Distribution Of Glycerol Dialkyl Glycerol Tetraethers Research Articles

Disentangling influences of climate variability and lake-system evolution on climate proxies derived from isoprenoid and branched glycerol dialkyl glycerol tetraethers (GDGTs): the 250 kyr Lake Chala record

Abstract. High-resolution paleoclimate records from tropical continental settings are greatly needed to advance understanding of global climate dynamics. The International Continental Scientific Drilling Program (ICDP) project DeepCHALLA recovered a 214.8 m long sediment sequence from Lake Chala, a deep and permanently stratified (meromictic) crater lake in eastern equatorial Africa, covering the past ca. 250 000 years (250 kyr) of continuous lacustrine deposition since the earliest phase of lake-basin development. Lipid biomarker analyses on the sediments of Lake Chala can provide quantitative records of past variation in temperature and moisture balance from this poorly documented region. However, the degree to which climate proxies derived from aquatically produced biomarkers are affected by aspects of lake developmental history is rarely considered, even though it may critically influence their ability to consistently register a particular climate variable through time. Modern-system studies of Lake Chala revealed crucial information about the mechanisms underpinning relationships between proxies based on isoprenoid (iso-) and branched (br-) glycerol dialkyl glycerol tetraethers (GDGTs) and the targeted climate variables, but the persistence of these relationships in the past remains unclear. Here we assess the reliability of long-term climate signals registered in the sediments of Lake Chala by comparing downcore variations in GDGT distributions with major phases in lake-system evolution as reflected by independent proxies of lake depth, mixing regime and nutrient dynamics: seismic reflection data, lithology and fossil diatom assemblages. Together, these records suggest that during early lake history (before ca. 180–200 ka) the distinct mixing-related depth zones with which specific GDGT producers are associated in the modern-day lake were not yet formed, likely due to more open lake hydrology and absence of chemical water-column stratification. Consequently absolute GDGT concentrations dating to this period are relatively low, proxies sensitive to water-column stratification (e.g., branched versus isoprenoid tetraether (BIT) index) display highly irregular temporal variability, and correlations between proxies are dissimilar to expectations based on modern-system understanding. A sequence of lake-system changes between ca. 180–200 and ca. 80 ka first established and then strengthened the chemical density gradient, promoting meromictic conditions despite the overall decrease in lake depth due to the basin gradually being filled up with sediments. From ca. 180 ka onward some GDGTs and derived proxies (e.g., crenarchaeol concentration, BIT index and IR6Me) display strong ∼ 23 kyr periodicity, likely reflecting the predominantly precession-driven insolation forcing of Quaternary climate variability in low-latitude regions. Our results suggest that GDGT-based temperature and moisture-balance proxies in Lake Chala sediments reflect the climate history of eastern equatorial Africa from at least ca. 160 ka onwards, i.e., covering the complete last glacial–interglacial cycle and the penultimate glacial maximum. This work confirms the potential of lacustrine GDGTs for elucidating the climate history of tropical regions at Quaternary timescales, provided they are applied to suitably high-quality sediment archives. Additionally, their interpretation should incorporate a broader understanding of the extent to which lake-system evolution limits the extrapolation back in time of proxy-climate relationships established in the modern system.

Environmental controls on the distribution of GDGT molecules in Lake Höglwörth, Southern Germany

