Distribution Of Glycerol Dialkyl Glycerol Tetraethers Research Articles

Glycerol dialkyl glycerol tetraethers in surficial coastal and open marine sediments around China: Indicators of sea surface temperature and effects of their sources

Accurate reconstruction of past sea surface temperature (SST) is important for the understanding of past climate and its variations. Recently, the TEX86 indicator (TetraEther indeX of tetraethers consisting of 86 carbon atoms), based on glycerol dialkyl glycerol tetraethers (GDGTs) has been developed into a promising proxy for SST reconstruction. In this study, we investigated the distribution of GDGTs in surficial sea bottom sediments from coastal and open marine settings around China between 18°N and 38°N in water depth of either <100 or >1000m.As the distribution patterns of GDGTs reflect their biological sources and their respective habitats these can be identified from the sediment samples investigated. The distributions of branched GDGTs (brGDGTs) in the Yellow Sea (YS) was found to be similar to that of the lower Yellow River basin indicating that the brGDGTs in the YS originated from terrestrial soil. While the variability of the cyclisation ratio of branched tetraethers (CBT)-derived pH values in the Pearl River estuary (PRE) suggested that brGDGTs might also be produced in situ in coastal sediments or in the water column. In the shallow areas (water depth <100m, the YS, East China Sea and PRE) TEX86H-based SST (SST86H) was overestimated or underestimated when compared with mean annual SSTsatellite, most likely caused by seasonality or overprint by a cold-biased terrestrial signal. In the South China Sea (SCS), at water depth >1000m, the SST86H matched well the mean annual SST determined by satellite, indicating the applicability of the TEX86H temperatures for paleoclimate investigations in these study areas and, potentially, in similar settings of deep water. These findings provide the basis for application of branched/isoprenoid index (BIT) and TEX86 as indicators for temperature and paleotemperature in coastal and open marine environments around China.

Distribution of bacterial and archaeal ether lipids in soils and surface sediments of Tibetan lakes: Implications for GDGT-based proxies in saline high mountain lakes

Bacterial and archaeal lipids, such as glycerol dialkyl glycerol tetraethers (GDGTs) and dialkyl glycerol diethers, are increasingly used as proxies for specific environmental parameters, such as air temperature and soil pH in lacustrine environments. Little is known, however, about the distribution and applicability of bacterial and archaeal lipids on the Tibetan Plateau. We investigated nine different watersheds across the plateau by way of sediments from lakes and rivers, as well as the surrounding soils. Our transect study included a salinity gradient and focused on saline lakes, which are rarely examined. We analyzed archaeal isoprenoid (i) and bacterial branched (b) GDGTs, as well as archaeol to trace their sources and environmental factors, influencing their distributions. We could show that iGDGTs were produced in situ and bGDGTs were primarily soil-derived although we could not exclude in situ production of bGDGTs in the lakes. The most important environmental variables correlating with GDGT distributions were temperature and salinity. Bacterial GDGT distributions correlated mainly with salinity, while archaeal lipid distributions correlated with temperature. Based on the correlation of methylation (MBT′) and cyclisation (CBT) indices of bGDGTs with pH and mean annual air temperature (MAAT), we established local calibrations for the Tibetan lakes. TEX86 could also be applied to reconstruct temperature, which was strongly biased towards measured summer lake water temperature, indicating enhanced production of iGDGTs in the summer months. Existing proxies show, therefore, potential for palaeoclimate reconstruction on the Tibetan Plateau if local calibrations are applied.

Sources of glycerol dialkyl glycerol tetraethers (GDGTs) in catchment soils, water column and sediments of Lake Rotsee (Switzerland) – Implications for the application of GDGT-based proxies for lakes

