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.     

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 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.     

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.     

青海湖钻孔沉积物中的羟基甘油二烷基甘油四醚类化合物及其环境意义

来源于古菌细胞膜脂的类异戊二烯甘油二烷基甘油四醚类化合物（isoGDGTs）是古环境重建的有力工具。最近的研究发现,自然环境中还存在着一类isoGDGTs烷基长链上含有羟基的OH-GDGTs,其相对含量与温度负相关,具有示踪古温度的潜力。然而,目前湖相环境中关于OH-GDGTs的研究还很少。我们通过高效液相色谱-大气压化学电离-质谱分析,在青海湖8ka以来沉积物中检测到了OH-GDGTs的存在,其含量（相对含量% OH-GDGTs及浓度）与奇古菌特征标志物crenarchaeol相对含量和奇古菌amoA基因丰度一致,表明青海湖中的OH-GDGTs可能主要来源于奇古菌。进一步与湖泊水位指标对比显示,青海湖中% OH-GDGTs的变化可能主要反映了湖水深度变化导致的古菌群落的变化。因此,认为湖泊沉积物中的OH-GDGTs可指示古水文条件变化。

     

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.     

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.     

Global distribution patterns of hydroxy glycerol dialkyl glycerol tetraethers

Archaea are ubiquitous in mesophilic and extremophilic environments. Variations in lipid composition of their unique tetraether membrane allow them to maintain integrity and permeability in moderate to extreme environmental conditions. The change in the number of cyclic moieties in their membrane lipids is argued to be an adaptation to ambient temperatures, which is used to estimate past water surface temperature via the TEX₈₆ index. A new class of GDGTs with a hydroxylation in one of the alkyl chains has recently been described in marine sediments. Here we report that these hydroxy-GDGTs are widespread and abundant in mesophilic marine and lacustrine environments. Moreover we observe increasing hydroxy-GDGT contributions towards higher latitudes and lower water temperatures. A significant correlation between the relative abundance of hydroxy-GDGTs and temperature is observed in surface sediments. As these compounds are found both in modern and downcore samples we suggest that the hydroxy-GDGTs could be included in the GDGT paleoproxy tool kit.     

羟基甘油二烷基甘油四醚脂类化合物研究进展

羟基甘油二烷基甘油四醚（Hydroxylated GDGTs,简称OH-GDGTs）脂类化合物广泛分布在全球不同海域以及湖泊环境,研究显示此类化合物的分布受控于温度,在高纬低温海域含量丰富,而在温度相对较高的低纬海域含量相对较低。前人研究表明,海洋表层沉积物中OH-GDGTs的分布与海水表层温度（Sea Surface Temperature,简称SST）之间有着明显的相关性,因此当其他生物标志化合物使用受限时,基于OH-GDGTs构建的指标成为一类较好的温度替代指标。基于此,文章主要介绍此类化合物的结构、生物来源,并阐述此类化合物在不同类型沉积载体（包括海洋以及湖泊）中的研究进展,为进一步了解此类化合物所携带的生物和环境信息提供依据。

     

Oxidation of methane in the water column of Lake Baikal

The rate of aerobic oxidation of methane was calculated based on average profiles of the tritiumhelium age of the Baikal waters and concentrations of the dissolved methane in the water column. In the deep lake zone (>200 m), the intensity of oxidation vertically decreases and is (2–0.3) × 10^?2 nl CH₄l^?1 days^?1 in southern and central Baikal and (2.8–1.0) × 10^?2 nl CH₄ l^?1 days^?1 in northern Baikal. The effective coefficient of the oxidation rate in the lake depressions is 3.6 × 10^?4, 3.3 × 10^?4, and 3.7 × 10^?4 days^?1, respectively. At current methane concentrations in the water column, about 80 t of methane is oxidized per year. Oxidation of the dissolved methane in the water column was estimated at a possible increase of its concentration.     

