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.     

Seasonal changes in glycerol dialkyl glycerol tetraether concentrations and fluxes in a perialpine lake: Implications for the use of the TEX86 and BIT proxies

To determine where and when glycerol dialkyl glycerol tetraether (GDGT) membrane lipids in lakes are produced, we collected descending particles in Lake Lucerne (Switzerland) using two sediment traps (at 42 and 72 m water depth) with a monthly resolution from January 2008 to late March 2009. Suspended particulate matter (SPM) was monthly filtered from the water column at three different depths. The potential application of GDGTs in palaeoenvironmental and palaeoclimatic reconstructions was investigated by comparing core lipids and their relative GDGT distribution, with lake water temperatures throughout the year. Fluxes of GDGTs and their concentrations in the water column vary according to a seasonal pattern, showing a similar trend in the SPM and sediment traps. Fluxes and concentrations of isoprenoid GDGTs increase with depth, maximum values being observed in the deeper part of the water column, indicating production of isoprenoid GDGTs by Thaumarchaeota in the deep (∼50 m), aphotic zone of Lake Lucerne. The flux-weighted averages of the proxies TEX₈₆ (0.27) and BIT (0.03) based on the total extracted GDGTs are similar at both trap depths. A sediment core from the same location showed that in the first few centimetres of the core TEX₈₆ and BIT values of 0.29 and 0.07, respectively, are similar to those recorded for descending particles and SPM, indicating that the sedimentary TEX₈₆ records the annual mean temperature of deeper waters in Lake Lucerne. TEX₈₆ values are slightly higher below 20 cm in the core. This offset is interpreted to be caused by the present-day trophic state of the lake, which probably resulted in a deeper niche of the Thaumarchaeota. Branched GDGTs represent only a minor fraction of the total GDGTs in the lake and their origin remains unclear. Our data reveal that GDGTs in lakes have a large potential for palaeoclimatic studies but indicate that knowledge of the system is important for accurate interpretation.     

Differential degradation of intact polar and core glycerol dialkyl glycerol tetraether lipids upon post-depositional oxidation

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 IPL-derived 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 CL-based TEX₈₆ paleotemperature estimates was negligible.     

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 (100–180 m), suggesting that this is the preferred niche of ammonia-oxidizing Thaumarchaeota. Despite evidence for anaerobic methane oxidation in deep anoxic water (300–1200 m) 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.     

Distribution of glycerol dialkyl glycerol tetraether lipids along an altitudinal transect on Mt. Xiangpi,NE Qinghai-Tibetan Plateau,China

The distribution of glycerol dialkyl glycerol tetraethers (GDGTs) can reflect continental environmental changes. Recently, the distribution of branched GDGTs (bGDGTs) has been proposed as a novel tool for paleoelevation reconstructions. Here we report the variation in TEX₈₆ (tetraether index of 86 carbon atoms) of isoprenoidal GDGTs (iGDGTs) and MBT (methylation of branched tetraether index) of bGDGTs along an altitudinal transect on Mt. Xiangpi, NE Qinghai-Tibetan Plateau. Both TEX₈₆ and MBT values of surface soils showed significant linear decreases with altitude (TEX₈₆: R² = 0.65; n = 50; MBT: R² = 0.69; n = 24). We suggest that the apparent relationships between the two indices and altitude may be related to temperature. Our preliminary investigation suggests that the TEX₈₆ index can potentially be applied as a paleoelevation indicator in addition to the MBT index on the Qinghai-Tibetan Plateau.     

巫山黄土微生物四醚膜脂分布特征及其古气候意义

"巫山黄土"是指分布于长江三峡地区的黄土状堆积物,是中国黄土的重要组成部分,具有重要的古气候环境意义.微生物四醚膜脂是反演古气候环境的灵敏指标,为了进一步理解巫山黄土中蕴含的古气候意义,通过测定巫山黄土中微生物醚类化合物（glycerol dialkyl glycerol tetraethers,GDGTs）并分析其分布特征,基于支链GDGTs（bGDGTs）的甲基化指数（methylation index of branched tetraethers,MBT）和环化指数（cyclization ration of branched tetraethers,CBT）重建该地44.4~22.8 ka.BP的古温度年平均气温（mean annual air temperature,MAAT）,MAAT与频率磁化率曲线和北大西洋沉积物有孔虫曲线对比,其变化趋势具有一致性,反映了其指标的可靠性.巫山黄土的陆源输入指数（BIT值,bGDGTs vs.crenarchaeol）在0.5~1.0之间,大部分值接近于1.0,但有几个极低值,分析为干旱事件.根据MAAT和BIT指标,巫山地区在冰期气候有剧烈的波动,在36.2±3.6 ka.BP、26.0±2.7 ka.BP、23.7±2.3 ka.BP时相对比较干旱,推测可能分别对应着H4、H3和H2事件,表明该区气候变化响应全球气候变化.      