We analysed glycerol dialkyl glycerol tetraether (GDGT) distributions in the water column, sediment and catchment soils of the Swiss Lake Rotsee to determine the sources of GDGTs in the lake sediment and to determine the implications for GDGT-based palaeoclimate proxies. The branched GDGT (brGDGT) distribution in the soils surrounding the lake showed significant heterogeneity, which may be partly explained by vegetation cover and soil moisture. One group of soils seems to provide the largest contribution of soil-derived GDGTs to the lake, or the distribution of GDGTs in these soils is affected by the relatively high soil moisture availability, creating lake-like conditions and GDGT distributions. Comparison of GDGT distributions in soils, water column and sediments indicated that brGDGTs and crenarchaeol in the sediment are partly soil derived, but that in situ production in the water column and/or sediment also takes place. Eutrophication seems to affect the distributions of brGDGTs by dilution of the supply of soil derived brGDGTs to the lake and by changing the degree of in situ production of brGDGTs in the water column. Furthermore, the eutrophic conditions in the lake promote methanogenic activity and subsequently cause a contribution of isoprenoid GDGTs (isoGDGTs) of methanogenic origin to the sediments. The aquatic production of GDGTs has implications for the reliability of GDGT-based proxy results. In particular, the application of the BIT and TEX86 indices is hampered by the mixed sources of the GDGTs in the lake. In contrast, global lake-specific brGDGT-based temperature calibrations resulted in temperature estimates that resemble measured mean annual and summer air temperatures. CBT-derived pH values agreed well with measured soil and water column values. Our results demonstrate that understanding the source of GDGTs in lake sediments is important for the robust interpretation of palaeoclimate records obtained from downcore proxy applications.

Flooding impact on the distribution of microbial tetraether lipids in paddy rice soil in China

Isoprenoid and branched glycerol dialkyl glycerol tetraethers (GDGTs) lipids were studied in flooded and non-flooded paddy soil in Wuhan, central China, to examine the response of the GDGTs distribution to the soil flooding. Samples were collected before and after the soil flooding in four specific months. Both core (CL) and intact polar (IPL) GDGTs were quantified. Increase in the abundance of archaeol and caldarchaeol may be indicative of the occurrence of methanogens in the flooded soil. A negative correlation was observed between the ratio of IPL branched GDGT-IIa to GDGT-Ia and the soil pH. The rise of the soil pH in the acid soil is known to be controlled by the redox conditions resulting from flooding. Thus, the branched GDGTs distribution may be controlled by the water content in the paddy soil. In addition, we suggest that the anoxic conditions resulting from flooding may also control the abundance of branched GDGTs relative to crenarchaeol, which in turn results in the increase of branched and isoprenoidal tetraethers (BIT) values, the index for the terrestrial input to the marine sediments.

Distribution of glycerol dialkyl glycerol tetraethers in soils from two environmental transects in the USA

Glycerol dialkyl glycerol tetraethers (GDGTs) of both archaeal and bacterial origin form the basis of new temperature proxies applicable to soil, and lake and marine sediments. In soil, branched GDGTs are prevalent and their abundance of methyl or cyclic groups has been calibrated to mean annual temperature (MAT) using MBT and CBT indices. However, soil pH is also known to be an important variable controlling the distribution of branched GDGTs. Precipitation amount helps control soil moisture, as well as pH, and soil moisture is a leading variable affecting microbial diversity and activity in soil. We have evaluated the distribution of GDGTs from two soil transects in the USA: a dry, western transect covering six western states and a wet, east coast transect from Maine to Georgia in order to assess the effect of precipitation on the distribution of soil GDGTs. Our results show distinctly different GDGT distributions across climatic regions, with dry western soils characterized predominantly by thaumarchaeotal isoprenoid (iso) GDGTs and as a consequence, low BIT index values (0.2–0.6) and moist-temperate, east coast transect soils expressing mostly branched (br) GDGTs and higher BIT values (0.9–1). The predominance of iso GDGTs in the western soils is related to the degree of aeration, which in turn is related to precipitation amount, and also to soil pH. We also observed a substantial increase in the offset between measured MAT and MBT/CBT-based MAT below an annual precipitation of 700–800mmyr−1, implying an impact of precipitation amount on MBT/CBT-based temperature reconstruction. The data suggest that, while soil tetraethers work well as a temperature proxy in moist-temperate regimes, they do not produce reliable measurements of temperature in sediments sourced from areas with <700–800mmyr−1 precipitation. Moreover, erosion of soils with low BIT values into lacustrine or marginal marine environments will not be detected via the BIT index, which can potentially affect paleotemperature reconstruction from sediments, and so provide erroneous estimates of soil carbon delivery. BIT index values also show a correlation with precipitation amount. The abundance of iso GDGTs in western transect soils allowed calculation of TEX86 values, but no correlation was found between TEX86 calculated temperature and mean annual temperature.

