Ether lipids in deep sea and swamp sediments

Methanogen ether lipids have been quantified in sediments from a Florida swamp and the Atlantic ocean. Swamp cores containing acyclic and monocyclic isopranyl ethers are clearly differentiated from deep sea sediments which also contain bicyclic compounds. A concentration maximum near the bottom of the sulfate reducing zone in deep sea sediments may reflect a biogeochemical system in which methanogenesis and sulfate reduction are coupled by the process of methane oxidation. Lipid diagenesis is evident in the deep sea sediments. Species zonation, possibly caused by oxygen sensitivity, is detected in the relative lipid abundances in swamp sediments.

Degradation of [14C]GlcDGD in the marine sediment by monitoring radioactivity in the aqueous and gas phase using liquid scintillation counting (LSC) techniques

An experiment was conceived in which we monitored degradation of GlcDGD. Independent of the fate of the [14C]glucosyl headgroup after hydrolysis from the glycerol backbone, the 14C enters the aqueous or gas phase whereas the intact lipid is insoluble and remains in the sediment phase. Total degradation of GlcDGD then is obtained by combining the increase of radioactivity in the aqueous and gaseous phases. We chose two different sediment to perform this experiment. One is from microbially actie surface sediment sampled in February 2010 from the upper tidal flat of the German Wadden Sea near Wremen (53° 38' 0N, 8° 29' 30E). The other one is deep subsurface sediments recovered from northern Cascadia Margin during Integrated Ocean Drilling Program Expedition 311 [site U1326, 138.2 meters below seafloor (mbsf), in situ temperature 20 °C, water depth 1,828 m. We performed both alive and killed control experiments for comparison. Surface and subsurface sediment slurry were incubated in the dark at in situ temperature, 4 °C and 20 °C for 300 d, respectively. The sterilized slurry was stored at 20 °C. All incubations were carried out under N2 headspace to ensure anaerobic conditions. The sampling frequency was high during the first half-month, i.e., after 1, 2, 7, and 14 d; thereafter, the sediment slurry was sampled every 2 months. At each time point, samples were taken in triplicate for radioactivity measurements. After 300 d of incubation, no significant changes of radioactivity in the aqueous phase were detected. This may be the result of either the rapid turnover of released [14C] glucose or the relatively high limit of detection caused by the slight solubility (equivalent to 2% of initial radioactivity) of GlcDGD in water. Therefore, total degradation of GlcDGD in the dataset was calculated by combining radioactivity of DIC, CH4, and CO2, leading to a minimum estimate.

Glycerol dialkyl glycerol tetraethers (GDGT) abundance of sediment core GeoB15103-1

Marine microorganisms adapt to their habitat by structural modification of their membrane lipids. This concept is the basis of numerous molecular proxies used for paleoenvironmental reconstruction. Archaeal tetraether lipids from ubiquitous marine planktonic archaea are particularly abundant, well preserved in the sedimentary record and utilized in several molecular proxies. We here introduce the direct, extraction-free analysis of these compounds in intact sediment core sections using laser desorption ionization (LDI) coupled to Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). LDI FTICR-MS can detect the target lipids in single sub-mm sized spots on sediment sections, equivalent to a sample mass in the nanogram range, and could thus pave the way for biomarker-based reconstruction of past environments and ecosystems at subannual to decadal resolution. We demonstrate that ratios of selected archaeal tetraethers acquired by LDI FTICR-MS are highly correlated with values obtained by conventional LC/MS protocols. The ratio of the major archaeal lipids, caldarchaeol and crenarchaeol, analyzed in a 6.2-cm intact section of Mediterranean sapropel S1 at 250-µm resolution (~4-year temporal resolution), provides an unprecedented view of the fine-scale patchiness of sedimentary biomarker distributions and the processes involved in proxy signal formation. Temporal variations of this lipid ratio indicate a strong influence of the 200-yr de Vries solar cycle on reconstructed sea surface temperatures with possible amplitudes of several degrees, and suggest signal amplification by a complex interplay of ecological and hydrological factors. Laser-based biomarker analysis of geological samples has the potential to revolutionize molecular stratigraphic studies of paleoenvironments.

Body measurements and blood plasma lipid, PCB and OH-PCB content of polar bear (U. maritimus) mothers and cubs, Svalbard