青藏高原东部现代泥炭GDGTs分布特征及环境意义

运用HPLC-APCI-MS详细分析了青藏高原东部红原现代泥炭(32°46'N,02°31'E)和越西现代泥炭(28°46'N,102°34'E)中甘油二烷基甘油四醚类脂物(glycerol dialkyl glycerol tetraethers,简称GDGTs)的组成及分布特征,检测出了丰富的GDGTs化合物,显示研究区分布着产甲烷菌、氨氧化古菌、细菌等多种微生物。其中,细菌支链GDGTs(branched GDGTs,简称bGDGTs)丰度明显高于古菌类异戊二烯GDGTs(isoprenoid GDGTs,简称iGDGTs)。无环的GDGT-0和archaeol是古菌iGDGTs的主要组分,说明古菌以产甲烷菌为主。bGDGTs中Ia与Ⅱa丰度最高,由CBT(环化指数)参数得到的pH值与泥炭实测pH值相近,但基于MBT'(甲基化指数)-CBT指标得到的年平均大气温度(MAT)与两研究区现代年平均温度有一定差别。通过该项工作发现今后进行区域细菌bGDGTs相关环境参数的校正是十分必要的。     

Impact of lateral transport on organic proxies in the Southern Ocean

Lateral transport of fine-grained organic carbon particles can complicate the interpretation of paleoclimate records based on organic proxies. Here we investigated the effect of lateral transport on newly developed temperature and soil organic matter proxies, TEX₈₆ and BIT index, respectively, in core MD88-769 recovered from the South East Indian Ridge. Our results show that TEX₈₆ and BIT records in comparison to diatom and foraminifera records were representative for more local climate changes while alkenones and n-alkanes originated from distant areas by oceanic and atmospheric transport, respectively. This suggests that TEX₈₆ and BIT paleoclimate records are primarily influenced by local conditions and less subjected to long-distance lateral transport than other organic proxies in the Southern Ocean.     

Fluxes and distribution of tetraether lipids in an equatorial African lake: Constraints on the application of the TEX86 palaeothermometer and BIT index in lacustrine settings

The distribution of isoprenoid and branched glycerol dialkyl glycerol tetraether (GDGT) lipids was studied in material from various sources in and around Lake Challa, a crater lake on the southeastern slope of Mt. Kilimanjaro (Tanzania), to examine the provenance of GDGTs in lake sediments and their potential application as palaeoenvironmental and palaeoclimatic proxies. The study material included samples collected at monthly intervals in a sediment trap over one complete annual cycle, particles suspended in the stratified water column, profundal surface sediments, and soils surrounding the lake. The sediment trap time series revealed that crenarchaeol and related isoprenoid GDGTs were predominantly produced in January and February, following the locally prominent short rain season (November-December). The TEX₈₆-inferred temperature derived from sedimenting particles corresponded well with lake surface-water temperature at this time of largest crenarchaeol flux. Molecular ecological analysis showed that Group 1.1a and 1.1b crenarchaeota are the most likely source organisms of these GDGTs. GDGT-0 in the lake sediments does not only originate from lake surface-dwelling crenarchaeota but seems predominantly derived from archaea residing in the deeper, anoxic part of the water column. The main flux of branched GDGTs to the sediment was during the short rain season and is most probably derived from eroded catchment soils in surface run-off. However, a contribution from in-situ production of branched GDGTs in the lake sediment or water, or in groundwater cannot be fully excluded. We conclude that palaeoclimatic reconstruction based on branched GDGT distributions in lake sediments should only be performed when the origin of those branched GDGTs is well constrained.     

Occurrence and distribution of tetraether membrane lipids in soils: Implications for the use of the TEX86 proxy and the BIT index

