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Ratios of glycerol dialkyl glycerol tetraethers (GDGT), which are membrane lipids of bacteria and archaea, are at the base of several paleoenvironmental proxies. They are frequently applied to soils as well as lake‐ and marine sediments to generate records of past temperature and soil pH. To derive meaningful environmental information from these reconstructions, high analytical reproducibility is required. Based on submitted results by 39 laboratories from across the world, which employ a diverse range of analytical and quantification methods, we explored the reproducibility of brGDGT‐based proxies (MBT′5ME, IR, and #ringstetra) measured on four soil samples and four soil lipid extracts. Correct identification and integration of 5‐ and 6‐methyl brGDGTs is a prerequisite for the robust calculation of proxy values, but this can be challenging as indicated by the large inter‐interlaboratory variation. The exclusion of statistical outliers improves the reproducibility, where the remaining uncertainty translates into a temperature offset from median proxy values of 0.3–0.9°C and a pH offset of 0.05–0.3. There is no apparent systematic impact of the extraction method and sample preparation steps on the brGDGT ratios. Although reported GDGT concentrations are generally consistent within laboratories, they vary greatly between laboratories. This large variability in brGDGT quantification may relate to variations in ionization efficiency or specific mass spectrometer settings possibly impacting the response of brGDGTs masses relative to that of the internal standard used. While ratio values of GDGT are generally comparable, quantities can currently not be compared between laboratories. Key Points: 39 laboratories participated in a round robin to determine the reproducibility of glycerol dialkyl glycerol tetraethers (GDGT) proxy values and quantitiesPeak selection impacts the ratio values and there is no apparent systematic impact of the extraction method and sample preparation stepsQuantification of GDGTs remains a problem, and comparison of GDGT concentrations between laboratories requires further method development [ABSTRACT FROM AUTHOR]

Long-chain diols are biomarkers commonly used in the marine realm to reconstruct several environmental parameters such as sea surface temperature and salinity. However, they are also produced in lacustrine and slow-flowing river environments, a characteristic that has proved to be useful to trace past riverine inputs in coastal sedimentary records. So far, their use in lacustrine settings is sparse as their controls are not well-known. Previous studies in two lakes have shown that long-chain diol distribution is linked to changes in temperature (in a small Spanish alpine lake), but also to water column stratification (in a large deep Swiss lake). To understand the controls on i) the presence of long-chain diols in lakes, and ii) the distribution of long-chain diol isomers, surface sediments from 52 Swiss lakes were studied. Long-chain diols are present in 57% of the lakes, and machine learning (i.e., random forest model) showed that their presence is mainly controlled by mean annual air temperature, sodium and potassium concentrations and area of the lakes. Long-chain diol isomer relative distribution seems to react to temperature, nutrient (here nitrate) and oxygen concentrations in the lakes. This new insight was tested on a short sedimentary core from Lake Zurich, and compared with other biomarker proxies (based on branched and isoprenoid glycerol dialkyl glycerol tetraethers), as well as with historical record of nutrient contents and temperature. Variations in the long-chain diol index (LDI) mirror measured temperature, but also reacted to changes in nutrients and oxygenation in the lake. This study highlights the potential of long-chain diols as a proxy to trace both nutrients and temperature in lakes, potentially on geological timescales. [ABSTRACT FROM AUTHOR]

The sole unifying feature of the incredibly diverse Archaea is their isoprenoid‐based ether‐linked lipid membranes. Unique lipid membrane composition, including an abundance of membrane‐spanning tetraether lipids, impart resistance to extreme conditions. Many questions remain, however, regarding the synthesis and modification of tetraether lipids and how dynamic changes to archaeal lipid membrane composition support hyperthermophily. Tetraether membranes, termed glycerol dibiphytanyl glycerol tetraethers (GDGTs), are generated by tetraether synthase (Tes) by joining the tails of two bilayer lipids known as archaeol. GDGTs are often further specialized through the addition of cyclopentane rings by GDGT ring synthase (Grs). A positive correlation between relative GDGT abundance and entry into stationary phase growth has been observed, but the physiological impact of inhibiting GDGT synthesis has not previously been reported. Here, we demonstrate that the model hyperthermophile Thermococcus kodakarensis remains viable when Tes (TK2145) or Grs (TK0167) are deleted, permitting phenotypic and lipid analyses at different temperatures. The absence of cyclopentane rings in GDGTs does not impact growth in T. kodakarensis, but an overabundance of rings due to ectopic Grs expression is highly fitness negative at supra‐optimal temperatures. In contrast, deletion of Tes resulted in the loss of all GDGTs, cyclization of archaeol, and loss of viability upon transition to the stationary phase in this model archaea. These results demonstrate the critical roles of highly specialized, dynamic, isoprenoid‐based lipid membranes for archaeal survival at high temperatures. Plain Language Summary: The preponderance of tetraether membrane‐spanning lipids in many archaeal clades indicates the fitness advantage of unique membranes for archaeal survival. The inability to rationally control the synthesis of tetraether and cyclized tetraether‐lipids has limited investigations into how dynamic shifts in lipid composition support archaeal growth and phase transitions. Employing the facile genetic system of the model hyperthermophilic archaeon Thermococcus kodakarensis that naturally synthesizes abundant tetraether lipids, we identified and targeted the genes necessary for tetraether lipid synthesis and derivatization. While impairing tetraether lipid biosynthesis is possible, the lack of specialized lipids dramatically impairs long‐term survival, supporting a critical role for dynamic lipidome changes in supporting archaeal life in the extremes. [ABSTRACT FROM AUTHOR]

The enzymology of the key steps in the archaeal phospholipid biosynthetic pathway has been elucidated in recent years. In contrast, the complete biosynthetic pathways for proposed membrane regulators consisting of polyterpenes, such as carotenoids, respiratory quinones, and polyprenols remain unknown. Notably, the multiplicity of geranylgeranyl reductases (GGRs) in archaeal genomes has been correlated with the saturation of polyterpenes. Although GGRs, which are responsible for saturation of the isoprene chains of phospholipids, have been identified and studied in detail, there is little information regarding the structure and function of the paralogs. Here, we discuss the diversity of archaeal membrane-associated polyterpenes which is correlated with the genomic loci, structural and sequence-based analyses of GGR paralogs. [ABSTRACT FROM AUTHOR]

Abstract Ratios of glycerol dialkyl glycerol tetraethers (GDGT), which are membrane lipids of bacteria and archaea, are at the base of several paleoenvironmental proxies. They are frequently applied to soils as well as lake‐ and marine sediments to generate records of past temperature and soil pH. To derive meaningful environmental information from these reconstructions, high analytical reproducibility is required. Based on submitted results by 39 laboratories from across the world, which employ a diverse range of analytical and quantification methods, we explored the reproducibility of brGDGT‐based proxies (MBT′5ME, IR, and #ringstetra) measured on four soil samples and four soil lipid extracts. Correct identification and integration of 5‐ and 6‐methyl brGDGTs is a prerequisite for the robust calculation of proxy values, but this can be challenging as indicated by the large inter‐interlaboratory variation. The exclusion of statistical outliers improves the reproducibility, where the remaining uncertainty translates into a temperature offset from median proxy values of 0.3–0.9°C and a pH offset of 0.05–0.3. There is no apparent systematic impact of the extraction method and sample preparation steps on the brGDGT ratios. Although reported GDGT concentrations are generally consistent within laboratories, they vary greatly between laboratories. This large variability in brGDGT quantification may relate to variations in ionization efficiency or specific mass spectrometer settings possibly impacting the response of brGDGTs masses relative to that of the internal standard used. While ratio values of GDGT are generally comparable, quantities can currently not be compared between laboratories.

The degree of cyclization, or ring index (RI), in archaeal glycerol dibiphytanyl glycerol tetraether (GDGT) lipids was long thought to reflect homeoviscous adaptation to temperature. However, more recent experiments show that other factors (e.g., pH, growth phase, and energy flux) can also affect membrane composition. The main objective of this study was to investigate the effect of carbon and energy metabolism on membrane cyclization. To do so, we cultivated Acidianus sp. DS80, a metabolically flexible and thermoacidophilic archaeon, on different electron donor, acceptor, and carbon source combinations (S0/Fe3+/CO2, H2/Fe3+/CO2, H2/S0/CO2, or H2/S0/glucose). We show that differences in energy and carbon metabolism can result in over a full unit of change in RI in the thermoacidophile Acidianus sp. DS80. The patterns in RI correlated with the normalized electron transfer rate between the electron donor and acceptor and did not always align with thermodynamic predictions of energy yield. In light of this, we discuss other factors that may affect the kinetics of cellular energy metabolism: electron transfer chain (ETC) efficiency, location of ETC reaction components (cytoplasmic vs. extracellular), and the physical state of electron donors and acceptors (gas vs. solid). Furthermore, the assimilation of a more reduced form of carbon during heterotrophy appears to decrease the demand for reducing equivalents during lipid biosynthesis, resulting in lower RI. Together, these results point to the fundamental role of the cellular energy state in dictating GDGT cyclization, with those cells experiencing greater energy limitation synthesizing more cyclized GDGTs. [ABSTRACT FROM AUTHOR]

Ancient lake deposits in the Mojave Desert indicate that the water cycle in this currently dry place was radically different under past climates. Here we revisit a 700 m core drilled 55 years ago from Searles Valley, California, that recovered evidence for a lacustrine phase during the late Pliocene. We update the paleomagnetic age model and extract new biomarker evidence for climatic conditions from lacustrine deposits (3.373–2.706 Ma). The MBT′5Me temperature proxy detects present‐day conditions (21 ± 3°C, n = 2) initially, followed by warmer‐than‐present conditions (25 ± 3°C, n = 17) starting at 3.268 and ending at 2.734 Ma. Bacterial and archeal biomarkers reveal lake salinity increased after 3.268 Ma likely reflecting increased evaporation in response to higher temperatures. The δ13C values of plant waxes (−30.7 ± 1.4‰, n = 28) are consistent with local C3 taxa, likely expanded conifer woodlands during the pluvial with less C4 than the Pleistocene. δD values (−174 ± 5‰, n = 25) of plant waxes indicate precipitation δD values (−89 ± 5‰, n = 25) in the late Pliocene are within the same range as the late Pleistocene precipitation δD. Microbial biomarkers identify a deep, freshwater lake and a cooling that corresponds to the onset of major Northern Hemisphere glaciation at marine isotope stage marine isotope stages M2 (3.3 Ma). A more saline lake persisted for ∼0.6 Ma across the subsequent warmth of the late Pliocene (3.268–2.734 Ma) before the lake desiccated at the Pleistocene intensification of Northern Hemisphere Glaciation. Plain Language Summary: During a generally warm period 3 million years ago, there were large lakes in the Mojave Desert, California. We measured organic matter preserved in ancient lake mud below today's salt flat in Searles Valley to investigate the climate changes that sustained these 3‐million‐year‐old lakes. We compiled evidence for a freshwater lake, increased rainfall, and woody plants around the lake during a cooler interval, with similar‐to‐modern temperatures, that interrupted what was generally a warm period between 5 and 3 million years ago. Today the valley contains a saltpan, the evaporated remains of the former lake, surrounded by open desert shrubland. We compare the evidence from the lake with other climate reconstructions and find the wetter conditions coincided with cooling both locally and at higher latitudes. Key Points: Lacustrine sediments in Mojave Desert sediment core span 3.373–2.706 MaMicrobial biomarkers record deep, fresh lake during cool period 3.373–3.268 MaLake salinity increases after 3.268 Ma, associated with warming [ABSTRACT FROM AUTHOR]