Tetraether lipids, such as glycerol dialkyl glycerol tetraethers (GDGTs), are an increasingly used proxy for reconstructing paleoclimatic and paleoenvironmental dynamics. On a global scale, environmental drivers controlling the distribution of GDGTs in lake systems have been described extensively. However, the drivers that control down-core sedimentary GDGT composition within single lake systems are still poorly constrained. Here, we analysed GDGTs in a sediment core collected from Lake Höglwörth (Bavaria, Germany) covering the last ∼1100 years. The increase in ratio ΣIIIa/ΣIIa values (a ratio which captures the variation of 3 structural isomers of penta- and hexamethylated brGDGTs respectively) reflects a higher contribution of branched (br) GDGTs from aquatic sources after 1800 CE. This is synchronous with a high nutrient input as a result of increased local anthropogenic activities. The climate proxy methylation of branched tetraethers (MBT'5ME) reveals a pattern that deviates from the anticipated temperature changes during the last millennium. Instead, high MBT'5ME values from ∼880 to 1120 CE coincide with a period of increased soil input, resulting from lake damming and/or construction of the Höglwörth monastery. Decreased values after 1800 CE until present date correspond to a higher contribution of aquatic brGDGTs, with changes in the dependency between Ia and IIa suggesting a direct influence of bacterial community changes on the MBT'5ME. The proxy cyclisation of branched tetraethers (CBT') shows a linear increase with time, and a stepwise increase at 1700 CE, when a creek stream inflow channel was rerouted. Over time, MBT’5ME decreases gradually, while CBT’ and ΣIIIa/ΣIIa increase. This is hypothesized to be potentially caused by decreasing water depth over time and/or post- or syn-sedimentary production of GDGTs. The degree of cyclization (DC') shows variations on shorter timescales, possibly driven by the lake mixing regime and water column redox conditions. Our results indicate that caution must be taken when interpreting GDGTs for paleoclimate and paleoenvironmental reconstruction considering the possible influence of shifts in the provenance of brGDGTs. Further studies focusing on both sedimentary and intact polar lipids are highly recommended to constrain the source (water column, or sedimentary production) of GDGTs in lake sediments.

Nitrosopumilus as main source of isoprenoid glycerol dialkyl glycerol tetraether lipids in the central Baltic Sea.

Nitrososphaeria in the phylum Crenarchaeota, is a widespread archaeal class in the oceanic realm, playing an important role in the marine carbon and nitrogen cycle. Nitrososphaeria-derived membrane lipids, i.e., isoprenoid glycerol dialkyl glycerol tetraethers (GDGTs), are commonly employed to reconstruct past water temperatures using the TetraEther indeX of 86 carbon atoms (TEX86). This index is of particular importance for the brackish Baltic Sea as to date it appears to be the only applicable organic temperature proxy. In this study, we investigated the distribution of intact and core GDGTs and their potential source organisms in the water column of three deep basins located in the central Baltic Sea to evaluate the application of TEX86. A lipidomic approach on suspended particulate matter was combined with the molecular techniques 16S rRNA gene amplicon sequencing and CARD-FISH. The archaeal community was dominated by Nitrosopumilus (~83-100% of the total archaeal sequences). As other detected taxa known to produce GDGTs each represented less than 2% of the total archaeal sequences, Nitrosopumilus is likely the most dominant GDGT producer in the central Baltic Sea. However, the occurrence of phosphohexose (PH), instead of hexose-phosphohexose (HPH) headgroups, suggested that Nitrosopumilus in the Baltic Sea may differ physiologically from representatives of marine settings and other marginal seas, such as the Black Sea. In the Baltic Sea, Nitrosopumilus is most abundant in the suboxic zone, where intact cells peak according to both CARD-FISH data and intact polar lipid concentrations. The presented data therefore suggest that TEX86 reflects subsurface rather than surface temperature in the central Baltic Sea.

Application of microbial membrane tetraether lipids in speleothems

Glycerol dialkyl glycerol tetraethers (GDGTs), which are derived from microbial membranes, occur widely in soils, peats, lake sediments, marine sediments, hot springs, and other environments. GDGTs respond sensitively to environmental changes and have become an important tool in paleoenvironmental reconstruction. However, their application in speleothems, one of the most important archives of the study of past climates, has been quite limited. In this paper, we review the recent progress in the study of GDGTs in speleothems, from their sources to their distribution characteristics and paleoenvironmental applications. GDGTs in speleothems have been shown to come from dripping water, and cave systems. The distribution of GDGTs in speleothems shows that archaeal isoprenoid GDGTs (isoGDGTs) dominate over bacterial branched GDGTs (brGDGTs). The proxies based on isoGDGTs (TEX86) and brGDGTs (MBT/CBT) are correlated with temperature, which may offer promising potential methods for reconstructing terrestrial palaeotemperature. Ultimately, we discuss the difficulties and problems to be solved in studying speleothem GDGTs and the possible future directions for this field.