Calibrating the glycerol dialkyl glycerol tetraether temperature signal in speleothems

Palaeotemperature proxies based on glycerol dialkyl glycerol tetraethers (GDGTs) lipids have been established for marine and lacustrine environments, but there has been relatively little study of their application in speleothems. In this study we analyse the GDGT content of 33 speleothem samples from 16 different sites around the globe, and test whether proxies based on isoprenoid tetraethers (TEX86) or branched tetraethers (MBT/CBT) are correlated with measured surface and cave mean annual air temperature (MAT). The results show that the TEX86 has a strong relationship with measured temperature (r2=0.78, standard error of the estimate 2.3°C, when calibrated with surface MAT). Furthermore, the MBT/CBT also showed a significant relationship with temperature (r2=0.73, standard error of the estimate 2.7°C, when calibrated with surface MAT). Some issues remain requiring future work, in particular the development of a larger calibration sample set with measured cave temperature data, and the investigation of controls other than temperature on GDGT distribution, but overall the results indicate that GDGT based proxies derived from speleothems may be highly viable new methods for reconstructing continental palaeotemperatures.

Impacts of temperature and pH on the distribution of archaeal lipids in Yunnan hot springs, China

In culture experiments and many low temperature environments, the distribution of isoprenoid glycerol dialkyl glycerol tetraethers (GDGTs) commonly shows a strong correlation with temperature; however, this is often not the case in hot springs. We studied 26 hot springs in Yunnan, China, in order to determine whether temperature or other factors control the distribution of GDGTs in these environments. The hot springs ranged in temperature from 39.0 to 94.0°C, and in pH from 2.35 to 9.11. Water chemistry including nitrogen-, sulfur-, and iron species was also determined. Lipids from the samples were analyzed using liquid chromatography–mass spectrometry (LC–MS). Distributions of GDGTs in these hot springs were examined using cluster analysis, which resulted in two major groups. Group 1 was characterized by the lack of dominance of any individual GDGTs, while Group 2 was defined by the dominance of GDGT-0 or thaumarchaeol. Temperature was the main control on GDGT distribution in Group 1, whereas pH played an important role in the distribution of GDGTs in Group 2. However, no correlations were found between the distribution of GDGTs and any of the nitrogen-, sulfur-, or iron species. Results of this study indicate the dominance of temperature or pH control on archaeal lipid distribution, which can be better evaluated in the context of lipid classification.

Effects of a short-term experimental microclimate warming on the abundance and distribution of branched GDGTs in a French peatland

Branched glycerol dialkyl glycerol tetraethers (GDGTs) are complex lipids of high molecular weight, recently discovered in soils and increasingly used as palaeoclimate proxies. Their degree of methylation, expressed in the MBT, was shown to depend on mean annual air temperature (MAAT) and to a lesser extent on soil pH, whereas the relative abundance of cyclopentyl rings of branched GDGTs, expressed in the CBT, was related to soil pH. To date, only a few studies were interested in the application of the MBT and CBT proxies in peatlands. In order to validate the applicability of branched GDGTs as temperature proxies in these environments, it is essential to investigate the effect of temperature on branched GDGT-producing bacteria and especially on the speed of adaptation of these microorganisms to temperature changes. The aim of this work was to study the effects of in situ experimental climate warming on the abundance and distribution of branched GDGTs in a Sphagnum-dominated peatland (Jura Mountains, France). Branched GDGTs either present as core lipids (CLs; presumed of fossil origin) or derived from intact polar lipids (IPLs, markers for living cells) were analysed. Air temperature was experimentally increased using a passive warming system consisting of open mini-greenhouses (open-top chamber – OTC). The effect of the OTCs was especially apparent in spring and summer, with (i) an increase in maximal air temperature of ca. 3°C during these two seasons and (ii) an increase in average air temperature of ca. 1°C in summer. Despite the short duration of the climate experiment (26months), branched GDGT distribution was significantly affected by this temperature rise, with higher MBT values in the OTCs than in the control plots, supporting the empirical relationship between MBT and MAAT established from a large range of soils. The difference in branched GDGT-derived temperatures between control and OTC plots (2–3°C) was in the same range as the increase in maximal (daytime) temperature induced by the OTCs in spring and summer, suggesting that branched GDGT-producing bacteria might be more active during the warmest months of the year. The OTC treatment had no significant effect on the abundance of branched GDGTs, which were mainly present as “fossil” CLs (70–85% of the total branched GDGT pool). Furthermore, no significant differences in branched GDGT distribution were observed between the CLs and IPLs, which both provided higher MBT and MAAT values for the OTCs. This suggests that the fossil pool of branched GDGTs has a very fast turnover (less than the 2year duration of the experiment) at the peat surface and that branched GDGT distribution may rapidly reflect changes in environmental conditions (at least air temperature) occurring in peat environments.