Long-chain diols are biomarkers commonly used in the marine realm to reconstruct several environmental parameters such as sea surface temperature and salinity. However, they are also produced in lacustrine and slow-flowing river environments, a characteristic that has proved to be useful to trace past riverine inputs in coastal sedimentary records. So far, their use in lacustrine settings is sparse as their controls are not well-known. Previous studies in two lakes have shown that long-chain diol distribution is linked to changes in temperature (in a small Spanish alpine lake), but also to water column stratification (in a large deep Swiss lake). To understand the controls on i) the presence of long-chain diols in lakes, and ii) the distribution of long-chain diol isomers, surface sediments from 52 Swiss lakes were studied. Long-chain diols are present in 57% of the lakes, and machine learning (i.e., random forest model) showed that their presence is mainly controlled by mean annual air temperature, sodium and potassium concentrations and area of the lakes. Long-chain diol isomer relative distribution seems to react to temperature, nutrient (here nitrate) and oxygen concentrations in the lakes. This new insight was tested on a short sedimentary core from Lake Zurich, and compared with other biomarker proxies (based on branched and isoprenoid glycerol dialkyl glycerol tetraethers), as well as with historical record of nutrient contents and temperature. Variations in the long-chain diol index (LDI) mirror measured temperature, but also reacted to changes in nutrients and oxygenation in the lake. This study highlights the potential of long-chain diols as a proxy to trace both nutrients and temperature in lakes, potentially on geological timescales.

Branched and isoprenoidal glycerol dialkyl glycerol tetraethers (br- and isoGDGTs) are membrane lipids produced by bacteria and archaea, respectively. These lipids form the basis of several frequently used paleoclimatic proxies. For example, the degree of methylation of brGDGTs (MBT' 5Me) preserved in mineral soils (as well as peats and lakes) is one of the most important terrestrial paleothermometers, but features substantial variability that is so far insufficiently constrained. The distribution of isoGDGTs in mineral soils has received less attention and applications have focused on the use of the relative abundance of the isoGDGT crenarchaeol versus brGDGTs (BIT index) as an indicator of aridity. To expand our knowledge of the factors that can impact the br- and isoGDGT distribution in mineral soils, including the MBT' 5Me index, and to improve isoGDGT-based precipitation reconstructions, we surveyed the GDGT distribution in a large collection of mineral surface soils (n = 229) and soil profiles (n = 22) across tropical South America. We find that the MBT' 5Me index is significantly higher in grassland compared to forest soils, even among sites with the same mean annual air temperature. This is likely a result of a lack of shading in grasslands, leading to warmer soils. We also find a relationship between MBT' 5Me and soil pH in tropical soils. Together with existing data from arid areas in mid-latitudes, we confirm the relationship between the BIT-index and aridity, but also find that the isoGDGT distribution alone is aridity dependent. The combined use of the BIT-index and isoGDGTs can strengthen reconstructions of past precipitation in terrestrial archives. In terms of site-specific variations, we find that the variability in BIT and MBT' 5Me is larger at sites that show on average lower BIT and MBT' 5Me values. In combination with modelling results, we suggest that this pattern arises from the mathematical formulation of these proxies that amplifies variability for intermediate values and mutes it for values close to saturation (value of 1). Soil profiles show relatively little variation with depth for the brGDGT indices. On the other hand, the isoGDGT distribution changes significantly with depth as does the relative abundance of br- versus isoGDGTs. This pattern is especially pronounced for the isoGDGT IsomerIndex where deeper soil horizons show a near absence of isoGDGT isomers. This might be driven by archaeal community changes in different soil horizons, potentially driven by the difference between aerobic and anaerobic archaeal communities. Finally, we use our extensive new dataset and Bayesian neural networks (BNNs) to establish new brGDGT-based temperature models. We provide a tropical soil calibration that removes the pH dependence of tropical soils (n = 404; RMSE = 2.0 °C) and global peat and soil models calibrated against the temperature of the months above freezing (n = 1740; RMSE = 2.4) and mean annual air temperature (n = 1740; RMSE = 3.6). All models correct for the bias found in arid samples. We also successfully test the new calibrations on Chinese loess records and tropical river sediments. Overall, the new calibrations provide improved temperature reconstructions for terrestrial archives. [ABSTRACT FROM AUTHOR]

Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are membrane-spanning lipids produced by bacteria that are ubiquitous in natural sedimentary archives and preserved over geologic timescales. The main influence on their distributions in the environment appears to be temperature, thus making them a potentially powerful proxy for paleotemperature reconstruction. Application of recent lacustrine brGDGT-based temperature calibration models to specific regions results in inaccurate reconstructed temperatures suggesting that regional or site-specific temperature calibration models may be necessary. Using an extended data set of 692 lake sediment samples from across the globe we determined whether brGDGT distributions in samples from the same regions or sites are significantly different from one another via hierarchical agglomerative clustering analysis (HAC). Results of HAC analysis showed four significant clusters with varying geographic distributions. Cluster 1 samples are mainly located at high latitudes (Mean Annual Air Temperature; MAAT = 3.10 ± 5.91 °C). Cluster 2 samples are concentrated in the Tibetan Plateau (MAAT = 1.54 ± 5.91 °C). Cluster 3 samples span temperate-tropical latitudes (MAAT = 17.26 ± 8.16 °C). Cluster 4 samples are mainly located in Central and South America (MAAT = 24.56 ± 4.01 °C). The clustering led us to develop random forest regression models to predict temperature (MAAT and Months Above Freezing, MAF, air temperature) based on samples within each cluster (cluster-specific temperature models). Model performance was the highest for Cluster 3 (MAF: R2 = 0.78, RMSE = 2.85 °C, n = 261; MAAT: R2 = 0.76, RMSE = 4.07 °C, n = 270), followed by Cluster 1 (MAF: R2 = 0.54, RMSE = 1.67 °C; n = 219; MAAT: R2 = 0.62, RMSE = 3.62 °C, n = 226) and Cluster 4 (MAF: R2 = 0.58, RMSE = 2.46, n = 67; MAAT: R2 = 0.59, RMSE = 2.52 °C, n = 67). The Cluster 2 model had the lowest model performance (MAF: R2 = 0.42, RMSE = 4.51, n = 38; MAAT: R2 = 0.51, RMSE = 1.74 °C, n = 129). We also developed a random forest classification model to predict the cluster assignment for new samples (cluster prediction model with an overall accuracy of 95%), which informs the user as to which cluster-specific temperature model(s) to apply to their samples. Finally, we applied our approach (i.e., cluster assignment followed by cluster-specific temperature reconstruction) to seven published lacustrine (paleo)records and illustrate pitfalls among the temperature reconstructions from brGDGT-based temperature calibration models. Overall, our study defines broad geographic relationships among lacustrine brGDGT distributions and air temperature while underscoring model limitations for paleotemperature reconstruction and subsequent interpretation. [ABSTRACT FROM AUTHOR]

Archaea adjust the number of cyclopentane rings in their glycerol dibiphytanyl glycerol tetraether (GDGT) membrane lipids as a homeostatic response to environmental stressors such as temperature, pH, and energy availability shifts. However, archaeal expression patterns that correspond with changes in GDGT composition are less understood. Here we characterize the acid and cold stress responses of the thermoacidophilic crenarchaeon Saccharolobus islandicus REY15A using growth rates, core GDGT lipid profiles, transcriptomics and proteomics. We show that both stressors result in impaired growth, lower average GDGT cyclization, and differences in gene and protein expression. Transcription data revealed differential expression of the GDGT ring synthase grsB in response to both acid stress and cold stress. Although the GDGT ring synthase encoded by grsB forms highly cyclized GDGTs with =5 ring moieties, S. islandicus grsB upregulation under acidic pH conditions did not correspond with increased abundances of highly cyclized GDGTs. Our observations highlight the inability to predict GDGT changes from transcription data alone. Broader analysis of transcriptomic data revealed that S. islandicus differentially expresses many of the same transcripts in response to both acid and cold stress. These included upregulation of several biosynthetic pathways and downregulation of oxidative phosphorylation and motility. Transcript responses specific to either of the two stressors tested here included upregulation of genes related to proton pumping and molecular turnover in acid stress conditions and upregulation of transposases in cold stress conditions. Overall, our study provides a comprehensive understanding of the GDGT modifications and differential expression characteristic of the acid stress and cold stress responses in S. islandicus. [ABSTRACT FROM AUTHOR]

The TEX86 paleothermometer has been extensively used to reconstruct past sea water temperatures, but it remains unclear which export depths the proxy represents. Here we used a novel approach to better constrain the proxy recording depths by investigating paleotemperature proxies (TEX86, U37K′ ${\mathrm{U}}_{37}^{{\mathrm{K}}^{\prime }}$, RI−OH and RI−OH′) from two pairs of proximal (<12 km apart) cores from Chilean and Angola margins, respectively. These cores are from steep continental slopes and lower shelves, which leads to a substantial difference in water depth between them despite being closely located. Surprisingly, the deep and the shallow U37K′ ${\mathrm{U}}_{37}^{{\mathrm{K}}^{\prime }}$ records at the Chilean margin show dissimilarities, in contrast to the similar records from the Angola margin, which may be due to post‐depositional alteration at the former sites. In contrast, the TEX86 records were statistically indistinguishable between the sites at both the locations, even though the GDGT [2]/[3] ratio suggests GDGTs derived from potentially different archaeal communities residing at different depths. A short‐lived difference between the TEX86 records is observed during the last glacial period at the Angola margin, possibly due to a contribution of Antarctic Intermediate Waters to the deep site. Modelling suggests that the TEX86 source signal at our core sites reaches its peak abundance at water depths shallower than 350 m. The RI−OH and RI−OH′ records show similar variability as the TEX86 records, although regional differences in their absolute temperature estimates exist. Our approach using proximal sediment cores at steep slopes appears useful to constrain the export depth of organic proxy signals for paleo‐reconstructions. Key Points: Source signal of TEX86 proxy is likely derived from depths shallower than 350 m at Chilean and Angola marginsOH‐GDGT based proxies show similar variability as TEX86 records, but show regional differences in their absolute temperature estimatesU37K′ ${\mathrm{U}}_{37}^{{\mathrm{K}}^{\prime }}$ proxy signal may be impacted by post‐depositional changes or lateral transport even for closely located cores [ABSTRACT FROM AUTHOR]