Distribution of Glycerol Dialkyl Glycerol Tetraethers (GDGTs) in Carbonate-Type and Sulfate-Type Lacustrine Sediments: Insight into the Influence of Ionic Composition on GDGTs

The distribution of glycerol dialkyl glycerol tetraethers (GDGTs) in carbonate-type and sulfate-type saline lacustrine sediments from the Ordos Plateau in China is investigated to explore the influence of ionic composition on GDGTs. In general, they are relatively small (1.2–6.0 km2 surface area) and shallow ponds (0.05–0.2 m water depth) and even seasonally dry lakes. The results reveal that the concentration of GDGTs has a good positive correlation with the (nCO32− + nHCO3−)/total ions, and the concentration of GDGTs in carbonate-type lake sediments is significantly higher than that in sulfate-type lake sediments. Most GDGT-based indices show no significant differences, and the distributions of GDGTs are similar in the two types of saline lake sediments. The lack of a positive correlation between the content of clay minerals and the concentration of GDGTs may imply that the ability of clay minerals to carry terrigenous organic matter is very limited in arid climates. The branched GDGTS (brGDGTs) in the two saline lake sediments may mainly come from in situ biological production and have low terrestrial inputs. The different weathering level of feldspar minerals in the two types of saline lakes results in the difference in organic matter content, which ultimately affects the concentration of GDGTs.

Archaeal lipids trace ecology and evolution of marine ammonia-oxidizing archaea

Archaeal membrane lipids are widely used for paleotemperature reconstructions, yet these molecular fossils also bear rich information about ecology and evolution of marine ammonia-oxidizing archaea (AOA). Here we identified thermal and nonthermal behaviors of archaeal glycerol dialkyl glycerol tetraethers (GDGTs) by comparing the GDGT-based temperature index (TEX86) to the ratio of GDGTs with two and three cyclopentane rings (GDGT-2/GDGT-3). Thermal-dependent biosynthesis should increase TEX86 and decrease GDGT-2/GDGT-3 when the ambient temperature increases. This presumed temperature-dependent (PTD) trend is observed in GDGTs derived from cultures of thermophilic and mesophilic AOA. The distribution of GDGTs in suspended particulate matter (SPM) and sediments collected from above the pycnocline-shallow water samples-also follows the PTD trend. These similar GDGT distributions between AOA cultures and shallow water environmental samples reflect shallow ecotypes of marine AOA. While there are currently no cultures of deep AOA clades, GDGTs derived from deep water SPM and marine sediment samples exhibit nonthermal behavior deviating from the PTD trend. The presence of deep AOA increases the GDGT-2/GDGT-3 ratio and distorts the temperature-controlled correlation between GDGT-2/GDGT-3 and TEX86. We then used Gaussian mixture models to statistically characterize these diagnostic patterns of modern AOA ecology from paleo-GDGT records to infer the evolution of marine AOA from the Mid-Mesozoic to the present. Long-term GDGT-2/GDGT-3 trends suggest a suppression of today's deep water marine AOA during the Mesozoic-early Cenozoic greenhouse climates. Our analysis provides invaluable insights into the evolutionary timeline and the expansion of AOA niches associated with major oceanographic and climate changes.

Identifying the drivers of GDGT distributions in alkaline soil profiles within the Serengeti ecosystem

Surface soil glycerol dialkyl glycerol tetraether (GDGT) distributions are influenced by mean annual air temperature as well as soil pH. However, the controls on GDGT distributions with depth in soil profiles are less well-known. We report a study of soil profiles in warm, carbonate-precipitating, alkali soils in the Serengeti ecosystem, Tanzania. Measurements of temperature, pH, salinity, and complementary data available from carbonates and organics from the same soil pits provide an interpretive framework for the observed patterns in branched (br-) and isoprenoidal (iso-) GDGTs in soil profiles. While brGDGT distributions at the soil surface primarily reflect mean annual temperature, a warm bias at depth indicates additional sub-surface controls on brGDGT distributions. We consider whether degradation or in situ production in response to alkaline pH and salinity also modulate brGDGTs. We find that the Archaeol Caldarchaeol Ecometric (ACE) index correlates with soil salinity, which both increase with depth. These results support in situ microbial production in deeper soil settings, with pH and salinity controlling the microbial community composition. We also compared brGDGT-predicted mean annual air temperatures (MAAT) to published clumped isotope thermometry on carbonates in the same soils and found that the median temperatures of both proxies were the same at 23 °C. We suggest further comparison of proxy performance in carbonate-bearing soils and geological archives. Differences in the nature of the proxy recorders may broaden sample availability for paleothermometry and help to identify confounding factors in each proxy system.

