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Isoprenoid glycerol dialkyl glycerol tetraethers (isoGDGTs) are membrane lipids of Archaea. Organic biomarker proxies associated with these lipids, such as the TEX86 paleothermometer and Branched and Isoprenoid Tetraether (BIT) index, are often used in paleoenvironmental reconstructions for the marine environment, but their general applicability in lacustrine settings is hampered by limited understanding of the biological sources and environmental drivers influencing isoGDGT production. To validate the use of isoGDGT proxies in lakes, we studied the occurrence of isoGDGTs in Lake Chala, a permanently stratified (meromictic) crater lake in equatorial East Africa. We analyzed the abundance and distribution of isoGDGTs in 17 depth profiles of suspended particulate matter (SPM) collected monthly between September 2013 and January 2015, and compared this with the abundance and composition of archaea based on 16S rRNA gene and quantitative PCR analysis. Both isoGDGTs and archaeal abundance in the SPM were exceptionally low throughout the study period. In the oxygenated part of the water column, higher fractional abundances of crenarchaeol are matched by a predominance of the ammonia-oxidizing Thaumarchaeota I.1b that are known to produce this GDGT, whereas deep anoxic water layers are characterized by high fractional abundances of GDGT-0 as well as the anaerobic heterotrophic Group C3 MCG Bathyarchaea and specific euryarchaeotal methanogens. Analysis of intact polar lipid (IPL) isoGDGTs using SPM depth profiles from three months representing distinct seasons during the study period revealed the presence of several IPLs of GDGT-0 in the anoxic lower water column, which are rarely found in natural settings. IPL GDGT-0 with a phosphatidylglycerol (PG-), monohexose-phosphatidylglycerol (MH-PG-) and dihexose-phosphatidylglycerol (DH-PG-) head-group was typically only present just above the lake bottom at 90 m depth and probably reflect specific communities of ana

Particulate pyrogenic carbon (PyC) transported by rivers and aerosols, and deposited in marine sediments, is an important part of the carbon cycle. The chemical composition of PyC is temperature dependent and levoglucosan is a source-specific burning marker used to trace low-temperature PyC. Levoglucosan associated to particulate material has been shown to be preserved during riverine transport and marine deposition in high- and mid-latitudes, but it is yet unknown if this is also the case for (sub)tropical areas, where 90% of global PyC is produced. Here, we investigate transport and deposition of levoglucosan in suspended and riverbed sediments from the Amazon River system and adjacent marine deposition areas. We show that the Amazon River exports negligible amounts of levoglucosan and that concentrations in sediments from the main Amazon tributaries are not related to long-term mean catchment-wide fire activity. Levoglucosan concentrations in marine sediments offshore the Amazon Estuary are positively correlated to total organic content regardless of terrestrial or marine origin, supporting the notion that association of suspended or dissolved PyC to biogenic particles is critical in the preservation of PyC. We estimate that 0.5-10 x 10(6) g yr(-1) of levoglucosan is exported by the Amazon River. This represents only 0.5-10 ppm of the total exported PyC and thereby an insignificant fraction, indicating that riverine derived levoglucosan and low-temperature PyC in the tropics are almost completely degraded before deposition. Hence, we suggest caution in using levoglucosan as tracer for past fire activity in tropical settings near rivers., Funding Agencies|European Research Council (ERC) under the European Unions Seventh Framework ProgramEuropean Research Council (ERC) [FP7/2007-2013, 339206]; DFG Excellence ClusterGerman Research Foundation (DFG) [307, KNR/97-4, MSM20/3]; FAPESPFundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP) [2018/15123-4, 2019/24349-9, 2011/06609-1, 2012/502260-6, 2016/02656-9, 2018/23899-2, 2019/24977-0]; CAPESCoordenacao de Aperfeicoamento de Pessoal de Nivel Superior (CAPES) [564/2015, 88881.313535/201901]; CNPqConselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPQ) [302607/2016-1, 422255/2016-5, 304727/20172]; Alexander von Humboldt FoundationAlexander von Humboldt Foundation; Eidgenossische Technische Hochschule Zurich

Fire causes dramatic energy and matter exchanges between biosphere and atmosphere on a regional to global scale. Predicting fires, however, is hindered by the complex interplay of fire, climate, and vegetation. Paleo-fire records provide critical information beyond instrumental records that cover only the past few decades and may be used to assess the role of fire in large-scale and long-term environmental changes. Here we present a 22,000-year multiproxy record of fire regime from a sediment core retrieved offshore South Java, Indonesia. We use microcharcoal in combination with two molecular markers of burning, levoglucosan and polycyclic aromatic hydrocarbons, to reconstruct fire occurrence as well as fire intensity in the past. We show that fire occurrence and intensity were high during the Last Glacial Maximum (LGM; around 21,000 years ago) and low during the Heinrich Stadial 1 and the early Holocene. Both fire regime and vegetation in tropical regions with high annual rainfall were primarily controlled by rainfall seasonality. However, fire additionally stabilized the savannah (rainforest)-dominated ecosystem during the LGM (early Holocene) but caused transitions between the two vegetation types during the deglaciation and the late Holocene.

