Absence of seasonal patterns in MBT-CBT indices in mid-latitude soils

The degree of methylation and cyclization of bacteria-derived branched glycerol dialkyl glycerol tetraether (GDGT) membrane lipids in soils depends on temperature and soil pH. Expressed in the methylation index of branched tetraethers (MBT) and cyclization ratio of branched tetraethers (CBT), these relationships are used to reconstruct past annual mean air temperature (MAT) based on the distribution of branched GDGTs in ancient sediments; the MBT-CBT proxy. Although it was shown that the best correlation of this proxy is with annual MAT, it remains unknown whether a seasonal bias in temperature reconstructions could occur, such as towards a seasonal period of optimal growth’ of the, as yet, unidentified soil bacteria which produce branched GDGTs. To investigate this possibility, soils were sampled from eight different plots in the USA (Minnesota and Ohio), The Netherlands (Texel) and the UK (Devon) in time series over 1 year and analyzed for their branched GDGT content. Further analyses of the branched GDGTs present as core lipids (CLs; the presumed fossil pool) and intact polar lipids (IPLs; the presumed extant pool) were undertaken for two of the investigated soil plots. The amount of IPL-derived branched GDGTs is low relative to the branched GDGT CLs, i.e. only 6–9% of the total branched GDGT pool.In all soils, no clear change was apparent in the distribution of branched GDGT lipids (either core or IPL-derived) with seasonal temperature change; the MBT–CBT temperature proxy gave similar temperature estimates year-round, which generally matched the mean annual soil temperature. In addition to a lack of coherent changes in relative distributions, concentrations of the branched GDGTs did not show clear changes over the seasons. For IPL-derived GDGTs these results suggest that their turnover time in soils is in the order of 1 year or more. Thus, our study does not provide evidence for seasonal effects on the distribution of branched GDGTs in soils, at least at mid-latitudes, and therefore, no direct evidence for a bias of MBT–CBT reconstructed temperatures towards a certain season of optimal growth of the source bacteria. If, however, there is a slight seasonal preference of branched GDGT production, which can easily be obscured by natural variability due to the heterogeneity of soils, then a seasonal bias may potentially still develop over time due to the long turnover time of branched GDGTs

Developing a genetic approach to target cyanobacterial producers of heterocyte glycolipids in the environment

Heterocytous cyanobacteria are important players in the carbon and nitrogen cycle. They can fix dinitrogen by using heterocytes, specialized cells containing the oxygen-sensitive nitrogenase enzyme surrounded by a thick polysaccharide and glycolipid layer which prevents oxygen diffusion and nitrogenase inactivation. Heterocyte glycolipids can be used to detect the presence of heterocytous cyanobacteria in present-day and past environments, providing insight into the functioning of the studied ecosystems. However, due to their good preservation throughout time, heterocyte glycolipids are not ideal to detect and study living communities, instead methods based on DNA are preferred. Currently cyanobacteria can be detected using untargeted genomic approaches such as metagenomics, or they can be specifically targeted by, for example, the use of primers that preferentially amplify their 16S rRNA gene or their nifH gene in the case of nitrogen fixing cyanobacteria. However, since not all cyanobacterial nitrogen fixers are heterocytous, there is currently no fast gene-based method to specifically detect and distinguish heterocytous cyanobacteria. Here, we developed a PCR-based method to specifically detect heterocytous cyanobacteria by designing primers targeting the gene (hglT) encoding the enzyme responsible for the last step in the biosynthesis of heterocyte glycolipid (i.e., a glycosyltransferase). We designed several primer sets using the publicly available sequences of 23 heterocytous cyanobacteria, after testing them on DNA extracts of 21 heterocyte-forming and 7 non-heterocyte forming freshwater cyanobacteria. The best primer set was chosen and successfully used to confirm the presence of heterocytous cyanobacteria in a marine environmental sample

Holocene subsurface temperature variability in the eastern Antarctic continental margin

We reconstructed subsurface (∼45-200m water depth) temperature variability in the eastern Antarctic continental margin during the late Holocene, using an archaeal lipid-based temperature proxy (TEX 86 L). Our results reveal that subsurface temperature changes were probably positively coupled to the variability of warmer, nutrient-rich Modified Circumpolar Deep Water (MCDW, deep water of the Antarctic circumpolar current) intrusion onto the continental shelf. The TEX 86 L record, in combination with previously published climatic records, indicates that this coupling was probably related to the thermohaline circulation, seasonal variability in sea ice extent, sea temperature, and wind associated with high frequency climate dynamics at low-latitudes such as internal El Nio Southern Oscillation (ENSO). This in turn suggests a linkage between centennial ENSO-like variability at low-latitudes and intrusion variability of MCDW into the eastern Antarctic continental shelf, which might have further impact on ice sheet evolution. Copyright 2012 by the American Geophysical Union