Improved protocols for large-volume injection and liquid chromatography–mass spectrometry analyses enable determination of various glycerol dialkyl glycerol tetraethers in a small amount of sediment and suspended particulate matter

Glycerol dialkyl glycerol tetraethers (GDGTs) have received considerable attention because they are useful indicators for paleoenvironment, organic matter source, and microbial community. In this study, a new simple method was developed for the analysis of GDGTs by using direct large-volume injection (LVI)–liquid chromatography (LC)–atmospheric pressure chemical ionization–mass spectrometry (APCI–MS) to reduce the usage of sediment or seawater suspended particulate matter (SPM) samples. The parameters of accelerated solvent extraction and LVI of target GDGTs were optimized. Under optimal conditions, the LVI approach (500 μL injection) coupled with LC–APCI–MS could determine various GDGTs even with 0.02–0.10 g of sediment samples or SPM samples collected from 0.2–1.0 L of marginal sea water or 10–20 L of open ocean seawater with satisfactory method precision (relative standard deviations ≤10.2%) and linearity (R2 ≥ 0.991). Compared with the classical method, the LVI–LC–APCI–MS required significantly reduced amount of sediment or SPM sample. Finally, the proposed method was applied to determine GDGTs in real sediment samples collected from hydrothermal vent sites at the Southwest Indian Ridges. Four groups of GDGTs, namely, isoprenoid GDGTs (isoGDGTs), branched GDGTs, H-GDGTs and OH-GDGTs, and archaeol, glycerol dialkanol diethers (GDDs) and glycerol monoalkanediol diethers (GMDs) were detected with only 0.02 g of sediment sample collected from Longqi and Tianzuo hydrothermal fields. The organic matter in the sediment sample from Tianzuo was significantly affected by hydrothermal activity. In addition, isoGDGTs in seawater SPM from the open area of Eastern Indian Ocean were investigated for the first time. Six common isoGDGTs were all detected in surface and subsurface SPM samples (filtering 10 L of seawater), which indicated that the LVI approach could noticeably reduce the workload of collecting seawater SPM on board and could be used to investigate conveniently the distribution of GDGTs in water column especially in open oceans and deep seas.

Controls on the distributions of GDGTs and n-alkane isotopic compositions in sediments of the Amazon River Basin

Lipid biomarker proxies from terrigenous sediments have been extensively used to understand variations in paleoenvironmental conditions, but many of the mechanisms affecting these proxies during riverine transport are still poorly understood. Here, we analyze glycerol dialkyl glycerol tetraether (GDGT) distributions and n-alkane isotopic compositions of soils and sediments from the Amazon River Basin. Our dataset includes suspended sediments of the Amazon River and its main tributaries, as well as soils and sediments of the Xingu River, a large clearwater tributary draining the easternmost part of the Amazon River Basin. Our sampling design aimed at understanding the processes behind spatially distinct GDGT distributions and n-alkane isotopic signatures across lowland Amazonia. Gradual changes in the fractional abundances of isoprenoid GDGTs and in 5- and 6- methyl branched GDGT ratios in suspended sediments of the Amazon River towards its mouth suggest that riverine production is an increasingly important control on the distribution of GDGTs in the lower parts of the system, while values from the western parts are more in line with a dominant soil sourcing. In the Xingu River, indices based on the fractional abundances of branched GDGTs and long-chain n-alkanes demonstrate a strong contribution of terrestrial organic material during the high-water season and an important aquatic component during low-water season. Meanwhile, average stable carbon (δ13C) and hydrogen (δD) isotopic signatures of long-chain n-alkanes in soils, riverbed and suspended sediments of the Xingu River are similar and reinforce the relatively conservative behaviour of these proxies within large river systems. The average compound-specific δ13C signatures of sediments in the Xingu River are within the expected range for C3 vegetation and do not seem to capture the signals from the nearby deforested areas. n-Alkanes δD signals in the Xingu Basin are similar to values obtained in the Amazon River mouth and indicate that n-alkanes sourced from easternmost Amazonian lowlands may predominate over signals from western areas.