The aim of this study was to examine the plasma concentrations and prevalence of polychlorinated biphenyls (PCBs) and hydroxylated PCB-metabolites (OH-PCBs) in polar bear (Ursus maritimus) mothers (n = 26) and their 4 months old cubs-of-the-year (n = 38) from Svalbard to gain insight into the mother-cub transfer, biotransformation and to evaluate the health risk associated with the exposure to these contaminants. As samplings were performed in 1997/1998 and 2008, we further investigated the differences in levels and pattern of PCBs between the two sampling years. The plasma concentrations of Sum(21)PCBs (1997/1998: 5710 ± 3090 ng/g lipid weight [lw], 2008: 2560±1500 ng/g lw) and Sum(6)OH-PCBs (1997/1998: 228 ± 60 ng/g wet weight [ww], 2008: 80 ± 38 ng/g ww) in mothers were significantly lower in 2008 compared to in 1997/1998. In cubs, the plasma concentrations of Sum(21)PCBs (1997/1998: 14680 ± 5350 ng/g lw, 2008: 6070 ± 2590 ng/g lw) and Sum(6)OH-PCBs (1997/1998: 98 ± 23 ng/g ww, 2008: 49 ± 21 ng/g ww) were also significantly lower in 2008 than in 1997/1998. Sum(21)PCBs in cubs was 2.7 ± 0.7 times higher than in their mothers. This is due to a significant maternal transfer of these contaminants. In contrast, Sum(6)OH-PCBs in cubs were approximately 0.53 ± 0.16 times the concentration in their mothers. This indicates a lower maternal transfer of OH-PCBs compared to PCBs. The majority of the metabolite/precursor-ratios were lower in cubs compared to mothers. This may indicate that cubs have a lower endogenous capacity to biotransform PCBs to OH-PCBs than polar bear mothers. Exposure to PCBs and OH-PCBs is a potential health risk for polar bears, and the levels of PCBs and OH-PCBs in cubs from 2008 were still above levels associated with health effects in humans and wildlife.

Concentrations of brominated and chlorinated contaminants in adipose tissue of polar bears (Ursus maritimus) between 1991-2007

Adipose tissue was sampled from the western Hudson Bay (WHB) subpopulation of polar bears at intervals from 1991 to 2007 to examine temporal trends of PCB and OCP levels both on an individual and sum-contaminant basis. We also determined levels and temporal trends of emerging polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), polybrominated biphenyls (PBBs) and other current-use brominated flame retardants. Over the 17-year period, sum DDT (and p,p'-DDE, p,p'-DDD, p,p'-DDT) decreased (-8.4%/year); alpha-hexachlorocyclohexane (alpha-HCH) decreased (-11%/year); beta-HCH increased ( + 8.3%/year); and sum PCB and sum chlordane (CHL), both contaminants at highest concentrations in all years (>1 ppm), showed no distinct trends even when compared to previous data for this subpopulation dating back to 1968. Some of the less persistent PCB congeners decreased significantly (-1.6%/year to -6.3%/year), whereas CB153 levels tended to increase (+ 3.3%/year). Parent CHLs (c-nonachlor, t-nonachlor) declined, whereas non-monotonic trends were detected for metabolites (heptachlor epoxide, oxychlordane). sum chlorobenzene, octachlorostyrene, sum mirex, sum MeSO2-PCB and dieldrin did not significantly change. Increasing sum PBDE levels (+13%/year) matched increases in the four consistently detected congeners, BDE47, BDE99, BDE100 and BDE153. Although no trend was observed, total-(alpha)-HBCD was only detected post-2000. Levels of the highest concentration brominated contaminant, BB153, showed no temporal change. As long-term ecosystem changes affecting contaminant levels may also affect contaminant patterns, we examined the influence of year (i.e., aging or "weathering" of the contaminant pattern), dietary tracers (carbon stable isotope ratios, fatty acid patterns) and biological (age/sex) group on congener/metabolite profiles. Patterns of PCBs, CHLs and PBDEs were correlated with dietary tracers and biological group, but only PCB and CHL patterns were correlated with year. DDT patterns were not associated with any explanatory variables, possibly related to local DDT sources. Contaminant pattern trends may be useful in distinguishing the possible role of ecological/diet changes on contaminant burdens from expected dynamics due to atmospheric sources and weathering.

Composition of free lipids in bottom sediments in the tropical West Pacific and South Atlantic

Contents of free lipids in the upper layers of slightly siliceous diatomaceous oozes from the South Atlantic and of calcareous foraminiferal oozes, of coral sediments and of red clays from the western tropical Pacific amount varies from 0.014 to 0.057% of dry sediment. Their content is inversely proportional to total content of organic matter. Relative content of low-polar compounds in total amount of lipids and content of hydrocarbons, fatty acids, and sterols in the composition of these compounds can serve as an index of degree of transformation of organic matter in sediment because these compounds are resistant to various degree to microbial and hydrolytic decomposition and, consequently, are selectively preserved under conditions of biodegradation of organic compounds during oxydation-reduction processes.

Lipids and nitrogen isotopes of deep-water corals

The lipid and organic nitrogen isotopic (delta15N) compositions of two common deep-water corals (Lophelia pertusa and Madrepora oculata) collected from selected locations of the NE Atlantic are compared to the composition of suspended particulate organic matter, in order to determine their principle food source. Initial results suggest that they may feed primarily on zooplankton. This is based on the increased abundances of mono-unsaturated fatty acids and alcohols and the different ratios of the polyunsaturated fatty acids, 22:6/20:5 of the corals when compared to those of the suspended particulate organic matter. There is enrichment in L. pertusa of mono-unsaturated fatty acids and of delta15N relative to M. oculata. It is unclear whether this reflects different feeding strategies or assimilation/storage efficiencies of zooplankton tissue or different metabolism in the two coral species.