Tracing soil organic carbon in the lower Amazon River and its tributaries using GDGT distributions and bulk organic matter properties

In order to trace the transport of soil organic carbon (OC) in the lower Amazon basin, we investigated the distributions of crenarchaeol and branched glycerol dialkyl glycerol tetraethers (GDGTs) by analyzing riverbed sediments and river suspended particulate matter (SPM) collected in the Solimões-Amazon River mainstem and its tributaries. The Branched and Isoprenoid Tetraether (BIT) index, a proxy for river-transported soil OC into the ocean, was determined from the distributions of these GDGTs. The GDGT-derived parameters were compared with other bulk geochemical data (i.e. C:N ratio and stable carbon isotopic composition). The GDGT-derived and bulk geochemical data indicate that riverine SPM and riverbed sediments in the lower Amazon River and its tributaries are a mixture of C3 plant-derived soil OC and aquatic-derived OC. The branched GDGTs in the SPM and riverbed sediments did not predominantly originate from the high Andes soils (>2500m in altitude) as was suggested previously. However, further constraint on the soil source area of branched GDGTs was hampered due to the deficiency of soil data from the lower montane forest areas in the Andes. Our study also revealed seasonal and interannual variation in GDGT composition as well as soil OC discharge, which was closely related to the hydrological cycle. By way of a simple binary mixing model using the flux-weighted BIT values at Óbidos, the last gauging station in the Amazon River, we estimated that 70–80% of the POC pool in the river was derived of soil OC. However, care should be taken to use the BIT index since it showed a non-conservative behaviour along the river continuum due to the aquatic production of crenarchaeol. Further investigation using a continuous sampling strategy following the full hydrological cycle is required to fully understand how soil-derived GDGT signals are transformed in large tropical river systems through their transport pathway to the ocean.

Distribution of glycerol dialkyl glycerol tetraethers in surface sediments of Lake Qinghai and surrounding soil

Glycerol dialkyl glycerol tetraethers (GDGTs) are increasingly used as proxies for paleoclimate studies of marine and lacustrine environments. While GDGT-based proxies have been applied to a number of lake environments globally, little is known about the distribution of GDGTs on the Qinghai-Tibet Plateau. We have investigated the isoprenoid GDGTs (iGDGTs) and branched GDGTs (bGDGTs) in Lake Qinghai sediments and the surrounding surface soil in order to examine their potential use as paleoclimate proxies on the Qinghai-Tibet Plateau. The results show that (i) the values of the iGDGT/bGDGT ratio for surrounding soil were at the higher end among globally distributed soils and consequently BIT values (avg. 0.71) at the lower end, (ii) the TEX86 values decreased while the MBT and CBT values increased along an onshore soil–nearshore sediment–offshore sediment transect, (iii) the TEX86 values for the offshore sediments were almost identical and their inferred temperatures were close to mean summer surface water temperature and (iv) the bGDGT-inferred mean annual air temperature (MAAT) and pH for soil were consistent with measured MAAT and pH. However, the CBT-inferred pH for offshore sediments seemed inconsistent with the pH of lake water or sediment. Our results suggest that (i) the higher pH may be an important factor leading to the higher iGDGT/bGDGT values (and lower BIT values) in surrounding surface soil, (ii) both iGDGTs and bGDGTs may originate from terrestrial input and in situ production for this saline lake, especially for nearshore sediments. However, for offshore sediments, terrestrial iGDGT input seems minor, and TEX86 may be useful for paleoclimate studies of Lake Qinghai.