Variations in dissolved O2 in a Chinese lake drive changes in microbial communities and impact sedimentary GDGT distributions

Glycerol dialkyl glycerol tetraethers (GDGTs) are widespread but unique membrane-spanning lipids of many Archaea and some Bacteria. However, their specific biological sources and the associated environmental controls on their distribution remain unclear, especially in lacustrine settings, hindering our understanding of these compounds and their application as environmental proxies. Here we investigated the GDGT distributions across a large bottom water dissolved oxygen (DO) gradient (0.10–7.20 mg/L) using surface sediments of Lake Yangzonghai, a warm monomictic lake in southwestern China. We show that the distributions of both branched (br) and isoprenoidal (iso) GDGTs co-vary significantly with bottom water DO concentration. The relative abundances of tetramethylated brGDGTs, 5-methyl penta- and hexamethylated brGDGTs and isoGDGT-0 show a stepwise increase as bottom water DO concentration decreases. On the other hand, the relative abundances of 6-methyl penta- and hexamethylated brGDGTs and crenarchaeol exhibit a stepwise decline with a decrease in bottom water DO concentration. Genetic data indicate these DO-induced changes in GDGT parameters are related to changes in the bacterial and archaeal communities across the oxycline in the lake. For example, the high abundance of isoGDGT-0 in low DO samples coincides with a high abundance of methanogenic archaea and Bathyarchaeota. We propose that brGDGT-producing bacteria might include a diversity of other phyla in addition to the proposed source organism acidobacteria; different groups of anaerobic and aerobic bacteria are likely to contribute to the increased abundance of 5-methyl brGDGTs and 6-methyl brGDGTs in low and high DO zones, respectively. Consequently, the MBT′ and MBT′6ME brGDGT indices display strong correlations with DO concentration. Importantly, the MBT′5ME index is not significantly influenced by changes in DO concentration, suggesting that this index might be more resilient to these impacts and more suitable to reconstruct temperature in lake systems.

Influence of hydrothermal vent activity on GDGT pool in marine sediments might be less than previously thought

Hydrothermal systems have a pronounced effect on deep-sea chemistry and some plumes are reported to occupy large parts of ocean volume. However, the impact of these systems on the marine organic carbon cycle is not well understood. Here, we compare the distribution of glycerol dialkyl glycerol tetraethers (GDGTs) in several short (0–23 cm) and one long (304 cm) sediment core of hydrothermal vent sites at the Central (CIR) and Southeast Indian Ridges (SEIR) and to those of nearby normal marine sediment as reference, to characterize the impact of hydrothermal activity on deep sea sediment organic matter. We detected a range of GDGTs in some of the sediments. BrGDGT and GMGTs were absent at the normal marine reference location, but present in some of the hydrothermal sediments with relatively high concentrations of brGMGT-IIIa and brGDGT-Ia, hinting at in situ hydrothermal production. The isoGDGT distributions were similar between the hydrothermal and normal marine sites, with predominance of GDGT-0 and crenarchaeol. isoGDGT-0/crenarchaeol ratios (G-0/Cren) < 2 suggested Thaumarchaeota as the major source of GDGTs in these sediments. Consistent with a dominant thaumarchaeotal source, TEX86 in the surface samples reflected modern sea surface temperature (SST) at the core locations. Increasing trends of δ13Corg values from surface to bottom sediments were observed only in hydrothermal influenced sediments and not at the reference station. Altogether these results indicate a minor impact of hydrothermal activity on the GDGT distribution in this region, urging for caution in up-scaling previous results which proposed a significant impact of hydrothermal vents system on nearby open ocean marine sediments.

Distribution of Glycerol Dialkyl Glycerol Tetraethers (GDGTs) in Microbial Mats From Holocene and Miocene Sabkha Sediments

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.

Glycerol dialkyl glycerol tetraethers (GDGT) distributions from soil to cave: Refining the speleothem paleothermometer

The glycerol dialkyl glycerol tetraether (GDGT) paleothermometer has potential application as a speleothem paleoclimate proxy. However, the sources of GDGTs found in speleothems are poorly understood, with multiple potential sources of GDGTs from the soil to the speleothem surface. Here we analysed GDGTs in soils, soil leachates, in-cave surfaces and cave drip waters at two Australian montane caves. We observed significantly different GDGT distributions between soils, soil leachates, in-cave surfaces and drip waters and significant spatial differences in in-cave GDGT distributions. Comparison with published modern in-cave and karst groundwater GDGT datasets from Australia, Europe and China shows that speleothem GDGT distributions are different from those of all potential sources. We hypothesise that speleothem surfaces have a calcifying, alkaline, oxic, wet, carbon-available, environment that supports a microbial community that is different from other possible karst GDGT sources. We propose that the presence of GDGTs related to anoxic or methanogenic conditions, and observed in cave drip water and on in-cave surfaces, can be used to identify GDGTs from these sources. We confirm that TEX86 based paleothermometers are robust speleothem GDGT paleothermometers, whose calibration can be further refined through improved understanding and measurement of cave temperatures.