Great Salt Lake (GSL), Utah, is a hypersaline terminal lake in the Great Basin, and the remnant of the late glacial Lake Bonneville. Holocene hydroclimate variations cannot be interpreted from the shoreline record, but instead can be investigated by proxies archived in the sediments. GLAD1‐GSL00‐1B was cored in 2000 and recently dated by radiocarbon for the Holocene section with the top 11 m representing ∼7 ka to present. Sediment samples every 30 cm (∼220 years) were studied for the full suite of microbial membrane lipids, including those responsive to temperature and salinity. The Archaeol and Caldarchaeol Ecometric (ACE) index detects the increase in lipids of halophilic archaea, relative to generalists, as salinity increases. We find Holocene ACE values ranged from 81 to 98, which suggests persistent hypersalinity with <50 g/L variability across 7.2 ka. The temperature proxy, MBTʹ5Me, yields values similar to modern mean annual air temperature for months above freezing (MAF = 15.7°C) over the last 5.5 ka. Several glycerol dialkyl glycerol tetraether metrics show a step shift in microbial communities and limnology at 5.5 ka. Extended archaeol detects elevated salinity during the regional mid‐Holocene drought, not readily detected in the ACE record that is often near the upper limit of the index. We infer that the mid‐Holocene GSL was shallower and saltier than the late Holocene. The current drying may be returning the lake to conditions not seen since the mid‐Holocene. Plain Language Summary: Great Salt Lake (GSL) in Utah is the remnant of a once much larger lake and is currently at a historically low level. We study a lake sediment core, collected in 2000 from the floor of GSL, and recently dated. We take new samples from the core and measure them for molecules made by microbes, whether living in the lake or washed in from the surrounding soils. We reconstruct lake conditions during the last 7,200 years and assess whether lake level fluctuated during that time. Over the past 7,200 years, we find evidence that the lake was shallower from 7,200 to 5,500 years ago but has been relatively stable until the modifications of the lake in the 20th century and the current drying trend. Key Points: Glycerol dialkyl glycerol tetraethers produced by bacteria and archaea detect Holocene limnological changes at Great Salt Lake (GSL)The Archaeol and Caldarchaeol Ecometric salinity index remains near its upper limit in GSL from 7.2 ka to presentA 5.5 ka step shift in microbial lipids suggests limnological change coeval with the end of a regional dry spell in the mid‐Holocene [ABSTRACT FROM AUTHOR]

Cellular membranes are essential for compartmentalization, maintenance of permeability, and fluidity in all three domains of life. Archaea belong to the third domain of life and have a distinct phospholipid composition. Membrane lipids of archaea are ether-linked molecules, specifically bilayer-forming dialkyl glycerol diethers (DGDs) and monolayer-forming glycerol dialkyl glycerol tetraethers (GDGTs). The antifungal allylamine terbinafine has been proposed as an inhibitor of GDGT biosynthesis in archaea based on radiolabel incorporation studies. The exact target(s) and mechanism of action of terbinafine in archaea remain elusive. Sulfolobus acidocaldarius is a strictly aerobic crenarchaeon thriving in a thermoacidophilic environment, and its membrane is dominated by GDGTs. Here, we comprehensively analyzed the lipidome and transcriptome of S. acidocaldarius in the presence of terbinafine. Depletion of GDGTs and the accompanying accumulation of DGDs upon treatment with terbinafine were growth phase-dependent. Additionally, a major shift in the saturation of caldariellaquinones was observed, which resulted in the accumulation of unsaturated molecules. Transcriptomic data indicated that terbinafine has a multitude of effects, including significant differential expression of genes in the respiratory complex, motility, cell envelope, fatty acid metabolism, and GDGT cyclization. Combined, these findings suggest that the response of S. acidocaldarius to terbinafine inhibition involves respiratory stress and the differential expression of genes involved in isoprenoid biosynthesis and saturation. [ABSTRACT FROM AUTHOR]

Archaea adjust the number of cyclopentane rings in their glycerol dibiphytanyl glycerol tetraether (GDGT) membrane lipids as a homeostatic response to environmental stressors such as temperature, pH, and energy availability shifts. However, archaeal expression patterns that correspond with changes in GDGT composition are less understood. Here we characterize the acid and cold stress responses of the thermoacidophilic crenarchaeon Saccharolobus islandicus REY15A using growth rates, core GDGT lipid profiles, transcriptomics and proteomics. We show that both stressors result in impaired growth, lower average GDGT cyclization, and differences in gene and protein expression. Transcription data revealed differential expression of the GDGT ring synthase grsB in response to both acid stress and cold stress. Although the GDGT ring synthase encoded by grsB forms highly cyclized GDGTs with ≥5 ring moieties, S. islandicus grsB upregulation under acidic pH conditions did not correspond with increased abundances of highly cyclized GDGTs. Our observations highlight the inability to predict GDGT changes from transcription data alone. Broader analysis of transcriptomic data revealed that S. islandicus differentially expresses many of the same transcripts in response to both acid and cold stress. These included upregulation of several biosynthetic pathways and downregulation of oxidative phosphorylation and motility. Transcript responses specific to either of the two stressors tested here included upregulation of genes related to proton pumping and molecular turnover in acid stress conditions and upregulation of transposases in cold stress conditions. Overall, our study provides a comprehensive understanding of the GDGT modifications and differential expression characteristic of the acid stress and cold stress responses in S. islandicus.

Archaeal membrane lipids known as glycerol dibiphytanyl glycerol tetraethers (GDGTs) are the basis of the TEX86 paleotemperature proxy. Because GDGTs preserved in marine sediments are thought to originate mainly from planktonic, ammonia-oxidizing Thaumarchaeota, the basis of the correlation between TEX86 and sea surface temperature (SST) remains unresolved: How does TEX86 predict surface temperatures, when maximum thaumarchaeal activity occurs below the surface mixed layer and TEX86 does not covary with in situ growth temperatures? Here we used isothermal studies of the model thaumarchaeon Nitrosopumilus maritimus SCM1 to investigate how GDGT composition changes in response to ammonia oxidation rate. We used continuous culture methods to avoid potential confounding variables that can be associated with experiments in batch cultures. The results show that the ring index scales inversely (R(2) = 0.82) with ammonia oxidation rate (ϕ), indicating that GDGT cyclization depends on available reducing power. Correspondingly, the TEX86 ratio decreases by an equivalent of 5.4 °C of calculated temperature over a 5.5 fmol·cell(-1)·d(-1) increase in ϕ. This finding reconciles other recent experiments that have identified growth stage and oxygen availability as variables affecting TEX86 Depth profiles from the marine water column show minimum TEX86 values at the depth of maximum nitrification rates, consistent with our chemostat results. Our findings suggest that the TEX86 signal exported from the water column is influenced by the dynamics of ammonia oxidation. Thus, the global TEX86-SST calibration potentially represents a composite of regional correlations based on nutrient dynamics and global correlations based on archaeal community composition and temperature.

The glycerol dialkyl glycerol tetraether (GDGT) lipids of archaea and bacteria have been extensively studied in both modern and ancient wetlands, but their specific biological sources and biogeochemical significance in such settings remain unclear. The stable carbon isotopic composition of GDGTs, and associated tetraether lipids such as butanetriol - DGTs (BDGTs), can help reveal aspects of the carbon metabolism of their source organism. Here we present an in-depth compound-specific analyses of archaeal (isoGDGTs and BDGT-0) and bacterial (brGDGTs) tetraether lipid δ13C values from the Florida Everglades wetland, supplemented by 16S rRNA gene profiling of the archaeal community. We interpret this alongside GDGT δ13C analyses from three additional freshwater wetland sediments, and two ancient wetland deposits (lignites) from the Miocene. Our data suggests that isoGDGT-0 δ13C values, which range from –22.5‰ to −36.5‰ across our wetland sites, could to some degree reflect the relative importance of the acetotrophic and CO 2 -reducing hydrogenotrophic methanogenic pathways, though definitively delineating between the two is challenging due to (a) potential incorporation of dissolved inorganic carbon (DIC) by CO 2 reducers, and (b) the diluting effect of GDGTs derived from seemingly heterotrophic/fermentative Bathyarchaeia, the most abundant archaeal class in the Everglades. In the Everglades, which harbours abundant Methanomassiliicoccales, BDGT-0 is significantly more 13C-depleted than all other lipids, with a δ13C signature at certain depths (∼−40.0 to −45.0‰) that is consistent with an important source from these (likely) methylotrophic methanogens. This adds to a growing body of evidence on the underappreciated role of methylotrophic methanogenesis, largely driven by Methanomassiliicoccales , in the freshwater methane cycle. However, slightly more 13C-enriched values (∼−35.0‰) at certain depths in the same site provide evidence for additional, possibly heterotrophic sources under certain conditions, and BDGT-0 δ13C values in the Miocene lignite (≈ δ13C of TOC) are consistent with a solely heterotrophic source. Where available for measurement, δ13C values of isoGDGTs-1 to -3, averaging –32.7 ± 2.3‰, were significantly more 13C-depleted than isoGDGT-0, suggesting a different mixture of sources, likely including an autotrophic/mixotrophic component derived from archaea belonging to the Crenarchaeota, Nitrososphaeria (formerly Thaumarchaeota) and/or MBG-D/DHVEG-1. Finally, brGDGT δ13C values are generally consistent with their proposed bacterial heterotrophic origin and biosynthetic effects, averaging out at around 4‰ depleted relative to total organic carbon (TOC). Importantly, we find no significant variation between the δ13C values of different brGDGTs across our wetland types. This highlights that spatial and temporal changes in commonly applied brGDGT-based proxies likely do not co-occur with changes in the heterotrophic lifestyle of their producer(s), discounting a possible confounding factor in brGDGT palaeothermometry. Taken together, our results yield insights into wetland archaeal communities and the lipids they produce, and underline the applicability of tetraether δ13C analyses in probing aspects of microbial carbon cycling in modern and ancient wetland sediments. [ABSTRACT FROM AUTHOR]

• isoGDDs are ubiquitous in the natural environment. • Abundance and degree of cyclisation of isoGDDs strongly correlated with isoGDGTs. • isoGDDs are predominantly a degradation product of isoGDGTs. Glycerol dialkyl diethers (GDDs) are membrane lipids and a variation of the more commonly known glycerol dialkyl glycerol tetraethers (GDGTs). GDGTs include both archaeal and bacterial membrane lipids that are both frequently used for paleoclimate reconstruction in a range of terrestrial and aquatic environments. In contrast to GDGTs, GDDs lack one of the terminal glycerol moieties. Although both isoprenoidal (iso) and branched (br) GDDs have been found, this study focuses on isoGDDs. These lipids have been found in a few terrestrial and aquatic environments. However, the origin of isoGDDs is debated and the extent of their distribution across the surface of the Earth is poorly constrained. Based on a few single site studies, previous authors hypothesised that isoGDDs are degradation products of isoGDGTs, but more recent studies that isolated isoGDDs from cultured nitrososphaerota (formerly thaumarchaeota) proposed a biological source through direct archaeal biosynthesis. Here we compiled a global dataset of isoGDD and isoGDGT abundance in environmental samples to thoroughly investigate the distribution of isoGDDs and the correlation with isoGDGTs on a global scale and across a variety of environments (peat, mineral soils, lake sediments, and marine sediments). We find that isoGDDs are present in most samples that we analysed. Their abundance is strongly proportional to isoGDGT abundance (r2 = 0.85), dominated by the GDGT-crenarchaeol/GDD-crenarchaeol ratio (r2 = 0.94) and supported by individual compound isoGDGT/isoGDD ratios (r2 = 0.56–0.94). In addition, the degree of cyclisation of isoGDDs, reflected in the ring index, is positively correlated (r2 = 0.84) with that of isoGDGTs across all environments. We conclude that isoGDDs are abundant on the surface of the Earth and predominantly originate from the degradation of isoGDGTs. [ABSTRACT FROM AUTHOR]