Origin of lipid biomarkers in mud volcanoes from the Alboran Sea, western Mediterranean

Mud volcanoes (MVs) are the most prominent indicators of active methane/hydrocarbon venting at the seafloor on both passive and active continental margins. Their occurrence in the western Mediterranean is patent at the West Alboran Basin, where numerous MVs develop overlaying a major sedimentary depocentre containing overpressured shales. Although some of these MVs have been studied, the detailed biogeochemistry of expelled mud so far has not been examined in detail. This work provides the first results on the composition and origin of organic matter, anaerobic oxidation of methane (AOM) processes and general characteristics on MV dynamics using lipid biomarkers as the main tool. Lipid biomarker analysis was performed on MV expelled material (mud breccias) and interbedded hemipelagic sediments from Perejil, Kalinin and Schneider's Heart MVs located in the northwest margin of the Alboran Sea. The n alkane distributions and n alkane-derived indices (CPI and ACL), in combination with the epimerization degree of hopanes (22S/(22S+22R)) indicate that all studied mud breccia have a similar biomarker composition consisting of mainly thermally immature organic matter with an admixture of petroleum-derived compounds. This concordant composition indicates that common source strata must feed all three studied MVs. The past or present AOM activity was established using lipid biomarkers specific for anaerobic methanotrophic archaea (irregular isoprenoids and dialkyl glycerol diethers) and the depleted carbon isotope composition (δ13C) of crocetane/phytane. The presence of these lipid biomarkers, together with the low amounts of detected glycerol dialkyl glycerol tetraethers, is consistent with the dominance of anaerobic methanotrophs of the ANME-2 over ANME-1, at least in mud breccia from Perejil MVs. In contrast, the scarce presence or lack of these AOM-related lipid biomarkers in sediments from Kalinin and Schneider's Heart MVs, suggests that no recent active methane seepage has occurred at these sites. Moreover, the observed methane concentrations support the current activity of Perejil MV, and the very low methane seepage activity in Kalinin and Schneider's Heart MVs.This study was supported by Project CTM2009-07715, CGL2011-1441 and CGL2012-32659 (MINECO, Spain), by the VENI grant from the Netherlands Organization for Scientific Research (NWO) and the Royal Netherland Institute for Sea Research (NIOZ via ZKOprogramme) (Texel, The Netherlands). C. F. López-Rodríguez was funded by a JAE-PhD fellowship from the CSIC (Spain)

Applicability of the Long Chain Diol Index (LDI) as a Sea Surface Temperature Proxy in the Arabian Sea

The long-chain diol index (LDI) is a relatively new proxy for sea surface temperature (SST) which has been rarely applied in upwelling regions. Here, we evaluated its application by comparison with other SST records obtained by commonly used proxies, that is, the Mg/Ca ratio of the planktonic foraminifera species Globigerinoides ruber and the alkenone paleothermometer U-37(K '). We focused on the last glacial-interglacial transition of four different sedimentary archives from the western and northern Arabian Sea, which are currently under the influence of monsoon-induced upwelling and the associated development of an oxygen minimum zone. The UK ' 37 ${{\mathrm{U}}{\mathrm{K}\prime }}_{37}$ and Mg/Ca-G.ruber SST records revealed an increase of 0.6-3.4 degrees C from the Last Glacial Maximum to the late Holocene with somewhat higher amplitude in the northern part of the Arabian Sea than compared to the western part. In contrast, the LDI SSTs did not reveal major changes during the last glacial-interglacial transition which was followed by a decreasing trend during the Holocene. The LGM versus the Holocene LDI SSTs ranged between -0.2 and -2.7 degrees C. Particularly at one record, offshore Oman, the SST decrease during the Holocene was high in amplitude, suggesting a potential cold bias, possibly related to changes in upwelling intensity. This indicates that care has to be taken when applying the LDI for annual mean SST reconstruction in upwelling regions

Rapid sulfurisation of highly branched isoprenoid (HBI) alkenes in sulfidic Holocene sediments from Ellis Fjord, Antarctica