In situ production of core and intact bacterial and archaeal tetraether lipids in groundwater

Groundwater ecosystems host diverse and complex microbial communities that play important roles in the biogeochemical processing of organic matter and in the maintenance of drinking water quality. Here we investigated the microbial community in suspended particulate matter (SPM) of biogeochemically distinct groundwaters (Hainich Critical Zone Exploratory) by analyzing branched and isoprenoid glycerol dialkyl glycerol tetraethers (GDGTs) from bacteria and archaea, respectively. The contributions of those lipids derived from dead and living organisms were determined by analyses of the core lipid distributions of core and intact polar GDGTs. We compared the groundwater GDGT distributions to the ones from soils of potential recharge areas and with archaeal 16S rRNA-gene based community reconstructions to estimate their origin in these terrestrial subsurface environments and thus their potential use for evaluating soil inputs into groundwater. In soils, the relative abundance of intact polar branched GDGTs (brGDGTs) was lower than that of isoprenoid GDGTs (isoGDGTs; 2% vs 5% of total GDGTs), while the opposite trend (71% vs 22% of total GDGTs) was observed in the core lipid pools. This supports previous observations that soil brGDGT-producing bacteria might be more active and thus have higher regeneration rates than the isoGDGT-producing archaea. We found similar trends in the groundwater that might indicate higher activity (i.e., cell division) of brGDGT-producing bacteria than of isoGDGT-producing archaea. The higher relative abundance of the hexamethylated brGDGT in the groundwater SPM (mean 65 ± 9%, n = 5) than in soils (mean 16 ± 7%, n = 22) indicated an in situ origin of brGDGT-producing bacteria. Higher contributions of penta- and tetra-methylated brGDGTs, which suggested some inputs from soil bacteria, was only detected in two out of seven groundwater samples. The strong correlation between core and intact polar isoGDGTs (R2 = 0.99, n = 7) in groundwater SPM indicated low disturbance (e.g., surface inputs) and suggested indigenous archaeal communities in the groundwater. This was supported by the results from a previous 16S rRNA-gene study that detected distinct archaeal groups in soils and groundwater. This first GDGT study in groundwater demonstrated that even dynamic karstic subsurface environments host an indigenous bacterial and archaeal community that is adapted to the living conditions. Furthermore, fast recharge events are likely detectable using tetraether lipids from the soil microbial community.

Distribution of glycerol ethers in Turpan soils: implications for use of GDGT-based proxies in hot and dry regions

Proxies based on glycerol dialkyl glycerol tetraethers (GDGTs), a suite of membrane lipids occurring ubiquitously in soils, have generated increasing interest in quantitative paleo-environmental reconstruction. Hot and dry climates are likely to have occurred in the geological past; however, the limitations and applicability of these proxies to hot and dry environments are still unknown. In this study, we analyzed the GDGT distribution in the Turpan (TRP) basin of China, where the highest soil temperature can be approximately 70°C, and the mean annual precipitation (MAP) is 15.3 mm. We compared GDGT-based proxies among TRP soils, Nanyang (NY) soils, and Kunming (KM) soils; these three sites exhibit similar mean annual air temperature (MAAT) albeit contrasting temperature seasonality and MAP. Archaeal isoprenoidal GDGTs (isoGDGTs) dominate over bacterial branched GDGTs (brGDGTs) in most TRP soils; this is a characteristic GDGT distribution pattern for soils from dry regions globally. Another feature is the anomalously high GDGT-0/crenarchaeol ratio, which is generally attributed to the contribution of anaerobic methanogenic archaea by previous studies; however, these anaerobic archaea are unlikely to be highly abundant in the dry TRP soils, indicating that certain uncultured halophilic Euryarchaeota are likely to produce a significant amount of GDGT-0 that finally results in a high GDGT-0/Cren ratio. The changes in the salinity of the TRP soils appear to be an important factor affecting the MBT’5ME and the relative abundance of 6- vs. 5-methyl pentamethylated brGDGTs (IRIIa’). This is likely to introduce certain scatters in the correlations between MBT’5ME and MAAT and that between IRIIa’ and pH determined at the global scale. A comparison of the MBT’5ME-inferred temperature between TRP, NY, and KM soils does not indicate a significant bias toward summer temperature, indicating that brGDGT paleothermometers in soils could reflect the MAAT.