Over the last decade, glycerol dialkyl glycerol tetraethers (GDGTs) have become one of the most investigated lipid classes in marine and terrestrial organic geochemical research. GDGTs are microbial membrane core lipids biosynthesized as multiple homolog series of isoprenoid or methyl-branched isomers [isoprenoid glycerol dialkyl glycerol tetraethers (isoGDGTs) and Branched GDGTs (brGDGTs), respectively], whose relative abundance depend on a range of environmental parameters, including temperature. This has led to the development of GDGT-based temperature proxies. A key aspect in the analysis of GDGTs and the further development of their use as environmental proxies is good chromatographic separation of the full range of structural and stereo-isomers, with potential for discovery of novel GDGT variants. Several HPLC methods have been developed to this extent, but partial co-elution of GDGTs remains an issue despite long run times. In this study, we investigate the effects of different types of reverse phase (RP) chromatography on the separation of GDGT isomers. We found that the use of a Kinetex C18-XB column gives good separation of isoGDGT isomers in comparison to the recently developed double column HILIC analysis operated in normal phase (NP) and has a shorter run time. In marine samples, the regularly reported isoprenoid GDGTs separated in a similar way as in NP, however an earlier eluting group was observed to elute with the crenarchaeol isomer used in the TEX86 proxy. In a Swedish peat bog sample, a large range of isoGDGT isomers were observed. We observed a range of brGDGT isomers in several samples often with near baseline separation. Exact identification of all these isomers remained elusive, due to the different mechanism of separation in RP, and the complexity of the brGDGT family. The C18-XB method is rapid and versatile and can be set up on either low-pressure HPLC systems (max 400 bar) with a sample run time of 25 min for brGDGTs and 45 min to include isoGDGTs. On UHPLC-MS systems (>600 bar) the sample run time is reduced to 15 min. Most importantly, the C18-XB method presented here gives unusual separation of both isoprenoid and brGDGTs and could be a useful tool for the further elucidation of the biological sources and environmental factors that play a role in the production of different GDGT isomers.

Reconstructing the timing of mountain range uplift and the evolution of high-altitude plateaus is important when attempting to understand potential feedbacks between tectonics and climate at geological timescales. This requires proxies that are able to accurately reconstruct elevation during different time periods in the past. Often, the sensitivity of climatic parameters to elevation gradients, recorded in geological archives such as soils, is used to estimate paleoelevations. However, most proxies reflect an indirect response to elevation change, adding uncertainties to reconstructions. In this study, we aim to identify those sources of uncertainty with respect to elevation reconstructions and test if the combined application of two such proxies, i.e., stable isotopes (δ2H) of plant waxes in modern soils and surface waters and bacterial membrane lipids (brGDGTs) in soils, which can potentially reduce uncertainties in the estimation of (paleo-) elevation. We performed this study in four Himalayan catchments (from west to east: Sutlej, Alaknanda, Khudi, and Arun), of which each individual catchment is subject to a unique precipitation regime, relative influences of moisture sources, and vegetation cover. In total, we analyzed 275 surface water samples, 9 precipitation samples, 131 xylem water samples, and 60 soil samples, which were collected between 2009 and 2014. The following key observations were made: Soil n C 31 -alkane δ2H values (δ2H wax) in the Sutlej, Alaknanda, Khudi, and Arun generally record surface water δ2H values, confirming that the first-order control on the plant wax isotopic signature is precipitation δ2H and, therefore, the elevation in orogenic settings. We identified aridity as the factor that introduces scatter to this relationship. BrGDGT-derived Mean Annual Temperature (MAT) correlates in a statistically significant manner with sample site elevation and a 14-year annual average of remotely sensed land-surface temperature, showing that the main process influencing the brGDGT distribution is the adiabatic cooling of air. In an effort to combine these proxies to improve uncertainties in elevation reconstruction, elevations were inferred from both the δ2H wax and brGDGT distributions. Arid, high elevation sites appear to underestimate actual sample site elevations using δ2H values while sites subject to high (>23–25 °C) annual temperatures overestimate the actual sample site elevation using brGDGT distributions. Elevations inferred from both proxies under such paleoclimatic conditions should be interpreted with caution. Elevations derived from the brGDGT distribution appear to most accurately reconstruct elevation. However, we show that the difference in elevation between the two proxies, described by the proposed Δ Elevation parameter, can provide information on the hydrological conditions of the soil's depositional environment. In conclusion, we emphasize that knowledge of the sample site's climatic conditions are essential to reconstruct elevation from paleoarchives. In particular, knowledge of moisture availability and annual air temperatures are important, as these have been found to cause the largest scatter in the observed data. [ABSTRACT FROM AUTHOR]

The Younger Dryas (YD, 12.9–11.7 ka) is the most recent, near‐global interval of abrupt climate change with rates similar to modern global warming. Understanding the causes and biodiversity effects of YD climate changes requires determining the spatial fingerprints of past temperature changes. Here we build pollen‐based and branched glycerol dialkyl glycerol tetraether‐based temperature reconstructions in eastern North America (ENA) to better understand deglacial temperature evolution. YD cooling was pronounced in the northeastern United States and muted in the north central United States. Florida sites warmed during the YD, while other southeastern sites maintained a relatively stable climate. This fingerprint is consistent with an intensified subtropical high during the YD and demonstrates that interhemispheric responses were more complex spatially in ENA than predicted by the bipolar seesaw model. Reduced‐amplitude or antiphased millennial‐scale temperature variability in the southeastern United States may support regional hotspots of biodiversity and endemism. Plain Language Summary: The Younger Dryas, circa 12,900 to 11,700 years ago, is a hemispheric abrupt climate change event that occurred at rates similar to those projected by the 21st century. Its cause has been linked to a reduction in northward oceanic heat transport in the Atlantic that led to Northern Hemispheric cooling and Southern Hemispheric warming. Here we present detailed reconstructions of Younger Dryas temperature variations in eastern North America that suggest a more complex spatial fingerprint than predicted by the standard global model. New England, Maritime Canada, and the Great Lakes Region all cooled, like Greenland and elsewhere in the Northern Hemisphere. However, regions south of Virginia experienced little temperature change and Florida warmed slightly. Possible mechanisms include atmospheric processes that enhanced advection from the subtropics and oceanic processes that transported heat northward from the equatorial Atlantic. These reconstructions also help explain the hotspot of biodiversity and endemic species in the southeastern United States, by showing that this region was buffered from past abrupt millennial‐scale climate reversals. Key Points: The spatial fingerprint of Younger Dryas (YD) temperature changes is reconstructed in eastern North America from brGDGTs and fossil pollenReconstructions demonstrate higher YD temperatures in Florida, no change south of 40°N, and cooling north of 40°NThese patterns are consistent with intensified subtropical highs during the YD and help explain high regional biodiversity [ABSTRACT FROM AUTHOR]

Tropical peatlands are an important carbon store and source of greenhouse gases, but the microbial component, particularly community structure, remains poorly understood. While microbial communities vary between tropical peatland land uses, and with biogeochemical gradients, it is unclear if their structure varies at smaller spatial scales as has been established for a variety of peat properties. We assessed the abundances of PLFAs and GDGTs, two membrane spanning lipid biomarkers in bacteria and fungi, and bacteria and archaea, respectively, to characterise peat microbial communities under two dominant and contrasting plant species, Campnosperma panamensis (a broadleaved evergreen tree), and Raphia taedigera (a canopy palm), in a Panamanian tropical peatland. The plant communities supported similar microbial communities dominated by Gram negative bacteria (38.9–39.8%), with smaller but significant fungal and archaeal communities. The abundance of specific microbial groups, as well as the ratio of caldarchaeol:crenarchaeol, isoGDGT: brGDGTs and fungi:bacteria were linearly related to gravimetric moisture content, redox potential, pH and organic matter content indicating their role in regulating microbial community structure. These results suggest that tropical peatlands can exhibit significant variability in microbial community abundance even at small spatial scales, driven by both peat botanical origin and localised differences in specific peat properties. [ABSTRACT FROM AUTHOR]

Archaea play an important role in marine biogeochemical cycle; however, their phylogenetic distribution and lipid composition in the hadal zone (6–11 km water depth) are poorly known. Here, we analyzed archaeal membrane lipids and 16S rRNA gene sequences in sediments from Mariana Trench (MT), Massau Trench (MS), and New Britain Trench (NBT), varying from 1,560 to 10,840 m depth. Forty‐two intact polar lipids (IPLs) were identified, including glycerol dialkyl glycerol tetraethers (GDGTs), OH‐GDGTs, glycerol dialkyl diethers (GDDs), and archaeol (AR) with polar headgroups of monohexose (1G), dihexose (2G), trihexose (3G), and hexose‐phosphohexose (HPH). Compositional and spatial distribution patterns of archaeal lipids suggest benthic Thaumarchaeota as a major source for IPLs, consistent with the predominance of Thaumarchaeota genes (>80%). The redundancy analysis (RDA) based on lipid and 16S rRNA data separates samples into three groups: extremely deep water (MT), significant terrestrial influence (NBT 1, 4, and 6), and predominant marine influence (MS, NBT 2, 3, 7, and 10). 1G‐GDDs and 1G‐AR positively correlate with water depth, likely reflecting the adaptation of benthic archaea to elevated hydrostatic pressure or variation of archaeal community in trench sediments. Bathyarchaeota are more abundant in sediments receiving terrestrial input; this pattern was attributed to their capability of utilizing terrestrial organic matter as an energy source. Our study highlights important environmental influences (e.g., pressure and organic matter quality and quantity) on benthic archaeal community and archaeal IPL compositions, which should be considered when IPLs and core lipids are applied as chemotaxonomic markers and paleo‐proxies. Key Points: Benthic archaea are a major source for IPLs in trench sedimentsSome IPLs positively correlate with water depth, reflecting adaption of archaea to hydrostatic pressure or changes of archaeal communityBathyarchaeota are more abundant in sediments receiving terrestrial input, attributed to utilization of terrestrial organic matter Plain Language Summary: This work is the first report on intact polar lipids (IPLs) of archaea in the hadal trenches, the deepest ocean realm with water depth exceeding 6,000 m. We have investigated in IPL biomarker 16S rRNA gene sequences and biogeochemical parameters in 19 sediments from the Mariana Trench, Massau Trench, and New Britain Trench. These samples are characterized by different water depth (1,560 to 10,840 m), net primary productivity (48 to 123 C m−2 year−1), and terrestrial influence. By comparing biomarker, gene data, and bulk geochemical parameters, we have achieved three key findings: (1) Benthic Thaumarchaeota are a major source for IPLs in hadal sediments; (2) Some IPLs positively correlate with water depth, likely reflecting an adaption mechanism of benthic archaea to elevated hydrostatic pressure or variation of archaeal community in different environments; and (3) Bathyarchaeota are more abundant in sediments receiving terrestrial input (New Britain Trench); this pattern is attributed to their capability of utilizing terrestrial organic matter as an energy source. Our findings provide important information toward understanding of the distribution and adaptation of hadal microbes to extremely high pressure, dark, and food‐depleted environments. [ABSTRACT FROM AUTHOR]