The TEX86 is a widely used paleotemperature proxy based on isoprenoid glycerol dibiphytanyl glycerol tetraethers (GDGTs) produced by Thaumarchaeota. Archaeal membranes are composed of GDGTs with polar head groups (IPL-GDGTs), most of which are expected to be degraded completely or transformed into more recalcitrant core lipid (CL)-GDGTs upon cell lysis. Here, we examined the differences in concentration and distribution of core lipid (CL)- and intact polar lipid (IPL)-GDGTs in surface sediments at different deposition depths, and different oxygen bottom water concentrations(<3–83 lmol L1). Surface sediments were sampled from 900 to 3000 m depth on a seamount (Murray Ridge), whose summit protrudes into the oxygen minimum zone of the Arabian Sea. Concentrations of organic carbon, IPL- and CL-GDGTs decreased linearly with increasing maximum residence time in the oxic zone of the sediment (tOZ), suggesting increasing sedimentary degradation of organic matter and GDGTs. IPL-GDGT-0 was the only exception and increased with tOZ, indicating that this GDGT was probably produced in situ in the surface sediment. Concentrations of crenarchaeol with glycosidic headgroups decreased with increasing tOZ, while crenarchaeol with a hexose, phosphohexose head (HPH) group, in contrast, showed an increase with increasing tOZ, indicating that the concentration of HPH crenarchaeol was primarily determined by in situ production in surficial sediments.TEX86 values of both IPL-derived GDGTs and CL-GDGTs decreased by0.08 units with increasing water depth, in spite of the sea surface temperatures being identical for the restricted area studied. In situ production in sediments could be excluded as the main cause, due to the slow production rates of GDGTs in sediments, and previous observations of the same trends in TEX86 in sediment trap material. Instead, the incorporation of GDGTs produced in the oxygen minimum zone (with high TEX86 values) and their preferential degradation during the sinkin

Glycerol dibiphytanyl glycerol tetraether (GDGT) lipids are part of the cellular membranes of Thaumarchaeota, an archaeal phylum composed of aerobic ammonia oxidizers, and are used in the paleotemperature proxy TEX86. GDGTs in live cells possess polar head groups and are called intact polar lipids (IPL-GDGTs). Their transformation to core lipids (CL) by cleavage of the head group was assumed to proceed rapidly after cell death, but it has been suggested that some of these IPL-GDGTs can, just like the CL-GDGTs, be preserved over geological timescales. Here, we examined IPL-GDGTs in deeply buried (0.2–186 mbsf, ~2.5 Myr) sediments from the Peru Margin. Direct measurements of the most abundant IPL-GDGT, IPL-crenarchaeol, specific for Thaumarchaeota, revealed depth profiles, which differed per head group. Shallow sediments (<1 mbsf) contained IPL-crenarchaeol with both glycosidic and phosphate head groups, as also observed in thaumarchaeal enrichment cultures, marine suspended particulate matter and marine surface sediments. However, hexose, phosphohexose-crenarchaeol is not detected anymore below 6 mbsf (~7 kyr), suggesting a high lability.In contrast, IPL-crenarchaeol with glycosidic head groups is preserved over timescales of Myr. This agrees with previous analyses of deeply buried (>1 m) marine sediments, which only reported glycosidic and no phosphate-containing IPL-GDGTs. TEX86 values of CL-GDGTs did not markedly change with depth, and the TEX86 of IPL-derived GDGTs decreased only when the proportions of monohexose- to dihexose-GDGTs changed, likely due to the enhanced preservation of the monohexose GDGTs. Our results support the hypothesis that in situ GDGT production and differential IPL degradation in sediments is not substantially affecting TEX86 paleotemperature estimations based on CL–GDGTs and indicates that likely only a small amount of IPL-GDGTs present in deeply buried sediments is part of cell membranes of active archaea. The amount of archaeal biomass