An overview of the occurrence of ether- and ester-linked iso-diabolic acid membrane lipids in microbial cultures of the Acidobacteria: Implications for brGDGT paleoproxies for temperature and pH

13,16-Dimethyl octacosanedioic acid (iso-diabolic acid) is a major membrane-spanning lipid of subdivisions (SDs) 1, 3 and 4 of the Acidobacteria, a highly diverse phylum within the Bacteria. It has been suggested that these lipids are potential building blocks for the orphan bacterial glycerol dialkyl glycerol tetraethers (GDGT) that occur widely in a variety of environmental settings. Here, we expand the knowledge on the occurrence of iso-diabolic acid in Acidobacteria by examining the lipid composition of six strains belonging to SDs 6, 8, 10, and 23 of the Acidobacteria, not previously analyzed for these lipids. In addition, we examined 12 new strains belonging to SDs 1, 3 and 4. Acid hydrolysis of total cell material released iso-diabolic acid in substantial quantities (25–39% of all fatty acids) from the strains of SDs 1 and 3 (except “Candidatus Solibacter usitatus”), and, for the first time, strains of SD 6 (6–25%), but not from SDs 8, 10, and 23. The monoglycerol ether derivative of iso-diabolic acid was only dominantly present in SD 4 strains (17–34%), indicating that the occurrence of ether-bound iso-diabolic acid is mainly restricted to SD 4 species. Methylated iso-diabolic acid derivatives were encountered in SDs 1, 3, 4, and 6, but only SD 4 species produced 5-methyl iso-diabolic acid derivatives, whereas the other SDs formed 6-methyl iso-diabolic acids. This suggests that the position of methylation of iso-diabolic acid may be controlled by the phylogenetic affiliation within the Acidobacteria and thus may not be a direct but an indirect response environmental to environmental conditions as inferred from the bacterial GDGT distributions in soil, peat and rivers.

Mid-late Holocene temperature and precipitation variations in the Guanting Basin, upper reaches of the Yellow River

The reconstruction of prehistoric temperature and precipitation variations in the upper reaches of the Yellow River is essential for understanding the cultural evolution of the region, but related information is sparse due to the limitations of the available proxies. Recent studies have shown that microbial glycerol dialkyl glycerol tetraethers (GDGTs) are promising tools for reconstructing mean annual temperature (MAT) and mean annual precipitation (MAP) in terrestrial deposits. In this study, we reconstructed mid-late Holocene climatic changes using GDGT distributions in a loess-paleosol sequence in the Lajia Ruins of the Neolithic Qijia Culture, Guanting Basin, in the southwestern end of the Chinese Loess Plateau. Our GDGT records show that MAP decreased from ca. 600 mm to 430 mm, while MAT decreased from 11.9 °C to 8.0 °C, during the past ca. 7000 yr, and a drastic decline in MAP (70 mm), accompanied by a 0.8 °C decline in MAT, occurred at 3800–3400 yr BP. Our results provide direct evidence supporting a hypothesis that the flourishing (4200–4000 yr BP) and decline (4000–3600 yr BP) of the Qijia culture (mainly based on millets cultivation) and subsequent rise of the Xindian/Kayue culture (3600–2600 yr BP), based on mixed agriculture of sheep husbandry and millets cultivation were triggered by climate change.

Distribution of glycerol dialkyl glycerol tetraethers in surface soils along an altitudinal transect at cold and humid Mountain Changbai: Implications for the reconstruction of paleoaltimetry and paleoclimate

Glycerol Dialkyl Glycerol Tetraethers (GDGTs) serve as important tools for the quantitative reconstruction of paleoclimate and paleoecology in both continental and marine environments. Previous studies of GDGTs in the terrestrial environments focused primarily on the soils from the relatively warm-humid or cold-dry regions. However, it is still unclear how GDGTs respond to environmental variables in the cold-humid regions. Here, we collected soils along an altitudinal transect of Mountain (Mt.) Changbai, which has a typical cold-humid climate, to investigate the distribution of GDGTs and the response of GDGT-based proxies to changes in climate along the transect. The shift in the distribution of archaeal isoprenoidal GDGTs (isoGDGTs) revealed that the archaeal community varied significantly along the transect, which can affect the relationship between TEX86 and mean annual air temperature (MAT). In addition, the increased temperature seasonality at higher altitudes exerted a significant impact on TEX86. We proposed a global calibration of TEX86 for the growing season temperature reconstruction in the soil environments: T =85.19×TEX86− 46.30 ( R 2=0.84, p 0.55 are diagnostic for the cold-humid climate. Thus, the combination of MBT′5me and MBT′6me has the potential as a tool for the identification of different types of paleoclimate.