Sabkhas are important settings for understanding early earth biological environments, and the algal mats associated with them are thought to be potential source rocks for hydrocarbon production. In this study we compare the sedimentological facies and distribution of branched, and isoprenoid glycerol dialkyl glycerol tetraethers (GDGTs) in modern and mid-Holocene sabkha sediments from Abu Dhabi with well-preserved Miocene (12–13 Ma) sabkha sediments recently recovered at IODP site U1464 off the north coast of Australia. We show that the facies of the Miocene sediments is very similar to Holocene and modern sabkhas. Furthermore, we show that there are distinct patterns of isoprenoid GDGT distributions in the modern sabkha and that these patterns are well preserved in both the buried Holocene and the Miocene algal mats. The sabkha sediments analyzed are characterized by high %GDGT-0 and methane index, dominance of branched GDGTs over crenarchaeol (high BIT index), an unusual distribution of isoprenoid GDGTs 1–3, and also low abundance of archeol. The distribution of branched GDGT differs between modern and Miocene sabkhas and is similar in Miocene sabkha and non-sabkha sediments suggesting that they may be of limited use to distinguish paleo-sabkha sediments. Overall, isoprenoid GDGT distributions appear to be different from those found in modern soils, lakes and marine sediments, as well as from those found in Miocene shallow water sediments right below the sabkha, therefore they could be used in combination with facies analysis to identify paleo-sabkha environments in sedimentary sequences.

Archaea are ubiquitous in the modern ocean where they are involved in the carbon and nitrogen biogeochemical cycles. However, the majority of Archaea remain uncultured. Archaeal specific membrane intact polar lipids (IPLs) are biomarkers of the presence and abundance of living cells. They comprise archaeol and glycerol dibiphytanyl glycerol tetraethers (GDGTs) attached to various polar headgroups. However, little is known of the IPLs of uncultured marine Archaea, complicating their use as biomarkers. Here, we analyzed suspended particulate matter (SPM) obtained in high depth resolution from a coastal and open ocean site in the eastern tropical South Pacific (ETSP) oxygen deficient zone (ODZ) with the aim of determining possible biological sources of archaeal IPL by comparing their composition by Ultra High Pressure Liquid Chromatography coupled to high resolution mass spectrometry with the archaeal diversity by 16S rRNA gene amplicon sequencing and their abundance by quantitative PCR. Thaumarchaeotal Marine Group I (MGI) closely related to Ca. Nitrosopelagicus and Nitrosopumilus dominated the oxic surface and upper ODZ water together with Marine Euryarchaeota Group II (MGII). High relative abundance of hexose phosphohexose- (HPH) crenarchaeol, the specific biomarker for living Thaumarchaeota, and HPH-GDGT-0, dihexose- (DH) GDGT-3 and -4 were detected in these water masses. Within the ODZ, DPANN (Diapherotrites, Parvarchaeota, Aenigmarchaeota, Nanoarchaeota, and Nanohaloarchaea) of the Woesearchaeota DHVE-6 group and Marine Euryarchaeota Group III (MGIII) were present together with a higher proportion of archaeol-based IPLs, which were likely made by MGIII, since DPANN archaea are supposedly unable to synthesize their own IPLs and possibly have a symbiotic or parasitic partnership with MGIII. Finally, in deep suboxic/oxic waters a different MGI population occurred with HPH-GDGT-1, -2 and DH-GDGT-0 and -crenarchaeol, indicating that here MGI synthesize membranes with IPLs in a different relative abundance which could be attributed to the different detected population or to an environmental adaptation. Our study sheds light on the complex archaeal community of one of the most prominent ODZs and on the IPL biomarkers they potentially synthesize.

Glycerol dibiphytanyl glycerol tetraethers (GDGTs) are distinctive archaeal membrane-spanning lipids with up to eight cyclopentane rings and/or one cyclohexane ring. The number of rings added to the GDGT core structure can vary as a function of environmental conditions, such as changes in growth temperature. This physiological response enables cyclic GDGTs preserved in sediments to be employed as proxies for reconstructing past global and regional temperatures and to provide fundamental insights into ancient climate variability. Yet, confidence in GDGT-based paleotemperature proxies is hindered by uncertainty concerning the archaeal communities contributing to GDGT pools in modern environments and ambiguity in the environmental and physiological factors that affect GDGT cyclization in extant archaea. To properly constrain these uncertainties, a comprehensive understanding of GDGT biosynthesis is required. Here, we identify 2 GDGT ring synthases, GrsA and GrsB, essential for GDGT ring formation in Sulfolobus acidocaldarius. Both proteins are radical S-adenosylmethionine proteins, indicating that GDGT cyclization occurs through a free radical mechanism. In addition, we demonstrate that GrsA introduces rings specifically at the C-7 position of the core GDGT lipid, while GrsB cyclizes at the C-3 position, suggesting that cyclization patterns are differentially controlled by 2 separate enzymes and potentially influenced by distinct environmental factors. Finally, phylogenetic analyses of the Grs proteins reveal that marine Thaumarchaeota, and not Euryarchaeota, are the dominant source of cyclized GDGTs in open ocean settings, addressing a major source of uncertainty in GDGT-based paleotemperature proxy applications. [ABSTRACT FROM AUTHOR]

"Candidatus Nitrosotenuis uzonensis" is the only cultured moderately thermophilic member of the thaumarchaeotal order Nitrosopumilales (NP) that contains many mesophilic marine strains. We examined its membrane lipid composition at different growth temperatures (37°C, 46°C, and 50°C). Its lipids were all membranespanning glycerol dialkyl glycerol tetraethers (GDGTs), with 0 to 4 cyclopentane moieties. Crenarchaeol (cren), the characteristic thaumarchaeotal GDGT, and its isomer (cren=) were present in high abundance (30 to 70%). The GDGT polar headgroups were mono-, di-, and trihexoses and hexose/phosphohexose. The ratio of glycolipid to phospholipid GDGTs was highest in the cultures grown at 50°C. With increasing growth temperatures, the relative contributions of cren and cren= increased, while those of GDGT-0 to GDGT-4 (including isomers) decreased. TEX86 (tetraether index of tetraethers consisting of 86 carbons)-derived temperatures were much lower than the actual growth temperatures, further demonstrating that TEX86 does not accurately reflect the membrane lipid adaptation of thermophilic Thaumarchaeota. As the temperature increased, specific GDGTs changed relative to their isomers, possibly representing temperature adaption-induced changes in cyclopentane ring stereochemistry. Comparison of a wide range of thaumarchaeotal core lipid compositions revealed that the "Ca. Nitrosotenuis uzonensis" cultures clustered separately from other members of the NP order and the Nitrososphaerales (NS) order. While phylogeny generally seems to have a strong influence on GDGT distribution, our analysis of "Ca. Nitrosotenuis uzonensis" demonstrates that its terrestrial, higher-temperature niche has led to a lipid composition that clearly differentiates it from other NP members and that this difference is mostly driven by its high cren= content. [ABSTRACT FROM AUTHOR]

The relative abundance of the C 32 1,15 long-chain alkyl diol (LCD) is an emerging proxy for the input of riverine aquatic particulate organic carbon (POC) into coastal oceans. This compound has the potential to complement other established proxies reflecting riverine terrestrial POC input and allows for a more nuanced assessment of riverine POC export to coastal seas. The current understanding of this proxy is, however, limited. In this study, we compare different indices for riverine sediment input to coastal marine waters (i.e. C 32 1,15-LCD, BIT index and Fe/Ca ratio) in a source-to-sink assessment in the Amazon River drainage system and the northeast South American continental margin, and we test their down-core applicability in a marine gravity core containing late Pleistocene fluvial Amazonian sediments. We show that the relative abundance of the C 32 1,15-LCD is highest in water bodies with low flow velocity and low turbidity such as the downstream portion of lowland tributaries and floodplain lakes. Relative C 32 1,15-LCD abundance is lowest in Andean white water tributaries where autotrophic productivity is hindered by high turbidity and high flow velocity. We also find that suspended particulate matter from all major tributaries during the extreme 2015 dry season has a similar LCD distribution to that of floodplain lakes. This indicates that the chemical composition of the tributaries is less relevant for the LCD distribution than their physical properties such as flow velocity and turbidity. Results from marine surface sediments offshore the Amazon River estuary show significant positive correlations between all three studied proxies. In contrast, we find that the relative C 32 1,15-LCD abundance in the down-core record is anti-correlated to the BIT index and Fe/Ca ratio. While BIT index and Fe/Ca ratio show high (low) values during Heinrich stadials (Dansgaard-Oeschger interstadials), the C 32 1,15-LCD proxy shows the opposite signal. BIT values are also higher during Marine Isotope Stage (MIS) 2 than during MIS 3, in contrast to trends in the C 32 1,15-LCD proxy. We posit that this pattern arises from a reduction in relative C 32 1,15-LCD abundance and total LCD productivity in the Amazon River during MIS 2 when less-humid conditions and lower sea level led to reduced area of floodplains. During Heinrich stadials, Andean sediment input increased and led to higher turbidity that resulted in lower C 32 1,15-LCD production. Our study shows that major changes in water discharge, sediment transport and river morphology can lead to discrepancies between the BIT index and the relative abundance of the C 32 1,15-LCD. Thus, we suggest that Amazonian aquatic and terrestrial POC pools had contrasting responses to changes related to both climate (e.g. increased Andean precipitation) and river morphology (e.g. steeper along-channel slope due to falling and low stand sea level). [ABSTRACT FROM AUTHOR]

This study evaluates the application of biomarkerbased temperature proxy data (alkenone with its resultant U 37 K ′ index and glycerol dialkyl glycerol tetraether (GDGT) with its resultant TEX86and TEX index) in the Ulleung Basin of the East Sea. Based U 37 K ′ on the and TEX86 indices from particles trapped for 10 days in December, 2015 and core-top sediment as well as the comparison of these indices to in situ seawater temperature data (from 2012 to 2016) from the Korea Oceanographic Data Center, this study confirms that the U 37 K ′ index of core-top sediment indicates the annual mean SST of the surface water. This study also suggests that TEX86 data of core-top sediment may represent the annual mean temperature of the subsurface water. However, a reliable calibration equation for GDGT will be required in this regional environment for the proper application of GDGT-based paleotemperature reconstruction. [ABSTRACT FROM AUTHOR]