Two commonly used proxies based on the distribution of glycerol dialkyl glycerol tetraethers (GDGTs) are the TEX86 paleothermometer for sea-surface temperature reconstructions and theBIT index for reconstructing soil organic matter input to the ocean. An initial round-robin studyof two sediment extracts, in which fifteen laboratories participated, showed relatively consistentTEX86 values (reproducibility ±3-4 °C when translated to temperature) but a large spread in BITmeasurements (reproducibility ±0.41 on a scale of 0 to 1). Here we report results of a secondround-robin study with thirty-five laboratories in which three sediments, one sediment extractand 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 1.3-3.0 °C when translated totemperature. These results are similar to those of other temperature proxies used inpaleoceanography. Comparison of the results obtained from one of the three sediments showed that TEX86 and BIT indices are not significantly affected by interlaboratory differences insediment 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 poorreproducibility and a large overestimation of the =true‘ (i.e., molar-based) BIT index. The latter is likely due to, amongst other factors, the higher mass spectrometric response of branched GDGTscompared to crenarchaeol, which also varies among mass spectrometers. Correction for thisdifferent mass spectrometric response showed a considerable improvement in the reproducibilityof BIT index measurements among laboratories, as well as a su

Archaeal and bacterial glycerol dialkyl glycerol tetraether lipids (GDGTs) are used in various proxies, such as TEX86 and the BIT index. In living organism, they contain polar head groups (intact polar lipids – IPLs). IPL GDGTs have also been detected in ancient marine sediments and it is unclear whether or not they are fossil entities or are part of living cells. In order to determine the extent of degradation of IPL GDGTs over geological timescales, we analyzed turbidite deposits, which had been partly reoxidized for several kyr after deposition on the Madeira Abyssal Plain. Analysis of core lipid (CL) and IPL-derived GDGTs showed a reduction in concentration by two orders of magnitude upon post-depositional oxidation, while IPL GDGTs with a mono- or dihexose head group decreased by 2–3 orders of magnitude. The BIT index for CL- and IPL-derived GDGTs increased substantially upon oxidation from 0.1 to up to 0.5. Together with changing MBT/CBT values, this indicates preferential preservation of soil-derived branched GDGTs over marine isoprenoid GDGTs, combined with in situ production of branched GDGTs in the sediment. The TEX86 value for IPL-derived GDGTs decreased by 0.07 upon oxidation, while that of CL GDGTs showed no significant change. Isolation of IPLs revealed that the TEX86 value for monohexose GDGTs was 0.55, while the that for dihexose GDGTs was substantially higher, 0.70. Thus, the decrease in TEX86 for IPLderived GDGTs was in agreement with the dominance of monohexose GDGTs in the oxidized turbidite, probably caused by a combination of in situ production as well as selective preservation of terrestrial isoprenoid GDGTs. Due to the low amount of IPL GDGTs vs. CL GDGTs, the impact of IPL degradation on CLbasedTEX86 paleotemperature estimates was negligible.

The TEX86 is a proxy based on a ratio of pelagic archaeal glycerol dibiphytanyl glycerol tetraether lipids (GDGTs), and used for estimating past sea water temperatures. Concerns exist that in situ production of GDGTs lipids by sedimentary Archaea may affect its validity. In this study, we investigated the influence of benthic GDGT production on the TEX86 by analyzing the concentrations and distributions of GDGTs present as intact polar lipids (IPLs) and as core lipids (CLs) in three sediment cores deposited under contrasting redox conditions across a depth range from 900 to 3000 m below sea level in and below the Arabian Sea oxygen minimum zone (OMZ). Direct analysis of IPLs with crenarchaeol as CL via HPLC/ESI-MS2 revealed that surface sediments in the OMZ were relatively depleted in the phospholipid hexose, phosphohexose (HPH)-crenarchaeol compared to suspended particulate matter from the water column, suggesting preferential and rapid degradation of this IPL. In sediment cores recovered from deeper, more oxic environments, concentrations of HPH-crenarchaeol peaked at the surface, probably due to in situ production by ammonia-oxidizing Archaea, followed by a rapid decrease with increasing depth. No surface maximum was observed in the sediment core from within the OMZ. In contrast, the glycolipids, monohexose-crenarchaeol and dihexose-crenarchaeol, did not change in concentration with depth in the sediment, indicating that they were relatively well preserved and likely mostly derived from fossil pelagic GDGTs.These results suggest that phospholipids are more sensitive to degradation, while glycolipids might be preserved over longer time scales, in line with previous incubation and modeling studies. Furthermore, in situ produced IPL-GDGTs did not accumulate as IPLs, and did not influence the CL-TEX86. This suggests that in-situ produced GDGT lipids were more susceptible to degradation than fossil CL and IPL and did not accumulate as CL. In agreement, no significant