Distribution of branched tetraether lipids in geothermally heated soils: Implications for the MBT/CBT temperature proxy

Branched glycerol dialkyl glycerol tetraether (GDGT) membrane lipids occur in soils and peat bogs and are assumed to be produced by anaerobic bacteria. Two indices based on the distribution of these lipids in soils, the Cyclisation of Branched Tetraethers (CBT) and the Methylation of Branched Tetraethers (MBT) index have been shown to linearly relate to pH, and to mean annual air temperature (MAT) and pH, respectively. To directly evaluate the impact of changes in soil temperature on the MBT/CBT proxy, we determined these indices in soils sampled from a transect away from two hot springs in California, which provided a set of soils similar in composition but with different temperatures (12–41 °C). The CBT values of these geothermally heated soils show a good relation with pH (R² 0.76), similar to that of a global MBT/CBT calibration set. Also, the relationship between MBT, soil pH and temperature for the geothermally heated soils is similar to that of a global soil calibration set, although the intercept for the geothermally heated soils is significantly lower, likely because our data set is based on in situ soil temperatures rather than MAT. The results confirm the dependence of the MBT index on soil temperature and pH and support the applicability of the MBT/CBT indices as a proxy for continental palaeotemperatures and past soil pH.     

Early diagenesis of organic matter in the water column and sediments: Microbial degradation and resynthesis of lipids in Lake Haruna

Particulate matter, sediment trap, and surface sediment samples collected in freshwater Lake Haruna were studied to understand early diageesis of organic materials in the water column and in bottom sediments. The samples were analyzed for biomarkers, including aliphatic and aromatic hydrocarbons, fatty alcohols, saturated and unsaturated fatty acids, β- and ω-hydroxyacids, and α,ω-dicar☐ylic acids. Decreases in concentrations of autochthonous saturated C₁₂–C₁₉ fatty acids and polyunsaturated C₁₈ acids relative to TOC occured with the settling of organic matter ot the lake bottom, whereas the amounts of terrestial saturated C₂₀–C₃₀ acids remained almost constant. Conversely, the concentrations of monosaturated fatty acids, branched chain fatty acids, and β- and ω-hydroxyacids, which are probably produced by microbial activity, increased. These results indicate that preferential degradation of algal lipids accompanies microbial resynthesis of lipids during settling, however, terrigenous lipids are relatively stable.     

Distribution of glycerol ether lipids in halophilic,methanogenic and hyperthermophilic archaea

Four representatives of methanogenic Euryarchaeota (Methanosarcina mazei strain Gö1, Methanosphaera stadtmanae, Methanobrevibacter smithii and Methanosaeta thermophila), the hyperthermophilic euryarchaeon Thermococcus kodakarensis and the halophilic euryarchaeon Haloferax volcanii were studied for their glycerol ether lipid composition. The predominant core membrane lipid in all of them was archaeol, which was accompanied by variable quantities of sn-2-hydroxyarchaeol in the methanogens M. mazei (Methanosarcinales) and M. stadtmanae (Methanobacteriales). All methanogenic and hyperthermophilic Euryarchaeota also contained comparatively high abundances of the glycerol dialkyl glycerol tetraether without a cyclopentane moiety (GDGT-0). The methanoarchaeon M. stadtmanae, in addition to GDGT-0, contained GDGT core lipid structures with 1–4 cyclopentane moieties (GDGTs 1–4). We also found minor amounts of a glycerol trialkyl glycerol tetraether (GTGT) and a glycerol dialkanol diether (GDD), both of which did not contain cyclopentane moieties, as well as methylated and dimethylated GDGT-0 in all the archaea with the exception of H. volcanii. Like its GDGT distribution, M. stadtmanae showed an extended range of GDD structures with up to two cyclopentane ring systems. Our results thus indicate that both methanogenic and hyperthermophilic Euryarchaeota may represent source organisms of GTGT-0, GDDs and methylated-GDGTs in natural environments. All the latter components have recently been reported to be ubiquitously distributed in marine sediments but their biological origin is largely unknown. Moreover, a suite of unsaturated GDGTs without a cyclopentane moiety and up to four double bonds in the hyperthermophile T. kodakarensis was tentatively assigned.     