Distribution of glycerol dialkyl glycerol tetraether lipids in the water column of Lake Tanganyika

We studied the distribution of glycerol dialkyl glycerol tetraethers (GDGTs) in suspended particulate matter from the water column of Lake Tanganyika (East Africa), where sediment studies had shown the applicability of the TEX86 proxy for reconstructing surface lake water temperature. GDGTs, in particular crenarchaeol, showed maximum abundance within the suboxic zone (100–180m), suggesting that this is the preferred niche of ammonia-oxidizing Thaumarchaeota. Despite evidence for anaerobic methane oxidation in deep anoxic water (300–1200m) no unambiguous evidence for an imprint of methanotrophic archaea on GDGT distribution was found. Comparison of TEX86 and BIT indices with those of surface sediments suggests that the sedimentary GDGTs are derived predominantly from the oxic zone and suboxic zone of the lake.

Biogeochemical controls on glycerol dialkyl glycerol tetraether lipid distributions in sediments characterized by diffusive methane flux

The TEX86 (TetraEther indeX of tetraethers consisting of 86 carbon atoms) is a proxy for sea surface temperature (SST) based on the distribution of isoprenoidal glycerol dialkyl glycerol tetraether (GDGT) membrane lipids synthesized by marine pelagic Thaumarchaeota. One of the caveats of this proxy is the production of additional GDGTs by sedimentary Euryarchaeota involved in anaerobic oxidation of methane (AOM) that occurs at deep-sea methane seeps but is also widespread in many continental shelf settings. Here, GDGT distributions are investigated through the sulfate-methane transition zone (SMTZ) in Aarhus Bay, Denmark, to examine the extent the TEX86 proxy is compromised in such a continental shelf setting where AOM is characterized by a diffusive rather than rapid advective methane flux. Both free extractable and non-extractable lipid fractions were analyzed as it was expected that pelagic-derived and sediment-derived GDGTs could become incorporated into the molecular and sedimentary matrix to a different extent. The results show a large change of TEX86 values mainly due to the relative high amounts of GDGT-2 produced by AOM-related Archaea, both in the free and non-extractable lipid fractions. This additional GDGT input renders calculation of SSTs based on TEX86 inappropriate at the SMTZ. The AOM-related GDGT signature, however, did not persist into deeper sediments, perhaps reflecting rapid remineralization of the GDGTs at the SMTZ. Although the process of AOM at Aarhus Bay might not be representative for all continental margin settings, it illustrates that AOM in a variety of settings, not just cold seeps, can influence sedimentary GDGT distributions.

Distributions of branched GDGTs in soils and lake sediments from western Uganda: Implications for a lacustrine paleothermometer

Bacterially produced branched glycerol dialkyl glycerol tetraethers (GDGTs) are ubiquitous in soils and lake sediments and can potentially be used to reconstruct past temperatures. In lakes, however, it is still unclear if these compounds are derived from eroded soils or if they are produced in situ. To better understand environmental controls on the distributions of these compounds and the sources of branched GDGTs to lake sediments, we compare branched GDGT distributions and concentrations in lake sediments and catchment soils within a 3600m altitudinal transect in western Uganda. Reconstructed mean annual air temperature (MAAT), determined from the degree of methylation (MBT) and cyclisation (CBT) of branched GDGTs in soils, decreases with increasing altitude, as is expected from the air temperature gradient in our transect. However, we observe significant offsets between observed and reconstructed temperatures in soils from wet, high elevation soils but not in most dry, low elevation soils. Branched GDGT distributions differ significantly between lake sediments and soils at all elevations, with greater differences at low elevations than at high elevations. These data support previous hypotheses that branched GDGTs are produced in situ in lakes and suggest that the abundance of water in soil environments may play a role in controlling the distribution of branched GDGTs. While branched GDGTs in lacustrine sediments can be used to reconstruct temporal temperature variations in lakes, we urge caution in utilizing this proxy in lacustrine systems with high soil loadings, especially if there is evidence of changing clastic fluxes through time.