Author Posting. © Elsevier B.V., 2007. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Organic Geochemistry 38 (2007): 128-139, doi:10.1016/j.orggeochem.2006.08.003.Samples of particulate organic matter from the water column and anoxic Holocene sediment layers from the Small Meromictic Basin (SMB) in Ellis Fjord (eastern Antarctica) were analyzed to study the early incorporation of reduced inorganic sulfur species into highly branched isoprenoid (HBI) alkenes. HBIs were not detected in the water column samples from austral winter, whereas compounds containing the C25 HBI skeleton were abundant in all analyzed Holocene sediment layers. The structure of the C25:2 HBI alkene together with its enriched stable carbon isotopic composition suggest that the HBI alkene is produced by a diatom or diatoms probably belonging to the Navicula genus present in the sea-ice which covers the area most of the year. Within just 500 years of deposition, all of the HBI alkene was sulfurised. A mixture of products was formed, including components tentatively identified as a C25 HBI thiane and three S-containing dimers composed of two C25:1 HBI skeletons linked together by a sulfide bond. Most of the HBI alkene, however, was converted to polar S-containing compounds. The observed reaction rate for sulfurisation the C25:2 HBI alkene is the highest observed so far in natural systems. Sterols and other lipids known to be prone to sulfurisation were only minimally sulfurised under these depositional conditions. The reason for this is presently unclear.Funding for the collection of the sediment and water samples (by MJLC and CW) was provided by ASAC grant 1166 to JKV. This work was further supported by a grant from the Netherlands Organization for Scientific Research (NWO; Netherlands Antarctic Research Proposals 851.20.006 to JSSD)

A 26 million year gap in the central Arctic record at the greenhouse-icehouse transition: Looking for clues

The Cenozoic record of the Lomonosov Ridge (central Arctic Ocean) recovered during Integrated Ocean Drilling Program (IODP) Expedition 302 revealed an unexpected 26 Ma hiatus, separating middle Eocene (�44.4 Ma) from lower Miocene sediments (�18.2 Ma). To elucidate the nature of this unconformity, we performed a multiproxy palynological (dinoflagellate cysts, pollen, and spores), micropaleontological (siliceous microfossils), inorganic, and organic (Tetra Ether Index of lipids with 86 carbon atoms (TEX86) and Branched and Isoprenoid Tetraether (BIT)) geochemical analysis of the sediments from �5 m below to �7 m above the hiatus. Four main paleoenvironmental phases (A–D) are recognized in the sediments encompassing the unconformity, two below (A–B) and two above (C–D): (A) Below the hiatus, proxies show relatively warm temperatures, with Sea Surface Temperatures (TEX86-derived SSTs) of about 8�C and high fresh to brackish water influence. (B) Approaching the hiatus, proxies indicate a cooling trend (TEX86-derived SSTs of �5�C), increased freshwater influence, and progressive shoaling of the Lomonosov Ridge drilling site, located close to or at sea level. (C) The interval directly above the unconformity contains sparse reworked Cretaceous to Oligocene dinoflagellate cysts. Sediments were deposited in a relatively shallow, restricted marine environment. Proxies show the simultaneous influence of both fresh and marine waters, with alternating oxic and anoxic conditions. Pollen indicates a relatively cold climate. Intriguingly, TEX86-derived SSTs are unexpectedly high, �15–19�C. Such warm surface waters may be partially explained by the ingression of warmer North Atlantic waters after the opening of the Fram Strait during the early Miocene. (D) Sediments of the uppermost interval indicate a phase of extreme oxic conditions, and a well-ventilated environment, which occurred after the complete opening of the Fram Strait. Importantly, and in contrast with classical postrifting thermal subsidence models for passive margins, our data suggest that sediment erosion and/or nondeposition that generated the hiatus was likely due to a progressive shoaling of the Lomonosov Ridge. A shallow water setting both before and after the hiatus suggests that the Lomonosov Ridge remained at or near sea level for the duration of the gap in the sedimentary record. Interacting sea level changes and/or tectonic activity (possibly uplift) must be invoked as possible causes for such a long hiatus

Organohalide-respiring Desulfoluna species isolated from marine environments

The online version of this article (https://doi.org/10.1038/s41396-019-0573-y) contains supplementary material, which is available to authorized usersThe genus Desulfoluna comprises two anaerobic sulfate-reducing strains, D. spongiiphila AA1T and D. butyratoxydans MSL71T, of which only the former was shown to perform organohalide respiration (OHR). Here we isolated a third strain, designated D. spongiiphila strain DBB, from marine intertidal sediment using 1,4-dibromobenzene and sulfate as the electron acceptors and lactate as the electron donor. Each strain harbors three reductive dehalogenase gene clusters (rdhABC) and corrinoid biosynthesis genes in their genomes, and dehalogenated brominated but not chlorinated organohalogens. The Desulfoluna strains maintained OHR in the presence of 20?mM sulfate or 20?mM sulfide, which often negatively affect other organohalide-respiring bacteria. Strain DBB sustained OHR with 2\% oxygen in the gas phase, in line with its genetic potential for reactive oxygen species detoxification. Reverse transcription-quantitative PCR revealed differential induction of rdhA genes in strain DBB in response to 1,4-dibromobenzene or 2,6-dibromophenol. Proteomic analysis confirmed expression of rdhA1 with 1,4-dibromobenzene, and revealed a partially shared electron transport chain from lactate to 1,4-dibromobenzene and sulfate, which may explain accelerated OHR during concurrent sulfate reduction. Versatility in using electron donors, de novo corrinoid biosynthesis, resistance to sulfate, sulfide and oxygen, and concurrent sulfate reduction and OHR may confer an advantage to marine Desulfoluna strains.We thank Johanna Gutleben and Maryam Chaib de Mares for sediment sampling, W. Irene C. Rijpstra for fatty acid analysis, and Andreas Marquardt (Proteomics Centre of the University of Konstanz) for proteomic analyses. We acknowledge the China Scholarship Council (CSC) for the support to PP and YL. The authors thank BE-BASIC funds (grants F07.001.05 and F08.004.01) from the Dutch Ministry of Economic Affairs, ERC grant (project 323009), the Gravitation grant (project 024.002.002) and the UNLOCK project (NRGWI.obrug.2018.005) of the Netherlands Ministry of Education, Culture and Science and the Netherlands Science Foundation (NWO), and National Natural Science Foundation of China (project No.51709100) for funding.info:eu-repo/semantics/publishedVersio