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.     

Occurrence and distribution of glycerol dialkanol diethers and glycerol dialkyl glycerol tetraethers in a peat core from SW Tanzania

Isoprenoid and branched glycerol dialkanol diethers (iso GDDs and br GDDs) have recently been detected in various environments, including sediment, soil and peat deposits. Their structures strongly resemble those of glycerol dialkyl glycerol tetraethers (GDGTs). Nevertheless, the origin of GDDs and their link to GDGTs remain unclear. Here we examined the concentration and distribution of iso GDDs and br GDDs, together with those of iso GDGTs and br GDGTs along a 4 m peat core from Tanzania. Whereas br GDDs have only been detected to date in their core lipid (CL) form, we report here, for the first time, br GDDs in both CL and intact polar lipid (IPL) forms, suggesting a biosynthetic origin for br GDDs. Concentrations of br GDGTs and br GDDs on one hand and of iso GDGTs and iso GDDs on the other hand, were observed to significantly co-vary (R² 0.49–0.58; p < 0.05), both for the CL and IPL fractions. Moreover, the fractional abundance of each GDD correlated significantly with that of its GDGT analogue (R² 0.33–0.97; p < 0.05). Taken together, the data show that GDDs and GDGTs are closely related and likely take part in common metabolic pathways, although the hypothesis of GDDs being degradation products of GDGTs cannot be excluded.     

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.     

Identification and distribution of intact polar branched tetraether lipids in peat and soil

Branched glycerol dialkyl glycerol tetraether lipids (GDGTs) are membrane lipids of soil bacteria that occur ubiquitously in soil, but their occurrence as intact polar lipids (IPLs) has not been well studied. Here, we report the identification and distribution of IPL-branched GDGTs throughout a depth profile of a Swedish peat bog. In addition to two reported glycosidic IPL branched GDGTs, we identified IPL branched GDGTs with a hexose-glycuronic acid, phospho-hexose, or hexose-phosphoglycerol head group, based on mass spectrometry. A selected reaction monitoring (SRM) assay was developed to monitor changes in head group distribution with depth. The abundance of the IPL branched GDGTs increased below the water table, suggesting that they were primarily produced in this part of the peat. This was supported by the concentrations of core lipid and IPL-derived branched GDGTs, which also substantially increased below the water table. However, individual IPL trends differed, which may be due to changes in the microbial community composition with depth or to different degradation rates for the different IPL branched GDGTs. The SRM method was also applied to two different soil types, which showed that similar IPL branched GDGTs as those in peat were present, albeit with different distributions.     

Isolation and compound specific radiocarbon dating of terrigenous branched glycerol dialkyl glycerol tetraethers (brGDGTs)

The relative abundances and distributions of branched glycerol dialkyl glycerol tetraethers (brGDGTs) in marine and lacustrine sediments have been recently used as paleo-environmental proxies for the input of soil organic matter and past continental temperatures, respectively. The putative main source of brGDGTs is soil bacteria. Therefore, these biomarkers are also part of the soil organic matter stock that accumulates in the terrigenous environment. Here we present a method for isolating and purifying these compounds from lake sediments, soils and peat for radiocarbon (¹⁴C) measurement using a combination of normal and reversed phase high performance liquid chromatography, allowing complete separation of co-eluting compounds. Radiocarbon analysis was performed on an accelerator mass spectrometer system equipped with a gas ion source. We assessed the accuracy and the necessary corrections with modern and radiocarbon-dead procedural blanks. Blank assessment revealed that the reverse phase step introduced significant amounts of extraneous carbon, while the normal phase step did not. We show that with our method and instrumentation it is possible to obtain accurate and precise ¹⁴C analyses of brGDGTs with sample amounts as small as 10 μg C. Finally we demonstrate the application of the measurement of ¹⁴C concentrations of several brGDGTs isolated from lake sediments and peat soils.