13,16-Dimethyl Octacosanedioic Acid ( iso -Diabolic Acid), a Common Membrane-Spanning Lipid of Acidobacteria Subdivisions 1 and 3

The distribution of membrane lipids of 17 different strains representing 13 species of subdivisions 1 and 3 of the phylum Acidobacteria, a highly diverse phylum of the Bacteria, were examined by hydrolysis and gas chromatography-mass spectrometry (MS) and by high-performance liquid chromatography-MS of intact polar lipids. Upon both acid and base hydrolyses of total cell material, the uncommon membrane-spanning lipid 13,16-dimethyl octacosanedioic acid (iso-diabolic acid) was released in substantial amounts (22 to 43% of the total fatty acids) from all of the acidobacteria studied. This lipid has previously been encountered only in thermophilic Thermoanaerobacter species but bears a structural resemblance to the alkyl chains of bacterial glycerol dialkyl glycerol tetraethers (GDGTs) that occur ubiquitously in peat and soil and are suspected to be produced by acidobacteria. As reported previously, most species also contained iso-C(15) and C(16:1ω7C) as major fatty acids but the presence of iso-diabolic acid was unnoticed in previous studies, most probably because the complex lipid that contained this moiety was not extractable from the cells; it could only be released by hydrolysis. Direct analysis of intact polar lipids in the Bligh-Dyer extract of three acidobacterial strains, indeed, did not reveal any membrane-spanning lipids containing iso-diabolic acid. In 3 of the 17 strains, ether-bound iso-diabolic acid was detected after hydrolysis of the cells, including one branched GDGT containing iso-diabolic acid-derived alkyl chains. Since the GDGT distribution in soils is much more complex, branched GDGTs in soil likely also originate from other (acido)bacteria capable of biosynthesizing these components.

Bacterial tetraether membrane lipids in peat and coal: Testing the MBT–CBT temperature proxy for climate reconstruction

Peatlands are widespread and important natural archives of environmental change. Here we explore the potential of the recently introduced MBT–CBT proxy (methylation index and cyclisation ratio of branched tetraethers) to estimate past annual mean air temperature (MAT) based on the distribution of bacterially-derived branched glycerol dialkyl glycerol tetraether (GDGT) membrane lipids in peat and coal. To this end, branched GDGTs in an ombrotrophic peat bog from Switzerland and three coal deposits of increasing maturity were analysed. For the surface of the bog, reconstructed annual MAT is higher than both measured annual MAT and measured in situ pore water temperature. Changes in the CBT ratio, considered a proxy for pH, with depth in the bog do not match with present day in situ pore water pH, but coincide with a peat stratigraphic boundary. This indicates that GDGTs down the bog profile are predominantly fossil and not derived from extant biomass. The MBT–CBT derived annual MAT record also shows a large drop at this stratigraphic boundary, which likely relates to past change in trophic status of the bog. Branched GDGTs are abundant in an immature lignite (vitrinite reflectance, R o 0.25%), but occur in low amount in a slightly more mature coal ( R o 0.32%). Annual MAT could be reconstructed for the lignite alone and is higher than other proxy-based estimates from approximately the same time and location. Our results indicate potential for the application of the MBT–CBT proxy in peat and immature coals, but improved constraints on the effects of different types of peat on branched GDGT distributions as well as improved calibration of MAT estimates are needed before the method can be confidently applied.

Occurrence of tetraether lipids in stalagmites: Implications for sources and GDGT-based proxies

Lipid biomarkers in stalagmites have potential in palaeoenvironmental reconstruction, but glycerol dialkyl glycerol tetraethers (GDGTs) in stalagmites have rarely been investigated. We report the occurrence of archaeal isoprenoid GDGTs and bacterial branched GDGTs in Heshang Cave stalagmites in central China. The archaeal component, crenarchaeol, dominated bacterial branched GDGTs in the stalagmites and on the weathered parent rock surface collected inside the cave. In contrast, the distribution of GDGTs in the overlying soil shows that branched GDGTs dominated archaeal GDGTs. Hence, the majority of archaeal GDGTs in stalagmites may be produced by Crenarchaeota inhabiting the cave rather than being inherited from the overlying soil. Bacterial branched GDGT distributions, expressed as MBT and CBT indices, showed remarkable differences between stalagmite and soil samples, implying that most branched GDGTs may also be produced in situ in the cave. The TEX 86 or TEX 86 ′ values were found to increase with more depleted δ 18O values representing much stronger monsoon and therefore usually higher temperatures, in the study region. However, the MBT/CBT index in stalagmites may be influenced by a variety of factors besides palaeotemperature.