A diverse collection of globally distributed soil samples was analyzed for its glycerol dialkyl glycerol tetraether (GDGT) membrane lipid content. Branched GDGTs, derived from anaerobic soil bacteria, were the most dominant and were found in all soils. Isoprenoid GDGTs, membrane lipids of Archaea, were also present, although in considerably lower concentration. Crenarchaeol, a specific isoprenoid membrane lipid of the non-thermophilic Crenarchaeota, was also regularly detected and its abundance might be related to soil pH. The detection of crenarchaeol in nearly all of the samples is the first report of this type of GDGT membrane lipid in soils and is in agreement with molecular ecological studies, confirming the widespread occurrence of non-thermophilic Crenarchaeota in the terrestrial realm. The fluvial transport of crenarchaeol and other isoprenoid GDGTs to marine and lacustrine environments could possibly bias the BIT index, a ratio between branched GDGTs and crenarchaeol used to determine relative terrestrial organic matter (TOM) input. However, as crenarchaeol in soils is only present in low concentration compared to branched GDGTs, no large effect is expected for the BIT index. The fluvial input of terrestrially derived isoprenoid GDGTs could also bias the TEX₈₆, a proxy used to determine palaeo surface temperatures in marine and lacustrine settings and based on the ratio of cyclopentane-containing isoprenoid GDGTs in marine and lacustrine Crenarchaeota. Indeed, it is shown that a substantial bias in TEX₈₆-reconstructed sea and lake surface temperatures can occur if TOM input is high, e.g. near large river outflows.     

http://www.sciencedirect.com/science/article/pii/S1674987111001332

Isoprenoidal glycerol dialkyl glycerol tetraethers（iGDGTs） from the Gulu hot springs （23-83.6℃,pH>7） and Yangbajing hot springs（80—128℃,pH>7） were analyzed in order to investigate the distribution of archaeal lipids among different hot springs in Tibet.A soil sample from Gulu was incubated at different temperatures and analyzed for changes in iGDGTs to help evaluate whether surrounding soil may contribute to the iGDGTs in hot springs.The sources of bacterial GDGTs（bGDGTs） in these hot springs were also investigated.The results revealed different profiles of iGDGTs between Gulu and Yangbajing hot springs. Core iGDGTs and polar iGDGTs also presented different patterns in each hot spring.The PCA analysis showed that the structure of polar iGDGTs can be explained by three factors and suggested multiple sources of these compounds.Bivariate correlation analysis showed significant positive correlations between polar and core bGDGTs.suggesting the in situ production of bGDGTs in the hot springs.Furthermore,in the soil incubation experiment,temperature had the most significant influence on concentration of bGDGTs rather than iGDGTs.and polar bGDGTs had greater variability than core bGDGTs with changing temperature.Our results indicated that soil input had little influence on the composition of GDGTs in Tibetan hot springs. On the other hand,ring index and TEX₈₆ values were both positively correlated with incubation temperature, suggesting that the structure of archaeal lipids changed in response to varying temperature during incubation.     

http://www.sciencedirect.com/science/article/pii/S1674987112001260

Archaea have unique glycerol dialkyl glycerol tetraether (GDGT) lipids that can be used to develop paleotemperature proxies such as TEX₈₆. This research is to validate proposed GDGT-proxies for paleotemperature determination in the South China Sea (SCS). Samples were collected from core-top sediments (0–5 cm) in the northern SCS. Total lipids were extracted to obtain core GDGTs, which were identified and quantified using liquid chromatography-mass spectrometry (LC-MS). The abundance of isoprenoidal GDGTs (iGDGTs) ranged from 271.5 ng/g dry sediment to 1266.3 ng/g dry sediment, whereas the branched GDGTs (bGDGTs), supposedly derived from terrestrial sources, ranged from 22.2 ng/g dry sediment to 56.7 ng/g dry sediment. The TEX₈₆-derived sea surface temperatures ranged from 20.9 °C in the coast (water depth < 160 m) to 27.9 °C offshore (water depth > 1000 m). TEX₈₆-derived temperatures near shore (<160 m water depth) averaged 23.1 ± 2.5 °C (n = 4), which were close to the satellite-derived winter mean sea surface temperature (average 22.6 ± 1.0 °C, n = 4); whereas the TEX₈₆-derived temperatures offshore averaged 27.4 ± 0.3 °C (n = 7) and were consistent with the satellite mean annual sea surface temperature (average 26.8 ± 0.4 °C, n = 7). These results suggest that TEX₈₆ may record the sea surface mean annual temperature in the open ocean, while it likely records winter sea surface temperature in the shallower water.     

