Comparison of extraction and work up techniques for analysis of core and intact polar tetraether lipids from sedimentary environments

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

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.     

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.     

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.     

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.     

Selective preservation of soil organic matter in oxidized marine sediments (Madeira Abyssal Plain)

In ocean margin sediments both marine and terrestrial organic matter (OM) are buried but the factors governing their relative preservation and degradation are not well understood. In this study, we analysed the degree of preservation of marine isoprenoidal and soil-derived branched glycerol dialkyl glycerol tetraethers (GDGTs) upon long-term oxygen exposure in OM-rich turbidites from the Madeira Abyssal Plain by analyzing GDGT concentrations across oxidation fronts. Relative to the anoxic part of the turbidites ca. 7-20% of the soil-derived branched GDGTs were preserved in the oxidized part while only 0.2-3% of the marine isoprenoid GDGT crenarchaeol was preserved. Due to these different preservation factors the Branched Isoprenoid Tetraether (BIT) index, a ratio between crenarchaeol and the major branched GDGTs that is used as a tracer for soil-derived organic matter, substantially increases from 0.02 to 0.4. Split Flow Thin Cell (SPLITT) separation of turbidite sediments showed that the enhanced preservation of soil-derived carbon was a general phenomenon across the fine particle size ranges (<38 μm). Calculations reveal that, despite their relatively similar chemical structures, degradation rates of crenarchaeol are 2-fold higher than those of soil-derived branched GDGTs, suggesting preferential soil OM preservation possibly due to matrix protection.     

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.     

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.     

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.     

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 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.     

Global sediment core-top calibration of the TEX86 paleothermometer in the ocean

The TEX₈₆ (TetraEther indeX of tetraethers consisting of 86 carbon atoms) paleothermometer is based on the relative distribution of archaeal lipids, i.e. isoprenoid glycerol dibiphytanyl glycerol tetraethers (GDGTs), and is increasingly used to reconstruct past sea water temperatures. To establish a more extensive, global calibration of the TEX₈₆ paleothermometer, we analyzed GDGTs in 287 (in comparison with 44 in currently used calibration) core-top sediments distributed over the world oceans and deposited at different depths. Comparisons of TEX₈₆ data with (depth-weighted) annual mean temperatures of the overlying waters between 0 m and 4000 m as well as with different seasonal mean temperatures at 0 m water depth showed that the TEX₈₆ proxy reflects mostly annual mean temperatures of the upper mixed layer. The relationship between TEX₈₆ values and sea-surface temperatures (SSTs) was non-linear mainly because below 5 °C the change in TEX₈₆ values was minor with temperature. This suggests that the TEX₈₆ proxy might not be directly applicable for the Polar Oceans. Nevertheless, between 5 °C and 30 °C, the TEX₈₆ proxy has a strong linear relationship with SSTs. Here, we, therefore, propose a new linear calibration model (T = −10.78 + 56.2 ∗ TEX₈₆, r² = 0.935, n = 223) for past SST reconstructions using the TEX₈₆ palaeothermometer.     

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.     

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.     

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.     

Absence of seasonal patterns in MBT-CBT indices in mid-latitude soils

The degree of methylation and cyclization of bacteria-derived branched glycerol dialkyl glycerol tetraether (GDGT) membrane lipids in soils depends on temperature and soil pH. Expressed in the methylation index of branched tetraethers (MBT) and cyclization ratio of branched tetraethers (CBT), these relationships are used to reconstruct past annual mean air temperature (MAT) based on the distribution of branched GDGTs in ancient sediments; the MBT-CBT proxy. Although it was shown that the best correlation of this proxy is with annual MAT, it remains unknown whether a seasonal bias in temperature reconstructions could occur, such as towards a seasonal period of ‘optimal growth’ of the, as yet, unidentified soil bacteria which produce branched GDGTs. To investigate this possibility, soils were sampled from eight different plots in the USA (Minnesota and Ohio), The Netherlands (Texel) and the UK (Devon) in time series over 1 year and analyzed for their branched GDGT content. Further analyses of the branched GDGTs present as core lipids (CLs; the presumed fossil pool) and intact polar lipids (IPLs; the presumed extant pool) were undertaken for two of the investigated soil plots. The amount of IPL-derived branched GDGTs is low relative to the branched GDGT CLs, i.e. only 6-9% of the total branched GDGT pool. In all soils, no clear change was apparent in the distribution of branched GDGT lipids (either core or IPL-derived) with seasonal temperature change; the MBT-CBT temperature proxy gave similar temperature estimates year-round, which generally matched the mean annual soil temperature. In addition to a lack of coherent changes in relative distributions, concentrations of the branched GDGTs did not show clear changes over the seasons. For IPL-derived GDGTs these results suggest that their turnover time in soils is in the order of 1 year or more. Thus, our study does not provide evidence for seasonal effects on the distribution of branched GDGTs in soils, at least at mid-latitudes, and therefore, no direct evidence for a bias of MBT-CBT reconstructed temperatures towards a certain season of optimal growth of the source bacteria. If, however, there is a slight seasonal preference of branched GDGT production, which can easily be obscured by natural variability due to the heterogeneity of soils, then a seasonal bias may potentially still develop over time due to the long turnover time of branched GDGTs.     

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.     

Comprehensive glycerol ether lipid fingerprints through a novel reversed phase liquid chromatography–mass spectrometry protocol

Glycerol ether lipid distributions have been developed as proxies for reconstructing past environmental change or, in their intact polar form, for fingerprinting the viable microbial community composition. However, due to their structural complexity, full characterization of glycerol ether lipids requires separate protocols for the analysis of the polar head groups and the alkyl chain moieties in core ether lipids. As a consequence, the valuable relationship between core ether lipid composition and specific polar head groups is often lost; this limits understanding of the diversity of ether lipids and their utility as biogeochemical proxies. Here, we report a novel reversed phase liquid chromatography–electrospray ionization-mass spectrometry (RP-ESI-MS) protocol that enables the simultaneous analysis of polar head groups (e.g. phosphocholine, phosphoglycerol, phosphoinositol, hexose and dihexose) and alkyl moieties (e.g. alkyl moieties modified with different numbers of cycloalkyl moieties, hydroxyl and alkyl groups and double bonds) in crude lipid extracts without further preparation. The protocol greatly enhances detection of archaeal intact polar lipids (IPLs) and core lipids (CLs) with double bond- and hydroxyl group-bearing alkyl moieties. With these improvements, widely used ratios that describe relative distributions of the core lipids, such as TEX₈₆ and ring index, can now be directly determined in specific intact polar lipids (IPL-specific TEX₈₆ and ring index). Since IPLs are the putative precursors of the environmentally persistent core lipids, their detailed examination using this protocol can potentially provide new insights into diagenetic and biological mechanisms inherent to these proxies. In a series of 12 samples from diverse settings, core and IPL-specific TEX₈₆ values followed the order: 2G-GDGTs > core GDGTs > 1G-GDGTs > 1G-GDGT-PI and the ring indices followed: 1G-GDGTs ≈ core GDGTs > 2G-GDGTs > 1G-GDGT-P1G > 2G-OH-GDGTs ≈ 1G-OH-GDGTs (1G, monoglycosyl; 2G, diglycosyl; P1G, phosphomonoglycosyl; GDGT, glycerol dialkyl glycerol tetraether).