Environmental controls on branched tetraether lipid distributions in tropical East African lake sediments

Quantifying past continental temperature changes is an important aspect of paleoclimate research as it allows us to constrain the amplitude of natural variability, test predictive climate models, and provide a proper context for changes that may arise in response to anthropogenically-induced climate change. The recently developed biomarker-based methylation index of branched tetraethers/cyclization ratio of branched tetraethers (MBT/CBT) proxy shows potential as a new method for continental temperature reconstruction, but thus far it has only been applied successfully in ocean margin sediments. To assess whether this proxy is also applicable to the sedimentary record in tropical lacustrine systems, we investigated the distribution of branched glycerol dialkyl glycerol tetraethers (GDGTs) in recently deposited sediments from 46 lakes in tropical East Africa. These lakes span a substantial range in surface elevation (770–4500 m above sea level), and thus also a wide gradient of mean annual temperature. We find that, saline lakes excepted, branched GDGTs are universally abundant in the lakes investigated and can be used to predict mean annual air temperature (MAAT) with a high degree of accuracy. However, the existing global MBT/CBT calibration for MAAT based on soils predicts inaccurate temperatures when applied to our African lake dataset. This observation, together with the fact that surface water pH, and to lesser extent, lake depth appear to influence the distribution of branched GDGTs among sites, leads us to conclude that in situ production of branched GDGTs in lakes is likely. The robust relationship between branched GDGT distribution and the temperature and pH of African freshwater lakes makes these compounds suitable for paleoenvironmental reconstruction, however we urge caution in using branched GDGTs in lake sediments to infer past temperatures, unless their exact origin can be determined.

Occurrence and distribution of glycerol dialkyl glycerol tetraethers in a French peat bog

The present study was aimed at examining the distribution and abundance of glycerol dialkyl glycerol tetraethers (GDGTs) of archaeal and bacterial origin in peat samples from surface and deep (ca. 50 cm) horizons of a peat bog in the Jura Mountains (northeastern France). Two principal types of GDGTs are present: extractable GDGTs, recoverable by solvent extraction, and non-extractable GDGTs, linked to the soil matrix. Within the extractable pool, “free” (i.e. core lipids) and “bound” (i.e. intact polar and/or ester-bound lipids) GDGTs can be distinguished. Extractable “free” and “bound” GDGTs were extracted using both accelerated solvent extraction (ASE) and a modified Bligh and Dyer technique. Both methods were shown to allow adequate extraction of “free” archaeal and bacterial GDGTs from soil samples. Both extraction protocols afforded similar relative distributions of archaeal and bacterial GDGTs, although poorer extraction of “bound” GDGTs was observed for ASE relative to Bligh and Dyer. Even though only low amounts of bacterial GDGTs were released after acid hydrolysis of solvent-extracted samples, non-extractable and total extractable GDGTs showed different distribution patterns in some samples. Consequently, these two lipid pools potentially reflect different proxy records of mean annual air temperature (MAAT) and pH. Last, the distribution of bacterial GDGTs differed between the different samples. Samples from deep horizons gave lower GDGT-derived MAAT values than those from surficial horizons, in agreement with measured soil temperatures at 7 cm and 50 cm depths from April to September. MAAT estimates more closely resemble spring and summer temperatures rather than annual soil temperature. The variability in bacterial GDGT distribution and resulting MAAT estimates probably also reflects the heterogeneity of peat samples and the variation in several environmental factors such as peat moisture level and oxygen availability.

