28 resultados para Intramolecular cyclization


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It has long been known that extreme changes in North African hydroclimate occurred during the late Pleistocene yet many discrepancies exist between sites regarding the timing, duration and abruptness of events such as Heinrich Stadial (HS) 1 and the African Humid Period (AHP). The hydroclimate history of the Nile River is of particular interest due to its lengthy human occupation history yet there are presently few continuous archives from the Nile River corridor, and pre-Holocene studies are rare. Here we present new organic and inorganic geochemical records of Nile Basin hydroclimate from an eastern Mediterranean (EM) Sea sediment core spanning the past 28 ka BP. Our multi-proxy records reflect the fluctuating inputs of Blue Nile versus White Nile material to the EM Sea in response to gradual changes in local insolation and also capture abrupt hydroclimate events driven by remote climate forcings, such as HS1. We find strong evidence for extreme aridity within the Nile Basin evolving in two distinct phases during HS1, from 17.5 to 16 ka BP and from 16 to 14.5 ka BP, whereas peak wet conditions during the AHP are observed from 9 to 7 ka BP. We find that zonal movements of the Congo Air Boundary (CAB), and associated shifts in the dominant moisture source (Atlantic versus Indian Ocean moisture) to the Nile Basin, likely contributed to abrupt hydroclimate variability in northern East Africa during HS1 and the AHP as well as to non-linear behavior of hydroclimate proxies. We note that different proxies show variable gradual and abrupt responses to individual hydroclimate events, and thus might have different inherent sensitivities, which may be a factor contributing to the controversy surrounding the abruptness of past events such as the AHP. During the Late Pleistocene the Nile Basin experienced extreme hydroclimate fluctuations, which presumably impacted Paleolithic cultures residing along the Nile corridor.

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We reconstruct the environmental evolution of the East China Sea in the past 14 kyr based on glycerol dialkyl glycerol tetraethers (GDGTs) in a sediment core from the subaqueous Yangtze River Delta. Two primary phases are recognized. Phase I (13.8-8 cal kyr BP) reflects a predominantly continental influence, showing distinctly higher concentrations of branched GDGTs (averaged 143 ng/g dry sediment weight, dsw) than isoprenoid GDGTs (averaged 36 ng/g dsw), high BIT index (branched vs. isoprenoid tetraethers) values (>0.78) and a fluctuating GDGT-0/crenarchaeol ratio (R0/5, varied from 0.52 to 3.81). Within this interval, temporal increases of terrestrial and marine influence are attributed to Younger Dryas (YD) (ca. 12.9-12.2 cal kyr BP) cold event and melt-water pulse (MWP) -1B (11.5-11.1 cal kyr BP), respectively. The prominent transition from 8 to 7.9 cal kyr BP shows a sharp decrease in BIT index value (<0.4) and increase in crenarchaeol, which marks the beginning of phase II. Afterwards, the proxies remain relatively constant, which indicates that phase II (7.9 cal kyr BP-present) is a shelf sedimentary environment with high stand of sea level. Overall, the BIT index in our record serves as a good marker for terrestrial influence at the site, and likely reflects the flooding history of the region. The TEX86 (TetraEther Index of tetraethers consisting of 86 carbons) proxy is not applicable in phase I because of an excess terrestrial influence; but it seems to be valid for revealing the annual SST in phase II (21.6±0.9°C, n=49). In contrast, the MBT'/CBT (Methylation of Branched Tetraethers and Cyclization of Branched Tetraethers) proxy appears to faithfully record the annual mean air temperature (MAT) (14.3±0.63°C, n=68) and presents an integrated signal over the middle and lower Yangtze River drainage basin.

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Glycolipids are prominent constituents in the membranes of cells from all domains of life. For example, diglycosyl-glycerol dibiphytanyl glycerol tetraethers (2Gly-GDGTs) are associated with methanotrophic ANME-1 archaea and heterotrophic benthic archaea, two archaeal groups of global biogeochemical importance. The hydrophobic biphytane moieties of 2Gly-GDGTs from these two uncultivated archaeal groups exhibit distinct carbon isotopic compositions. To explore whether the isotopic compositions of the sugar headgroups provide additional information on the metabolism of their producers, we developed a procedure to analyze the d13C values of glycosidic headgroups. Successful determination was achieved by (1) monitoring the contamination from free sugars during lipid extraction and preparation, (2) optimizing the hydrolytic conditions for glycolipids, and (3) derivatizing the resulting sugars into aldononitrile acetate derivatives, which are stable enough to withstand a subsequent column purification step. First results of d13C values of sugars cleaved from 2Gly-GDGTs in two marine sediment samples, one containing predominantly ANME-1 archaea and the other benthic archaea, were obtained and compared with the d13C values of the corresponding biphytanes. In both samples the dominant sugar headgroups were enriched in 13C relative to the corresponding major biphytane. This 13C enrichment was significantly larger in the putative major glycolipids from ANME-1 archaea (~15 per mil) than in those from benthic archaea (<7 per mil). This method opens a new analytical window for the examination of carbon isotopic relationships between sugars and lipids in uncultivated organisms.

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The transition from the last Glacial to the current Interglacial, the Holocene, represents an important period with climatic and environmental changes impacting ecosystems. In this study, we examined the interplay between the Indian Ocean Summer Monsoon (IOSM) and the Westerlies at lake Nam Co, southern Tibet to understand the climatic effects on the ecosystem. Different organic geochemical proxies (n-alkanes, glycerol dialkyl glycerol tetraethers, dD, d13Corg, d15N) are applied to reconstruct the environmental and hydrological changes on one of the longest available paleorecords at the Tibetan Plateau. Based on our paleohydrological dD proxies, the aquatic signal lags the terrestrial one due to specific ecological thresholds, which, in addition to climatic changes, can influence aquatic organisms. The aquatic organisms' response strongly depends on temperature and associated lake size, as well as pH and nutrient availability. Because the terrestrial vegetation reacts faster and more sensitively to changes in the monsoonal and climatic system, the dD of n-C29 and the reconstructed inflow water signal represent an appropriate IOSM proxy. In general, the interplay of the different air masses seems to be primarily controlled by solar insolation. In the Holocene, the high insolation generates a large land-ocean pressure gradient associated with strong monsoonal winds and the strongest IOSM. In the last glacial period, however, the weak insolation promoted the Westerlies, thereby increasing their influence at the Tibetan Plateau. Our results help to elucidate the variable IOSM, and they illustrate a remarkable shift in the lake system regarding pH, d13Corg and d15N from the last glacial to the Holocene interglacial period.