The Indo-Pacific Warm Pool is the largest source of heat and rainfall on Earth, but the mechanisms driving long-term climate variability in this region remain uncertain. Some studies suggest that precessional variations in insolation exert a primary role; alternatively, sea level change may be more important, with exposure of the Sunda and Sahul shelves leading to weakened Walker circulation across the Indian Ocean during glacial periods. The limited number of paleoclimate records from the warm pool that extend beyond the Last Glacial Maximum makes it difficult to test these competing hypotheses. Here, we present a 450,000-year long reconstruction of sea surface temperatures, sub-surface temperatures, and regional vegetation from southern Sumatra. We show that the dominant signal in each record is the 100 ky glacial cycle. We find that both surface and sub-surface temperatures cool during glacial periods, but the sub-surface cools more, reflecting a shoaling of the thermocline. Southern Sumatra and western Java consistently exhibit increased C 4 grass coverage and an enhanced dry season during glacial periods. The observed changes in the thermocline and rainfall seasonality are consistent with the shelf exposure mechanism, suggesting that sea level changes exert a prominent role in warm pool climate over glacial-interglacial timescales. • Tropical eastern Indian Ocean thermocline shoaled during last five glacial periods. • C 4 grasses expand over exposed Sunda Shelf during glacial periods. • Enhanced rainfall seasonality supports glacial drying over the Sunda Shelf. • The 100 ky glacial cycle dominates precession-driven insolation in our records. • Sea level exerts long-term control on coupled climate in the Indo-Pacific. [ABSTRACT FROM AUTHOR]

• A multi-biomarker record from Lake Elsinore, CA sediment core spans 32–9 ka. • Deglacial warming and storm-track shifts are consistent with prior studies nearby. • Plant wax hydrogen isotopes indicate storm-track changes during the last glacial. • Lipids show temperatures varied during the last glacial, including extreme warmth. Reconstructions of past hydroclimate provide a means to understand precipitation responses to global ocean-atmosphere climate dynamics beyond the scope of that in the instrumental record. Late glacial climate was characterized by abrupt variability in ice and ocean dynamics, however the implications for hydroclimate are not as well known. Here we present organic geochemical proxy evidence for precipitation isotopes based on plant leaf wax hydrogen isotopic compositions (δ D wax) and temperature proxy evidence based upon the branched glycerol dialkyl glycerol tetraethers (brGDGTs), that derive from the membrane lipids of bacteria, each extracted from a sedimentary archive in Lake Elsinore, California spanning 32–9 ka. We add proxy evidence for vegetation and salinity from additional biomarker analyses and compare to prior pollen and sedimentological evidence from the same core. Our record indicates a strong deglacial warming of 10 °C in Lake Elsinore (beginning at 14.5 ka) that accompanied a D-enrichment of precipitation of +90‰ and more C 4 vegetation (12–10 ka), after a cold, wet and C 3 -dominated phase (20–14.5 ka), indicating winter-dominated precipitation during the Last Glacial Maximum and Heinrich Stadial 1. During the late glacial (32–20 ka) we find abrupt variability, with precipitation isotopic shifts (∼70‰) that are independent of temperature swings implicating changes in storm track, rather than local temperature as drivers of the precipitation isotope signal. Temperature is however not irrelevant for hydroclimate: we find extreme warmth at 29.4 ka and 26.8 ka, the latter coincident with existing reports of an extended dry period (27.5–25.5 ka), suggesting a long hot and dry interlude during the generally cooler glacial period. We compare δ D wax with speleothem δ 18 O from Nevada, also within the winter-dominated precipitation region. Our results corroborate the Last Glacial Maximum and deglacial signals, and fill gaps revealing storm-track instability from 32–20 ka, however the pacing and magnitude of the biomarker signals merit cautious interpretation. [ABSTRACT FROM AUTHOR]

• Suspended particular matter from Lake Malawi was analyzed for isoprenoid GDGTs. • HPH-crenarchaeol concentrations were greatest just below the chlorophyll maximum. • Maximum CL concentrations likely reflect degradation of recently produced IPL GDGTs. • A second, deeper-dwelling Thaumarchaeotal population exists near the chemocline. Several long paleoclimate records generated from Lake Malawi sediments rely on an assumption that the TEX 86 paleothermometer reflects annual mean lake surface temperatures. Thaumarchaeota, the producers of the isoprenoid glycerol dialkyl glycerol tetraether (iGDGT) lipids that are the basis of the TEX 86 proxy, can occupy a wide range of habitats in the upper water column of lacustrine systems, so it is crucial to specifically constrain the ecology of Thaumarchaeota in Lake Malawi to properly interpret its sedimentary TEX 86 record. To investigate the spatial and vertical distribution of Thaumarchaeotal iGDGT production in Lake Malawi, suspended particulate matter (SPM) was collected from the upper water column (>300 m) at three sites spanning the north, central, and south basins of the lake and analyzed for intact polar (IPL) and core (CL) iGDGT lipid abundances. Samples were collected in January during the austral summer when the lake is strongly stratified. Concentrations of the most labile IPL, hexose-phosphohexose (HPH)-crenarchaeol, were greatest just below the deep chlorophyll maximum at ∼50 m water depth in the deeper north and central basins and ∼30 m in the shallow south basin. Maximum CL concentrations occur below the maximum HPH-crenarchaeol concentrations and therefore possibly reflect the accumulation of recently produced IPL GDGT degradation products. If the export of CLs to the sediments is dominated by this CL pool, sedimentary TEX 86 would reflect Thaumarchaeota living within the thermocline during the stratified season and therefore may have a cool bias rather than reflecting true surface water temperatures. An increase in abundances of GDGT-2, crenarchaeol isomer, and monohexose (MH)-crenarchaeol at ∼150–200 m suggests that a secondary Thaumarchaeotal population, likely Group I.1b Thaumarchaeota, inhabits the subsurface water column near the anoxic-suboxic boundary. Total production of iGDGTs by this group appears to be much lower than the surface-dwelling clade, but its imprint on sedimentary TEX 86 is unknown. An analysis of iGDGT production in the water column throughout the annual cycle is needed to resolve the timing and magnitude of export of CLs to the sediments from these two Thaumarchaeotal populations. [ABSTRACT FROM AUTHOR]

Lacustrine sediments generally record landscape development in the lake's catchment area controlled by palaeoclimatic and human induced changes. To improve our understanding on the anthropogenic and climatic influences on landscape development in Southern Greece for the last 2500 years, we report a 2 m-long, continuous high-resolution sedimentary record from shallow Lake Stymphalia (Peloponnese, Greece). Our proxies record climatically as well as anthropogenically induced landscape changes, influencing the lake area and lake depth. The Classical-Hellenistic era reflects a moderate, stable Mediterranean climate with low sedimentation rates. The parallel existence of the highly populated, major ancient city of Stymphalos, on the contemporary lake edge, doesn't seem to have caused lasting alterations in the record. The construction of the Hadrianic Aqueduct in the Roman era, ca. 130 AD, however causes an influential transformation in the lake development. It has a lasting effect on the lake hydrology as well as the vulnerability of this ecosystem. During Late Roman times, 5th to 6th century cal AD, the abandonment of the aqueduct combined with cooler climate conditions allows lake levels to recover. A phase of very high climatic instability was identified for the subsequent Early Byzantine (EB) period, during the 7th and 8th century cal AD. For this period, the later phase of the Late Antique Little Ice Age (LALIA), our proxies indicate further cooling and highly fluctuating water availability in a rather small lake area. The Middle Byzantine (MB) Period (9th-12th century AD) is characterized by an over fivefold increase in sedimentation rates. Since local population was still well below Classical levels, we explain this singular period through an interaction of modest increase in land use but marked by careless management of deforested areas, warm and wet climatic conditions during the Medieval Warm Period and long-term effects of vulnerability caused by the aqueduct construction. Probably during this phase, the lake level rose through unparalleled sedimentary infill to flood and bury a significant part of the Lower Town of the abandoned ancient city. The Late Byzantine Period (13th and 14th century AD) sees core evidence for erosion of established, non-vegetated soils (high magnetic susceptibility), in a period of almost total depopulation. In the subsequent Ottoman era (late 15th – early 19th centuries AD) local settlement made only slight recovery, the climatic conditions seem less stable during the Little Ice Age (LIA) and the lake seasonally and later periodically starts to dry up, cumulating in a longer dry phase at the end of the 19th century AD, when agricultural activity on the polje floor was possible. The conclusion conforms with recent modelling of environmental change, critical of mono-causation, rather focussing on complex interactions of human and natural factors in the inception of landscape transformation. [ABSTRACT FROM AUTHOR]

Archaea are ubiquitous in the modern ocean where they are involved in the carbon and nitrogen biogeochemical cycles. However, the majority of Archaea remain uncultured. Archaeal specific membrane intact polar lipids (IPLs) are biomarkers of the presence and abundance of living cells. They comprise archaeol and glycerol dibiphytanyl glycerol tetraethers (GDGTs) attached to various polar headgroups. However, little is known of the IPLs of uncultured marine Archaea, complicating their use as biomarkers. Here, we analyzed suspended particulate matter (SPM) obtained in high depth resolution from a coastal and open ocean site in the eastern tropical South Pacific (ETSP) oxygen deficient zone (ODZ) with the aim of determining possible biological sources of archaeal IPL by comparing their composition by Ultra High Pressure Liquid Chromatography coupled to high resolution mass spectrometry with the archaeal diversity by 16S rRNA gene amplicon sequencing and their abundance by quantitative PCR. Thaumarchaeotal Marine Group I (MGI) closely related to Ca. Nitrosopelagicus and Nitrosopumilus dominated the oxic surface and upper ODZ water together with Marine Euryarchaeota Group II (MGII). High relative abundance of hexose phosphohexose- (HPH) crenarchaeol, the specific biomarker for living Thaumarchaeota, and HPH-GDGT-0, dihexose- (DH) GDGT-3 and -4 were detected in these water masses. Within the ODZ, DPANN (Diapherotrites, Parvarchaeota, Aenigmarchaeota, Nanoarchaeota, and Nanohaloarchaea) of the Woesearchaeota DHVE-6 group and Marine Euryarchaeota Group III (MGIII) were present together with a higher proportion of archaeol-based IPLs, which were likely made by MGIII, since DPANN archaea are supposedly unable to synthesize their own IPLs and possibly have a symbiotic or parasitic partnership with MGIII. Finally, in deep suboxic/oxic waters a different MGI population occurred with HPH-GDGT-1, -2 and DH-GDGT-0 and -crenarchaeol, indicating that here MGI synthesize membranes with IPLs in a different relative abundance which could be attributed to the different detected population or to an environmental adaptation. Our study sheds light on the complex archaeal community of one of the most prominent ODZs and on the IPL biomarkers they potentially synthesize. [ABSTRACT FROM AUTHOR]