Occurrence and distribution of extractable glycerol dialkyl glycerol tetraethers in podzols

The abundance and distribution of glycerol dialkyl glycerol tetraethers (GDGTs) were compared in two contrasting environments: a temperate podzol located 40 km north of Paris (France) and a tropical podzol from the Amazon Basin (Brazil). Five samples were collected from the profile of the temperate podzol, including the litter layer. Five others were obtained from three profiles from the tropical soil sequence, which is representative of the transition between a latosol and a well-developed podzol. GDGTs can occur as core lipids (i.e. as extractable “free” lipids) within the soil organic extract. They may also be present in ester- and/or glycosidic ether-bound form (i.e. as extractable “bound” lipids) in the extract. To date, most studies of GDGTs in soil have considered extractable “free” GDGTs but have not investigated extractable “bound” GDGTs. The extractable “free” and “bound” GDGT pools were therefore both investigated. Accelerated solvent extraction (ASE) was used to extract total extractable (i.e. “free” and “bound”) GDGTs. Half of these extracts was then submitted to acid methanolysis to release ester- and/or glycosidic ether-bound GDGTs, allowing subsequent analysis of total extractable GDGTs using high performance liquid chromatography–mass spectrometry (HPLC/MS). The other half was directly analysed for “free” GDGTs. Branched GDGTs derived from soil bacteria were present in all the samples, along with GDGTs of archaeal origin, although the latter were detected in much lower abundance than bacterial GDGTs. A higher degree of methylation was observed for the alkyl branched GDGTs from the temperate samples than for the tropical ones, in agreement with differences in air temperature. The amount of bacterial and archaeal GDGTs in the surficial sample from the well-developed part of the tropical podzol was greater than in the latosol and transition profiles. The difference could be related to a lower pH in the developed podzol than in the other two profiles. Furthermore, branched GDGTs were detected in the litter layer from the temperate podzol, which may indicate the presence of branched GDGT-producing bacteria in the litter, probably in anoxic microsites. Last, GDGT abundance and distribution were comparable in the extractable “free” and total extractable lipid fractions of most of the soil samples, suggesting that GDGTs mainly occur as “free” lipids in the extracts of all these soils and that similar data concerning past air temperature and soil pH could be derived from both extractable “free” and total extractable GDGT distributions.

Effects of long term oxic degradation on the [formula omitted], TEX 86 and BIT organic proxies

One of the primary prerequisites for the application of organic proxies is that they should not be substantially affected by diagenesis. However, studies have shown that oxic degradation of biomarker lipids can affect their relative distribution. We tested the diagenetic stability of the U 37 K ′ and TEX 86 palaeothermometers upon long term oxygen exposure. For this purpose, we studied the distributions of alkenones and glycerol dialkyl glycerol tetraethers (GDGTs) in different sections of turbidites at the Madeira Abyssal Plain (MAP) that experienced different degrees of oxygen exposure. Sediments were deposited anoxically on the shelf and then transported by turbidity currents to the MAP, which has oxic bottom water. This resulted in partial degradation of the turbidite organic matter as a result of long term exposure to oxic bottom water. Concentrations of GDGTs and alkenones were reduced by one to two orders of magnitude in the oxidized parts of the turbidites compared to the unoxidized parts, indicating substantial degradation. High-resolution analysis of the Pleistocene F-turbidite showed that the U 37 K ′ index of long chain alkenones increased only slightly (0.01, corresponding to <0.5 °C) in the oxidized part of the turbidite, suggesting minor preferential degradation of the C 37:3 alkenone, in agreement with previous studies. TEX 86 values showed a small increase (0.02, corresponding to ∼2 °C) in the F-turbidite, like U 37 K ′ , while for other Pliocene/Miocene turbidites it either remained unchanged or decreased substantially (up to 0.06, corresponding to ∼6 °C). Previous observations showed that the BIT index, a proxy for the contribution of soil organic matter to total organic carbon, was always substantially higher in the oxidized part in all the turbidites, as a result of preferential degradation of marine-derived GDGTs. This relative increase in soil-derived GDGTs affects TEX 86, as the isoprenoid GDGT distribution on the continent can be quite different from that in the marine environment. Our results indicate that the organic proxies are affected by long term oxic degradation to different extents; this should be taken into account when applying these proxies in palaeoceanographic studies of sediments which have been exposed to prolonged oxic degradation.