Evaluating Production of Cyclopentyl Tetraethers by Marine Group II Euryarchaeota in the Pearl River Estuary and Coastal South China Sea: Potential Impact on the TEX86 Paleothermometer.

TEX86 [TetraEther indeX of glycerol dialkyl glycerol tetraethers (GDGTs) with 86 carbon atoms] has been widely applied to reconstruct (paleo-) sea surface temperature. Marine Group I (MG-I) Thaumarchaeota were thought to be the primary source of GDGTs constituting the TEX86 formula; however, recent research has suggested that Marine Group II (MG-II) Euryarchaeota may also contribute significantly to the GDGT pool in the ocean. Little is known regarding the potential impact of MG-II Euryarchaeota-derived GDGTs on TEX86 values recorded in marine sediments. In this study, we assessed the relationship between distributions of GDGTs and MG-II Euryarchaeota and evaluated its potential effect on the TEX86 proxy. Lipid and DNA analyses were performed on suspended particulate matter and surface sediments collected along a salinity gradient from the lower Pearl River (river water) and its estuary (mixing water) to the coastal South China Sea (SCS, seawater). TEX86-derived temperatures from the water column and surface sediments were significantly correlated and both were lower than satellite-based temperatures. The ring index (RI) values in these environments were higher than predicted from the calculated TEX86-RI correlation, indicating that the GDGT pool in the water column of the PR estuary and coastal SCS comprises relatively more cyclopentane rings, which thereby altered TEX86 values. Furthermore, the abundance of MG-II Euryarchaeota 16S rRNA gene in the mixing water was two to three orders of magnitude higher than those observed in the river or seawater. Significant linear correlations were observed between the gene abundance ratio of MG-II Euryarchaeota to total archaea and the fractional abundance of GDGTs with cyclopentane rings. Collectively, these results suggest that MG-II Euryarchaeota likely produce a large proportion of GDGTs with 1–4 cyclopentane moieties, which may bias TEX86 values in the water column and sediments. As such, valid interpretation of TEX86 values in the sediment record, particularly in coastal oceans, should consider the contribution from MG-II Euryarchaeota.

Hydrologic controls on seasonal and inter-annual variability of Congo River particulate organic matter source and reservoir age

We present dissolved organic carbon (DOC) concentrations, particulate organic matter (POM) composition (δ13C, δ15N, ∆14C, N/C), and particulate glycerol dialkyl glycerol tetraether (GDGT) distributions from a 34-month time-series near the mouth of the Congo River. An end-member mixing model using δ13C and N/C indicates that exported POM is consistently dominated by C3 rainforest soil sources, with increasing contribution from C3 vegetation and decreasing contribution from phytoplankton at high discharge. Large C4 inputs are never observed despite covering≈13% of the catchment. Low and variable ∆14C values during 2011 [annual mean=(−148±82) ‰], when discharge from left-bank tributaries located in the southern hemisphere reached record lows, likely reflect a bias toward pre-aged POM derived from the Cuvette Congolaise swamp forest. In contrast, ∆14C values were stable near −50‰ between January and June 2013, when left-bank discharge was highest. We suggest that headwater POM is replaced and/or diluted by C3 vegetation and pre-aged soils during transit through the Cuvette Congolaise, whereas left-bank tributaries export significantly less pre-aged material. GDGT distributions provide further evidence for seasonal and inter-annual variability in soil provenance. The cyclization of branched tetraethers and the GDGT-0 to crenarchaeol ratio are positively correlated with discharge (r≥0.70; p-value≤4.3×10−5) due to the incorporation of swamp-forest soils when discharge from right-bank tributaries located in the northern hemisphere is high. Both metrics reach record lows during 2013, supporting our interpretation of increased left-bank contribution at this time. We conclude that hydrologic variability is a major control of POM provenance in the Congo River Basin and that tropical wetlands can be a significant POM source despite their small geographic coverage.