Molecular evidence of Late Archean archaea and the presence of a subsurface hydrothermal biosphere

Author Posting. © National Academy of Sciences of the USA, 2007. This is the author's version of the work. It is posted here by permission of National Academy of Sciences of the USA for personal use, not for redistribution. The definitive version was published in Proceedings of the National Academy of Sciences 104 (2007): 14260-14265, doi:10.1073/pnas.0610903104.Highly cracked and isomerized archaeal lipids and bacterial lipids, structurally changed by thermal stress, are present in solvent extracts of 2,707-2,685 million year old (Ma) metasedimentary rocks from Timmins, Ontario, Canada. These lipids appear in conventional gas chromatograms as unresolved complex mixtures (UCMs) and include cyclic and acyclic biphytanes, C36-C39 derivatives of the biphytanes, and C31-C35 extended hopanes. Biphytane and extended hopanes are also found in high pressure catalytic hydrogenation (HPCH) products released from solvent-extracted sediments,indicating that archaea and bacteria were present in Late Archean sedimentary environments. Post-depositional, hydrothermal gold mineralization and graphite precipitation occurred prior to metamorphism (~2,665 Ma). Late Archean metamorphism significantly reduced the kerogen’s adsorptive capacity and severely restricted sediment porosity, limiting the potential for post-Archean additions of organic matter to the samples. Argillites exposed to hydrothermal gold mineralization have disproportionately high concentrations of extractable archaeal and bacterial lipids relative to what is releasable from their respective HPCH product and what is observed for argillites deposited away from these hydrothermal settings. The addition of these lipids to the sediments likely results from a Late Archean subsurface hydrothermal biosphere of archaea and bacteria.This project was supported by NASA Exobiology grant #NAG5-13446 to Fabien Kenig. SEM analysis was supported by NSF grant EAR 0318769 to Juergen Schieber. GC×GC analysis was supported by NSF grant IIS-0430835 and the Seaver Foundation to Christopher M. Reddy

An interlaboratory study of TEX86 and BIT analysis of sediments, extracts and standard mixtures.

Two commonly used proxies based on the distribution of glycerol dialkyl glycerol tetraethers (GDGTs) are the TEX86 (TetraEther indeX of 86 carbon atoms) paleothermometer for sea surface temperature reconstructions and the BIT (Branched Isoprenoid Tetraether) index for reconstructing soil organic matter input to the ocean. An initial round-robin study of two sediment extracts, in which 15 laboratories participated, showed relatively consistent TEX86 values (reproducibility ±3-4°C when translated to temperature) but a large spread in BIT measurements (reproducibility ±0.41 on a scale of 0-1). Here we report results of a second round-robin study with 35 laboratories in which three sediments, one sediment extract, and two mixtures of pure, isolated GDGTs were analyzed. The results for TEX86 and BIT index showed improvement compared to the previous round-robin study. The reproducibility, indicating interlaboratory variation, of TEX86 values ranged from 1.3 to 3.0°C when translated to temperature. These results are similar to those of other temperature proxies used in paleoceanography. Comparison of the results obtained from one of the three sediments showed that TEX86 and BIT indices are not significantly affected by interlaboratory differences in sediment extraction techniques. BIT values of the sediments and extracts were at the extremes of the index with values close to 0 or 1, and showed good reproducibility (ranging from 0.013 to 0.042). However, the measured BIT values for the two GDGT mixtures, with known molar ratios of crenarchaeol and branched GDGTs, had intermediate BIT values and showed poor reproducibility and a large overestimation of the "true" (i.e., molar-based) BIT index. The latter is likely due to, among other factors, the higher mass spectrometric response of branched GDGTs compared to crenarchaeol, which also varies among mass spectrometers. Correction for this different mass spectrometric response showed a considerable improvement in the reproducibility of BIT index measurements among laboratories, as well as a substantially improved estimation of molar-based BIT values. This suggests that standard mixtures should be used in order to obtain consistent, and molar-based, BIT values