Application of the TEX86 temperature proxy to the southern North Sea

A novel temperature proxy, the tetraether index of lipids with 86 carbon atoms (TEX₈₆), was applied to the suspended particulate organic matter (POM) and sediment core tops from eight sites in the southern North Sea in different seasons. The TEX₈₆-derived temperatures in many samples did not correlate with mean annual sea surface temperature (SST), but were shifted toward winter SST, apparently because Crenarchaeota are more abundant and metabolically active during periods of low primary production. This indicates that TEX₈₆-derived SST estimates do not necessarily reflect annual mean SST and may provide essential information about seasonal SST palaeoreconstruction. High TEX₈₆-derived SSTs were measured in the water of the river Rhine and in the sediment core tops and seawater from several stations in the southern North Sea. These sites were all characterised by important input of organic matter from soil and peat, as revealed by the relatively high values obtained with the new terrestrial proxy, the branched and isoprenoid tetraether (BIT) index. These data demonstrate that to reconstruct palaeotemperatures it is essential to estimate both TEX₈₆ and BIT indices to check that TEX₈₆ temperatures are not biased as a result of large terrestrial input. Important seasonal variations in TEX₈₆-derived SST were also evident for the surface sediments of several stations characterised by extremely low sedimentation rates, indicating temporary settlement of laterally transported organic matter with a warmer temperature signal. This implies that sediment core top correlations between TEX₈₆ and mean annual SST should not be carried out in areas characterised by transient sediment deposition.     

Origins of archaeal tetraether lipids in sediments: Insights from radiocarbon analysis

Understanding the supply and preservation of glycerol dibiphytanyl glycerol tetraethers (GDGTs) in marine sediments helps inform their use in paleoceanography. Compound-specific radiocarbon measurements of sedimentary alkenones from multiple environments have been used to gain insight into processes that affect paleotemperature reconstructions. Similar analyses are warranted to investigate how analogous processes affecting GDGTs impact TEX₈₆ paleotemperatures. Here we present radiocarbon measurements on individual GDGTs from Bermuda Rise and Santa Monica Basin sediments and discuss the results in the context of previous studies of co-depositional alkenones and foraminifera. The ¹⁴C contents of GDGTs and planktonic foraminifera in Bermuda Rise are very similar, suggesting a local source; and TEX₈₆-derived temperatures agree more closely with foraminiferal temperatures than do temperatures. In contrast, GDGTs in Santa Monica Basin are depleted in ¹⁴C relative to both alkenones and foraminifera, and TEX₈₆ temperatures agree poorly with known surface water values. We propose three possible factors that could explain these results: (i) GDGTs may be labile relative to alkenones during advective transport through oxic waters; (ii) archaeal production deep in the water column may contribute ¹⁴C-depleted GDGTs to sediments; and (iii) some GDGTs also may derive from sedimentary archaeal communities. Each of these three processes is likely to occur with varying relative importance depending on geographic location. The latter two may help to explain why TEX₈₆ temperature reconstructions from Santa Monica Basin do not appear to reflect actual sea surface temperatures. Terrigenous GDGTs are unlikely to be major contributors to Bermuda Rise or Santa Monica Basin sediments, based on values of the BIT index. The results also indicate that the crenarchaeol regioisomer is governed by processes different from other GDGTs. Individual measurements of the crenarchaeol regioisomer are significantly depleted in ¹⁴C relative to co-occurring GDGTs, indicating an alternative origin for this compound that presently remains unknown. Re-examination of the contribution of crenarchaeol regioisomer to the TEX₈₆ index shows that it is a significant influence on the sensitivity of temperature reconstructions.     

A lacustrine GDGT-temperature calibration from the Scandinavian Arctic to Antarctic: Renewed potential for the application of GDGT-paleothermometry in lakes

Quantitative climate reconstructions are fundamental to understand long-term trends in natural climate variability and to test climate models used to predict future climate change. Recent advances in molecular geochemistry have led to calibrations using glycerol dialkyl glycerol tetraethers (GDGTs), a group of temperature-sensitive membrane lipids found in Archaea and bacteria. GDGTs have been used to construct temperature indices for oceans (TEX₈₆ index) and soils (MBT/CBT index). The aim of this study is to examine GDGT-temperature relationships and assess the potential of constructing a GDGT-based palaeo-thermometer for lakes. We examine GDGT-temperature relationships using core top sediments from 90 lakes across a north-south transect from the Scandinavian Arctic to Antarctica including sites from Finland, Sweden, Siberia, the UK, Austria, Turkey, Ethiopia, Uganda, Chile, South Georgia and the Antarctic Peninsula. We examine a suite of 15 GDGTs, including compounds used in the TEX₈₆ and MBT/CBT indices and reflecting the broad range of GDGT inputs to small lake systems.GDGTs are present in varying proportions in all lakes examined. The TEX₈₆ index is not applicable to our sites because of the large relative proportions of soil derived and methanogenic components. Similarly, the MBT/CBT index is also not applicable and predicts temperatures considerably lower than those measured. We examine relationships between individual GDGT compounds and temperature, pH, conductivity and water depth. Temperature accounts for a large and statistically independent fraction of variation in branched GDGT composition. We propose a GDGT-temperature regression model with high accuracy and precision (R² = 0.88; RMSE = 2.0 °C; RMSEP = 2.1 °C) for use in lakes based on a subset of branched GDGT compounds and highlight the potential of this new method for reconstructing past temperatures using lake sediments.     