Glycerol dibiphytanyl glycerol tetraether-based intact polar lipids (IPL GDGTs) are used as biomarkers for living Archaea and are analyzed utilizing a variety of extraction and quantification techniques. Most IPL GDGT studies have used a modified Bligh–Dyer extraction method, but it has been suggested that Soxhlet extraction may be more efficient for environmental samples and biomass. We investigated the impact of three different extractions (Soxhlet, Bligh–Dyer and accelerated solvent extraction, ASE), two IPL quantification methods and two work up techniques (Na2SO4 and SiO2 column) on the amount and distribution of CL (core lipid)- and IPL-derived GDGTs and crenarchaeol-based IPLs in marine sediments from the Arabian Sea and Icelandic shelf, as well as a microbial mat from a Dutch beach. The different extraction procedures gave a similar yield of CL- and IPL-derived GDGTs. Direct analysis of crenarchaeol IPLs showed, however, that, while GDGTs with a monohexose head group were not affected by the extraction method, there was a large effect on IPL GDGTs containing dihexose or hexose, phosphohexose head groups. Quantification of IPL-derived GDGTs by way of either separation over a silica column or by subtraction of CL GDGTs in the total lipid extract before and after hydrolysis gave similar results, butthe ‘subtraction-method’ had a relatively large quantification error. However, the silica column, as wellas drying over a Na2SO4 column, resulted in a loss of the hexose, phosphohexose IPLs by up to 80%.Based on the results, a modified Bligh–Dyer extraction with as little further treatment as possible isrecommended to allow measurement of the full range of IPL GDGTs in sediments.

Branched Glycerol Dialkyl Glycerol Tetraethers (GDGTs) are membrane spanning lipids synthesised by as yet unknown bacteria that thrive in soils and peat. In order to obtain more information on their ecological niche, the stable carbon isotopic composition of branched GDGT-derived alkanes, obtained upon ether bond cleavage, has been determined in a peat and various soils, i.e. forest, grassland and cropland, covered by various vegetation types, i.e., C3- vs. C4-plant type. These δ13C values are compared with those of bulk organic matter and higher plant derived n-alkanes from the same soils. With average δ13C values of −28‰, branched GDGTs in C3 soils are only slightly depleted (ca. 1‰) relative to bulk organic carbon and on average 8.5‰ enriched relative to plant wax-derived long-chain n-alkanes ( nC29–nC33). In an Australian soil dominantly covered with C4 type vegetation, the branched GDGTs have a δ13C value of −18‰, clearly higher than observed in soils with C3 type vegetation. As with C3 vegetated soils, branched GDGT δ13C values are slightly depleted (1‰) relative to bulk organic carbon and enriched (ca. 5‰) relative to n-alkanes in this soil. The δ13C values of branched GDGT lipids being similar to bulk organic carbon and their co-variation with those of bulk organic carbon and plant waxes, suggest a heterotrophic life style and assimilation of relatively heavy and likely labile substrates for the as yet unknown soil bacteria that synthesise the branched GDGT lipids. However, a chemoautotrophic lifestyle, i.e. consuming respired CO2, could not be fully excluded based on these data alone. Based on a natural labelling experiment of a C3/C4 crop change introduced on one of the soils 23 years before sampling and based on a free-air CO2 enrichment experiment with labelled CO2 on another soil, a turnover time of ca. 18 years has been estimated for branched GDGTs in these arable soils.

Objective: This study aimed to identify the oncogenes at 20q involved in colorectal adenoma to carcinoma progression by measuring the effect of 20q gain on mRNA expression of genes in this amplicon. Methods: Segmentation of DNA copy number changes on 20q was performed by array CGH (comparative genomic hybridisation) in 34 non-progressed colorectal adenomas, 41 progressed adenomas (ie, adenomas that present a focus of cancer) and 33 adenocarcinomas. Moreover, a robust analysis of altered expression of genes in these segments was performed by microarray analysis in 37 adenomas and 31 adenocarcinomas. Protein expression was evaluated by immunohistochemistry on tissue microarrays. Results: The genes C20orf24, AURKA, RNPC1, TH1L, ADRM1, C20orf20 and TCFL5, mapping at 20q, were significantly overexpressed in carcinomas compared with adenomas as a consequence of copy number gain of 20q. Conclusion: This approach revealed C20orf24, AURKA, RNPC1, TH1L, ADRM1, C20orf20 and TCFL5 genes to be important in chromosomal instability-related adenoma to carcinoma progression. These genes therefore may serve as highly specific biomarkers for colorectal cancer with potential clinical applications.