraction, large volumes of oil sands process water (OSPW) are generated, which are contaminated with a large range of water-soluble organic compounds. The acids are thought to be derived from hydrocarbons via natural biodegradation pathways such as α- and β-oxidation of alkyl substituents, which could produce mono- and diacids, for example. However, while several monoacids ('O2' species) have been identified, the presence of diacids (i.e. 'O4' species) has only been deduced from results obtained via Fourier transform infrared (FTIR) spectroscopy, Fourier transform ion cyclotron resonance high-resolution mass spectrometry (FTICR-HRMS) and nuclear magnetic resonance (1H-NMR) spectroscopy and the structures have never been confirmed. METHODS An extract of an OSPW from a Canadian tailings pond was analysed and the retention times and the electron ionization mass spectra of some analytes were compared with those of bis-methyl esters of authentic diacids by gas chromatography × gas chromatography/time-of-flight mass spectrometry (GCxGC/TOFMS) in nominal and accurate mass configurations. RESULTS Two diamondoid diacids (3-carboxymethyladamantane-1-carboxylic acid and adamantane-1,3-dicarboxylic acid) were firmly identified as their bis-methyl esters by retention time and mass spectral matching and several other structural isomers were more tentatively assigned. Diacids have substantially increased polarity over the hydrocarbon and monoacid species from which they probably derive: as late members of biodegradation processes they may be useful indicators of weathering and ageing, not only of OSPW, but potentially of crude oil residues more generally. CONCLUSIONS Structures of O4 species in OSPW have been identified. This confirms pathways of microbial biodegradation, which were only postulated previously, and may be a further indication that remediation of OSPW toxicity can occur by natural microbial action. The presence and abundance of these diacids might therefore be useful as a measure of biodegradation and weathering. Copyright © 2013 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

The Cretaceous-Paleogene (K-Pg) boundary marks one of the five major mass extinctions of the Phanerozoic. The ways in which the climate system responded to a bolide impact and extensive volcanism at this time over different time scales are highly debated. We used the distribution of branched tetraether lipids (brGDGT) from fossil peats at two sites in Saskatchewan, Canada (paleolatitude -55°N), to generate a high-resolution (millennial) record of mean annual air temperature (MAAT) spanning the last -4 k.y. of the Cretaceous and the first -30 k.y. of the Paleogene. Our study shows that MAATs ranged from 16 to 29 °C, with the highest value in the first millennia of the Paleogene. The earliest Paleogene averaged -25 °C--maintaining or enhancing warmth from the latest Cretaceous--followed by a general cooling to -20 °C over the following -30 k.y. No abrupt postboundary cooling (e.g., an "impact winter") or abrupt warming is evident in our data, implying that if such phenom- ena occurred, their duration was relatively short-lived (i.e., sub-millennial-scale). Further, no long-term impact- or volcanism-driven warming is evident. The range of temperature change observed is considerably greater than that derived from marine proxy records over the same time interval. Our findings therefore more properly place bounds on the magnitude and duration of temperature change on land during this critical interval--the main setting for the demise of nonavian dinosaurs and the rise of mammals. [ABSTRACT FROM AUTHOR]