The organic geochemistry of glycerol dialkyl glycerol tetraether lipids: A review

Glycerol dialkyl glycerol tetraether (GDGT) lipids are membrane lipids which were long thought to be synthesized mainly by archaea, organisms thought to be limited to extreme environments. Analysis of environmental samples over the last decade has shown, however, that their structural diversity and sources are much wider than anticipated and that they occur ubiquitously in a wide range of environments, such as oceans and lakes, and their (sub)surface sediments, as well as soils. Several GDGTs have been unambiguously identified and can be used as biomarker lipids, since they are preserved in immature sediments <140 Ma. Close examination of the distributions has led to the discovery that GDGTs might be used as proxies for certain environmental parameters, such as the input of soil organic matter to marine environments, soil pH, air temperature and sea and lake water temperature. Here, we review the progress made over the last decade in the analysis, occurrence and recognition of sources of GDGTs, their applications as biomarker lipids, and the development and application of proxies based on their distributions.     

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.     

Distribution of Crenarchaeota tetraether membrane lipids in surface sediments from the Red Sea

The Red Sea represents an extreme marine environment, with high salinity, high temperature and low level of nutrients, complicating the application of standard geochemical palaeotemperature proxies. In order to investigate the applicability of the TEX₈₆ (TetraEther indeX of GDGTs with 86 carbons) proxy for sea surface temperature (SST) in the Red Sea, the distribution of glycerol dialkyl glycerol tetraether membrane lipids (GDGTs) in sediments from the Red Sea and the Gulf of Aden were examined. Against expectations, TEX₈₆ values for the Red Sea do not show a simple linear relationship with SST and deviate from the global core top calibration. In the northern Red Sea, at temperatures between 25 and 28 °C, the values increase linearly with SST, whereas in the southern Red Sea, at temperatures above 28 °C, TEX₈₆ decreases with increasing temperature. Factors like seasonality and depth of production, salinity and nutrient availability, as well as diagenetic overprint or influence of allochtonous terrestrial lipids, cannot explain this pattern. However, the observed TEX₈₆ relationship with SST could be explained by the presence of a hypothetical endemic Crenarchaeota population in the Red Sea with a specific TEX₈₆ vs. SST relationship. In the Southern Red Sea, a two-component mixing model implies an exponential decrease in the endemic population towards the Gulf of Aden. Thus, the application of the TEX₈₆ as a palaeotemperature proxy in the Red Sea is likely only possible for the northern Red Sea area with the specific SST vs. TEX₈₆ relationship determined in this study and potentially for the whole Red Sea basin during glacials, when water exchange with the Indian Ocean was more restricted than today and the endemic archaeal lipid distribution was not affected by transport from the Indian Ocean. Our results suggest that distinct populations of Crenarchaeota in extreme environments such as evaporitic basins may have different membrane composition, necessitating application of another calibration than the global core top calibration for TEX₈₆ palaeothermometry.     

Influence of lake water pH and alkalinity on the distribution of core and intact polar branched glycerol dialkyl glycerol tetraethers (GDGTs) in lakes

Branched glycerol dialkyl glycerol tetraethers (GDGTs) are bacterial membrane lipids, ubiquitously present in soils and peat bogs, as well as in rivers, lakes and lake sediments. Their distribution in soil is controlled mainly by pH and mean annual air temperature, but the controls on their distribution in lake sediments are less well understood. Several studies have found a relationship between the distribution of branched GDGTs in lake sediments and average lake water pH, suggesting an aquatic source for them, besides that for soil transported to the lake via erosion. We sampled the surface water suspended particulate matter (SPM) from 23 lakes in Minnesota and Iowa (USA), that vary widely in pH, alkalinity and trophic state. The SPM was analyzed for the concentration and distributions of core lipid (presumed fossil origin) and intact polar lipid (IPL, presumed to derive from living cells) branched GDGTs. The presence of substantial amounts (18–48%) of IPL-derived branched GDGTs suggests that branched GDGTs are likely of autochthonous origin. Temperature estimates based on their distribution using lake-specific calibrations agree reasonably with water temperature at time of sampling and average air temperature of the season of sampling. Importantly, a strong correlation between the distribution of branched GDGTs and lake water pH was found (r² 0.72), in agreement with a predominant in situ production. An stronger correlation was found with lake water alkalinity (r² 0.83), although the underlying mechanism that controls the relationship is not understood. Our results raise the potential for reconstructing pH/alkalinity of past lake environments, which could provide important knowledge on past developments in lake water chemistry.