Highlights • Selective sn 2 ether cleavage reveals the glycerol configurations of GDGTs. • GDGTs in marine sediment have a predominantly parallel glycerol configuration. • Both crenarchaeol and its regioisomer possess the parallel glycerol configuration. • Branched GDGTs in the Messel shale and marine sediment are mainly antiparallel. Abstract The glycerol configurations of glycerol dialkyl glycerol tetraethers (GDGTs) in environmental samples were investigated using a selective sn 2 ether cleavage protocol. Using this procedure, GDGTs with a parallel glycerol configuration afford two types of derivatives, diols and diallylethers, whereas only one kind, monoallylethers, originate from their antiparallel isomers. Isoprenoidal GDGTs from a marine sediment are shown to be predominately parallel based on the distributions of these ether cleavage products. Crenarchaeol and its so-called regioisomer both have parallel configurations with the cyclohexane ring located on the sn 3,3 ether bonded tricyclic biphytanyl moiety. A Messel shale sample containing isoprenoidal GDGTs contributed mainly by methanogenic archaea has a substantial portion with the antiparallel configuration. Branched (non-isoprenoidal) GDGTs in both the Messel shale and the marine sediment are mainly antiparallel. This selective sn 2 ether cleavage approach provides a potentially powerful analytical tool to investigate not only the exact molecular structures of GDGT constitutional isomers and their biosynthetic pathways but also the heterogeneous inputs of sedimentary GDGT and their isotopic signatures, if different source species synthesize GDGTs with unique glycerol configurations. Further analyses of this type will reveal the glycerol configurations of the GDGTs of a broad range of microbial cultures and environmental samples. [ABSTRACT FROM AUTHOR]

The Paleocene-Eocene Thermal Maximum (PETM, ∼56 Ma) was an extreme climate warming event of the early Cenozoic. The development and ecology of carbonate platforms are highly sensitive to changes in SSTs, sea level and terrestrial detrital input. However, no record of SST changes during the PETM has yet been reported from a shallow marine carbonate platform. Here, we reconstruct SSTs for two shallow marine carbonate PETM sections in present-day southern Tibet from the distribution of isoprenoid glycerol dialkyl glycerol tetraethers (isoGDGT). Our dataset demonstrates that the temperature of the tropical eastern Tethys likely increased 3 to 5 °C during the PETM (depending on the TEX 86 calibration used), and it supports a reduction of 2 °C in the meridional gradient between middle and low latitudes. Elemental data and quartz content imply an increase in terrigenous flux prior to the onset of the CIE, possibly linked to initial PETM warming. However, inconsistent changes in terrigenous flux at other PETM sections in the eastern Tethys suggest a variable response modulated by sea-level change and hinterland weathering, erosion and sediment delivery. • First TEX 86 -derived SST data from a carbonate platform across the PETM. • TEX 86 -derived SST indicate a warming of 3 to 5 °C in tropical eastern Tethys area. • Changes in clastic flux accompanied greenhouse warming. [ABSTRACT FROM AUTHOR]

Archaea have many unique physiological features of which the lipid composition of their cellular membranes is the most striking. Archaeal ether-linked isoprenoidal membranes can occur as bilayers or monolayers, possess diverse polar head groups, and a multiplicity of ring structures in the isoprenoidal cores. These lipid structures are proposed to provide protection from the extreme temperature, pH, salinity, and nutrient-starved conditions that many archaea inhabit. However, many questions remain regarding the synthesis and physiological role of some of the more complex archaeal lipids. In this study, we identify a radical S-adenosylmethionine (SAM) protein in Sulfolobus acidocaldarius required for the synthesis of a unique cyclopentyl head group, known as calditol. Calditollinked glycerol dibiphytanyl glycerol tetraethers (GDGTs) are membrane spanning lipids in which calditol is ether bonded to the glycerol backbone and whose production is restricted to a subset of thermoacidophilic archaea of the Sulfolobales order within the Crenarchaeota phylum. Several studies have focused on the enzymatic mechanism for the synthesis of the calditol moiety, but to date no protein that catalyzes this reaction has been discovered. Phylogenetic analyses of this putative calditol synthase (Cds) reveal the genetic potential for calditol-GDGT synthesis in phyla other than the Crenarchaeota, including the Korarchaeota and Marsarchaeota. In addition, we identify Cds homologs in metagenomes predominantly from acidic ecosystems. Finally, we demonstrate that deletion of calditol synthesis renders S. acidocaldarius sensitive to extremely low pH, indicating that calditol plays a critical role in protecting archaeal cells from acidic stress. [ABSTRACT FROM AUTHOR]

The TEX86 proxy, based on the distribution of isoprenoid glycerol dialkyl glycerol tetraethers (iGDGTs) from planktonic Thaumarchaeota, is widely used to reconstruct sea surface temperature (SST). Recent observations of species‐specific and regionally dependent TEX86‐SST relationships in cultures and the modern ocean raise the question of whether nonthermal factors may have impacted TEX86 paleorecords. Here we evaluate the effects of ecological changes on TEX86 using one Pliocene and two Pleistocene sapropels from the Mediterranean Sea. We find that TEX86‐derived SSTs deviate from U37K'‐derived SSTs before, during, and after each sapropel event. U37K'‐derived SSTs vary by less than 6 °C, while TEX86‐derived SSTs vary by up to 15 °C within a single record. Compound‐specific carbon isotope compositions indicate minimal confounding influence on TEX86 from exogenous sources. Some of the variation can be accounted for by changes in nitrogen cycling intensity affecting thaumarchaeal iGDGT biosynthesis, as demonstrated by an inverse relationship between TEX86 and δ15NTN. TEX86‐derived SSTs also consistently show warm anomalies in the Pleistocene, while the Pliocene samples exhibit both warmer and cooler relative offsets. These anomalies result from systematic differences between Plio‐Pleistocene iGDGT distributions and both modern Mediterranean and modern, globally distributed core top samples. Through characteristic GDGT distributions, we suggest the existence of three distinct endemic populations of Thaumarchaeota in the Pliocene, Pleistocene, and modern Mediterranean Sea, respectively. Importantly, these communities prevailed during both sapropel and oligotrophic conditions. Our results demonstrate that ecological and community‐specific effects must be considered when applying the TEX86 proxy to paleorecords. Key Points: Mediterranean Pliocene‐Pleistocene sapropels were investigated for TEX86, archaeal lipid carbon isotopic compositions, and UK'37Nontemperature effects on TEX86 ocean temperature reconstructions are observed in all sapropels and surrounding marlsDistinct archaeal lipid distributions could be indicative of changing thaumarchaeal communities through time [ABSTRACT FROM AUTHOR]

Terrestrial paleoclimate archives such as lake sediments are essential for our understanding of the continental climate system and for the modeling of future climate scenarios. However, quantitative proxies for the determination of paleotemperatures are sparse. The relative abundances of certain bacterial lipids, i.e., branched glycerol dialkyl glycerol tetraethers (brGDGTs), respond to changes in environmental temperature, and thus have great potential for climate reconstruction. Their application to lake deposits, however, is hampered by the lack of fundamental knowledge on the ecology of brGDGT-producing microbes in lakes. Here, we show that brGDGTs are synthesized by multiple groups of bacteria thriving under contrasting redox regimes in a deep meromictic Swiss lake (Lake Lugano). This niche partitioning is evidenced by highly distinct brGDGT inventories in oxic vs. anoxic watermasses, and corresponding vertical patterns in bacterial 16S rRNA gene abundances, implying that sedimentary brGDGT records are affected by temperatureindependent changes in the community composition of their microbial producers. Furthermore, the stable carbon isotope composition (δ13C) of brGDGTs in Lake Lugano and 34 other (peri-)Alpine lakes attests to the widespread heterotrophic incorporation of 13C-depleted, methane-derived biomass at the redox transition zone of mesotrophic to eutrophic lake systems. The brGDGTs produced under such hypoxic/ methanotrophic conditions reflect near-bottom water temperatures, and are characterized by comparatively low δ13C values. Depending on climate zone and water depth, lake sediment archives predominated by deeper water/low-13C brGDGTsmay providemore reliable records of climate variability than those where brGDGTs derive from terrestrial and/or aquatic sources with distinct temperature imprints. [ABSTRACT FROM AUTHOR]

The distribution of branched glycerol dialkyl glycerol tetraethers (brGDGTs) in soils, peats, and lake sediments has been shown to correlate with mean annual air temperature (MAAT) and has provided valuable new climate reconstructions. Here we use an improved chromatographic method to quantify the fractional abundances of 5- and 6-methyl isomers in surface sediments from 65 East African lakes spanning temperatures 1.6–26.8 °C, and investigate the relationships between these fractional abundances and temperature, lake pH, and other environmental variables. We find that temperature exerts a strong control on brGDGT distributions, including the relative abundances of 5- and 6-methyl isomers, whereas other environmental variables, including lake pH, are weakly correlated to the fractional abundances of the brGDGTs. The distributions of brGDGTs in our lake sediments differ from those of soils and peats, leading to temperature offsets if soil- and peat-based brGDGT temperature calibrations are applied. We develop new calibrations for MAAT for use in lake sediment based upon the MBT′5Me and Index 1 ratios, as well as a multivariate regression of brGDGT fractional abundances on temperature using stepwise forward selection. We obtain root mean square errors (RMSE) between ∼ 2.1 and 2.5 °C for these calibrations, highlighting the potential for brGDGTs to provide precise temperature reconstructions using lake sediment cores. Calibrations for lake pH perform more poorly, likely due to weak correlations between pH and brGDGT distributions in East African lakes. These results indicate that quantification of 5- and 6-methyl isomers separately in lake sediment can improve paleoclimatic reconstructions. [ABSTRACT FROM AUTHOR]

Our understanding of deglacial climate history in the southern Great Lakes region of the United States is primarily based upon fossil pollen data, with few independent and multi-proxy climate reconstructions. Here we introduce a new, well-dated fossil pollen record from Stotzel-Leis, OH, and a new deglacial temperature record based on branched glycerol dialkyl glycerol tetraethers (brGDGTs) at Silver Lake, OH. We compare these new data to previously published records and to a regional stack of pollen-based temperature reconstructions from Stotzel-Leis, Silver Lake, and three other well-dated sites. The new and previously published pollen records at Stotzel-Leis are similar, but our new age model brings vegetation events into closer alignment with known climatic events such as the Younger Dryas (YD). brGDGT-inferred temperatures correlate strongly with pollen-based regional temperature reconstructions, with the strongest correlation obtained for a global soil-based brGDGT calibration (r 2  = 0.88), lending confidence to the deglacial reconstructions and the use of brGDGT and regional pollen stacks as paleotemperature proxies in eastern North America. However, individual pollen records show large differences in timing, rates, and amplitudes of inferred temperature change, indicating caution with paleoclimatic inferences based on single-site pollen records. From 16.0 to 10.0ka, both proxies indicate that regional temperatures rose by ∼10 °C, roughly double the ∼5 °C estimates for the Northern Hemisphere reported in prior syntheses. Change-point analysis of the pollen stack shows accelerated warming at 14.0 ± 1.2ka, cooling at 12.6 ± 0.4ka, and warming from 11.6 ± 0.5ka into the Holocene. The timing of Bølling-Allerød (B-A) warming and YD onset in our records lag by ∼300–500 years those reported in syntheses of temperature records from the northern mid-latitudes. This discrepancy is too large to be attributed to uncertainties in radiocarbon dating, and correlation between pollen and brGDGT temperature reconstructions rules out vegetation lags as a cause. However, the YD termination appears synchronous among the brGDGT record, regional pollen stack, and Northern Hemisphere stack. The cause of the larger and lagged temperature changes in the southern Great Lakes relative to Northern Hemisphere averages remains unclear, but may be due to the effects of continentality and ice sheet extent on regional climate evolution. [ABSTRACT FROM AUTHOR]

The TEX 86 paleotemperature proxy is based on the distribution of archaeal glycerol dibiphytanyl glycerol tetraether (GDGT) lipids preserved in marine sediments, yet both the influence of different physiological factors on the structural distribution of GDGTs and the mechanism(s) by which GDGTs is(are) exported to marine sediments remain(s) unresolved. We investigated the abundance and structural distribution of GDGTs in the South-west and Equatorial Atlantic Ocean in four water column profiles spanning 48 degrees of latitude. The depth distribution was consistent with production by ammonia-oxidizing Thaumarchaeota; maximum GDGT concentration occurred at the base of the NO 2 − maximum, core GDGTs dominated the structural distribution in surface waters above the NO 2 − maximum, and intact polar GDGTs – potentially indicating live cells – were more abundant below the NO 2 − maximum. Between 0 and1000 m, > 98% of the integrated GDGT inventory was present in waters at and below the NO 2 − maximum. Depth profiles of TEX 86 temperature values displayed local minima at the NO 2 − maximum, while the ratio of GDGT-2:GDGT-3 increased with depth. A model based on the results predicts an average depth of origin for GDGTs exported to sediments between ca. 80–250 m. In the model, exported TEX 86 values are remarkably insensitive to change in the average depth of origin of GDGTs. However, TEX 86 values exported from the water column appear to reflect euphotic zone productivity, possibly due to the correlative intensity of organic matter remineralization providing substrates for ammonia oxidation. Predicting the influence of these regional controls on sedimentary TEX 86 records requires a better understanding of the interaction between GDGT production, particle dynamics, and the depth of origin for exported organic matter. [ABSTRACT FROM AUTHOR]

Glycerol monobiphytanyl glycerol diethers (GMGDs) have recently been identified as degradation products of glycerol dibiphytanyl glycerol tetraethers (GDGTs) and occur as regioisomers. The distribution patterns of GMGD regioisomers are diagnostic for the glycerol configuration of their precursor GDGTs. We systematically examined the distributions of GMGDs and other regioisomer-specific degradation products in a suite of marine sediments and methane seep carbonates. The distinctly different patterns of GMGD compounds in these contrasting environments affords a new way of examining and elucidating the structures of the GDGT precursors. In contrast to the prevalent assumption of a predominant antiparallel GDGT glycerol arrangement in marine sediments, we show that the pool of GDGT-typical marine sediments, which harbor the remains of predominantly planktonic Thaumarchaeota, is composed largely of parallel regioisomers. In the contrasting environments of methane seep carbonates and Cascadia Margin subsurface sediment impacted by anaerobic methane oxidation, the patterns of the GMGD regioisomers indicate a substantial antiparallel GDGT fraction, implying that this may be a feature of methane-metabolizing Euryarchaeota. Crenarchaeol, presently considered specific to planktonic Thaumarchaeota, has an exclusively parallel glycerol arrangement with its tricyclic biphytane moiety bound to the sn 3 carbon of glycerol on both sides. We provide data to show that the compound widely known as the ‘crenarchaeol regioisomer’, a compound factored into the widely used TEX 86 paleotemperature proxy, rather than having an antiparallel glycerol arrangement, actually possesses a different ring configuration on its tricyclic biphytane moiety. [ABSTRACT FROM AUTHOR]

We analyzed the abundance and distribution of branched glycerol dialkyl glycerol tetraethers (brGDGTs) in grain size fractions of 7 globally distributed river flank sediments and catchment soils in order to determine if and how the initial soil-brGDGT signature is influenced by hydrodynamic sorting upon entering a river and during subsequent transport from land to sea. BrGDGTs are hypothesized to form associations with high-surface-area fine-grained minerals in soils. Such associations, if maintained during transport, may impart resistance to degradation and promote downstream transport, reducing potential interferences by aquatic brGDGTs. We find that brGDGTs are indeed primarily associated with organic carbon (OC) bound to the clay-silt fraction (

A sudden change from normal marine to extreme paleoenvironmental conditions occurred approximately 6 Ma ago in the Mediterranean Basin at the onset of the late Miocene Messinian salinity crisis, one of the most severe ecological crises in Earth history. Strong evaporation and tectonics led to hypersaline conditions, resulting in widespread deposition of evaporites and the apparent annihilation of the marine metazoan biosphere. In contrast to the prominent occurrence of evaporites elsewhere in the Mediterranean, evaporites did not form in the deeper part of some marginal basins at the onset of the crisis. The strata of the Pollenzo section (Piedmont Basin, NW Italy) studied here were deposited in such a paleogeographic setting. Instead of evaporites, a cyclic succession of organic-rich shales and carbonates formed during the early phase of the crisis in the study area. These sediments record a sharp increase in the contents of archaeal molecular fossils that are mostly represented by isoprenoidal dialkyl glycerol diethers (DGDs) and isoprenoidal glycerol dialkyl glycerol tetraethers (GDGTs). Such an expansion of archaeal biomass is best explained by a change of the archaeal communities at the onset of the Messinian salinity crisis. In particular, the appearance of molecular fossils of extremophilic archaea, mostly producing DGDs (archaeol and extended archaeol), suggests the emergence of halophilic archaea. At the same time, lipids of planktonic Thaumarchaeota, especially crenarchaeol, are present across the entire section, suggesting the local persistence of normal marine conditions. In agreement with the sudden appearance of tetrahymanol in the upper part of the section, the persistence of crenarchaeol indicates the establishment of water column stratification after the advent of the Messinian salinity crisis. To further investigate the Piedmont Basin paleoenvironmental conditions, we test the Archaeol Caldarchaeol Ecometric (ACE), a proxy developed for identifying high paleosalinities in waters and possibly in sediments. Despite high ACE values found for the Messinian salinity crisis samples, these values are in contrast with the absence of any lithological evidence for high salinities as well with other biomarker-independent information, indicating low to normal seawater salinities. This apparent contradiction is likely explained by the complexity of the sources of archaeal lipids, especially of caldarchaeol and archaeol, limiting the utility of the ACE for the reconstruction of paleosalinities for Messinian strata. [ABSTRACT FROM AUTHOR]

The history of the Amazon River is a much-discussed subject, and the timing of the development of a transcontinental system in particular is a matter of some controversy, with estimations varying between the Early Miocene and the Pliocene or even the Pleistocene. To shed further light on this, we studied the sediment provenance of an Oligocene to Late Pleistocene marine sedimentary section from the Ceará Rise (ODP Site 925), a topographic high in the central Atlantic Ocean, using major element concentrations and Nd isotopic composition in 85 samples. In addition, the carbon isotopic composition of bulk organic matter and changes in the distribution of glycerol dialkyl glycerol tetraethers (GDGTs) were used to identify periods of increased river outflow. On the basis of these results, we suggest that the history of the development of the Amazon River is characterized by specific steps. During the late Oligocene/Early Miocene (30–18.3 Ma), the terrigenous mass accumulation rates (TARs) were high, and sediment and GDGT compositions suggest that a large river system existed, which at times received weathering products from a younger and probably Andean sediment source. A shift to a younger Andean sediment provenance after 8.7 Ma indicates that the Amazon River became permanently connected with the Andes. Between 18.3 and 4.5 Ma, TARs were generally low, and GDGTs were derived for the most part from in situ production in marine waters. Around 4.5 Ma, the river expanded, probably due to ongoing tectonic activity, and uplift in the Andes increased Andean rock erosion. This led to a strong increase in terrigenous sediment deposition and enhanced organic matter preservation on the Ceará Rise, and the delivery of terrestrial (both soil and riverine) branched GDGTs to the Ceará Rise. [ABSTRACT FROM AUTHOR]

We investigated glycerol dialkyl glycerol tetraethers (GDGTs) in sediments taken from a 97 m long borehole core in the estuary of the Ohno River, Kyushu, Japan. Our aim was to understand the influence of estuary-produced branched GDGTs on MBT′/CBT indices and the terrestrial contribution on TEX 86 in estuary sediments by comparing with soils in its drainage basin and offshore marine sediments. In borehole sediments covering the last 8000 years, TEX 86 and MBT′/CBT records are inconsistent with other paleoclimate records from western and central Japan, implying that the application of TEX 86 and MBT′/CBT as paleotemperature proxies to this sample set was unsuccessful. The isoprenoid GDGT compositions of the study site were closer to those of the surface soils in the Ohno River drainage area rather than those in Beppu Bay sediments. TEX 86 reflects a mixing ratio of estuary and soil GDGTs. In contrast to isoprenoid GDGTs, the branched GDGT compositions were closer to those of Beppu Bay sediments rather than those of surface soils, implying that the branched GDGTs were mainly of estuary origin. Variation in BIT shows a consistent pattern with that of water depth reconstructed from a molluskan fossil record. The input of terrestrial labile organic matter could contribute to the production of branched GDGTs. In turn, the BIT indirectly reflects the contribution of terrestrial organic matter. [ABSTRACT FROM AUTHOR]

Glycerol dialkyl glycerol tetraethers (GDGTs) are membrane-spanning lipids from Bacteria and Archaea that are ubiquitous in a range of natural archives and especially abundant in peat. Previous work demonstrated that the distribution of bacterial branched GDGTs (brGDGTs) in mineral soils is correlated to environmental factors such as mean annual air temperature (MAAT) and soil pH. However, the influence of these parameters on brGDGT distributions in peat is largely unknown. Here we investigate the distribution of brGDGTs in 470 samples from 96 peatlands around the world with a broad mean annual air temperature (−8 to 27 °C) and pH (3–8) range and present the first peat-specific brGDGT-based temperature and pH calibrations. Our results demonstrate that the degree of cyclisation of brGDGTs in peat is positively correlated with pH, pH = 2.49 × CBT peat + 8.07 ( n = 51, R 2 = 0.58, RMSE = 0.8) and the degree of methylation of brGDGTs is positively correlated with MAAT, MAAT peat (°C) = 52.18 × MBT 5me ′ − 23.05 ( n = 96, R 2 = 0.76, RMSE = 4.7 °C). These peat-specific calibrations are distinct from the available mineral soil calibrations. In light of the error in the temperature calibration (∼4.7 °C), we urge caution in any application to reconstruct late Holocene climate variability, where the climatic signals are relatively small, and the duration of excursions could be brief. Instead, these proxies are well-suited to reconstruct large amplitude, longer-term shifts in climate such as deglacial transitions. Indeed, when applied to a peat deposit spanning the late glacial period (∼15.2 kyr), we demonstrate that MAAT peat yields absolute temperatures and relative temperature changes that are consistent with those from other proxies. In addition, the application of MAAT peat to fossil peat (i.e. lignites) has the potential to reconstruct terrestrial climate during the Cenozoic. We conclude that there is clear potential to use brGDGTs in peats and lignites to reconstruct past terrestrial climate. [ABSTRACT FROM AUTHOR]