Search Results (9)

Glycerol Dialkyl Glycerol Tetraethers (GDGTs) are microbial membrane lipids that can provide crucial information for identifying organic carbon sources and understanding paleoenvironments. Despite numerous studies reporting the presence of GDGTs in various terrestrial and marine environments, there is a paucity of reports concerning GDGTs in mangrove wetlands that are characterized by unique hydrological conditions and disproportionately high accumulation rates of blue carbon (i.e., carbon sequestered in coastal ecosystems, where tidal flooding and anaerobic sediments facilitate exceptional long-term carbon storage). This study investigates GDGTs in 81 sediment samples from 5 sediment cores collected from three Asian mangrove wetlands in Bangladesh, Hong Kong, and Guangxi Province, China. The Hong Kong mangrove sediments had the highest GDGT concentration (370.18 ± 58.00 ng·g⁻¹ dws), followed by Bangladesh mangrove sediments (136.70 ± 41.70 ng·g⁻¹ dws), while Guangxi mangrove sediments had the lowest (100.80 ± 28.71 ng·g⁻¹ dws). All samples demonstrated high BIT index values (>0.8), low IIIa/IIa index values (0.09–0.19) and the predominance of tetramethylated brGDGTs (70.38 ± 2.21%), indicating that terrestrial inputs are the primary source of organic carbon. Despite overall low methylation index (MI) values (0.15–0.35) and GDGT-0/Cren ratios, deeper sediment samples in the lower part of HK exhibited GDGT-0/Cren > 2, likely reflecting enhanced contributions of methanogenic archaea under distinct redox conditions compared to upper sediments. This in situ production may complicate the application of GDGT-based paleo-proxies, as indicated by the substantial deviations between CBT’-pH (MBT’_5ME-temperature) and measured pH (instrumental temperature). The dominant bacterial phyla in the mangrove sediments of Guangxi and Bangladesh were Proteobacteria, Actinobacteriota, Chloroflexi, Acidobacteriota, and Firmicutes (>70% relative abundance). However, correlations between microbial community compositions and brGDGT isomers are different among sampling sites. Our study emphasizes that site- and depth-specific microbial activity may significantly contribute to organic matter cycling and the in situ production of GDGTs in mangrove sediments. These factors should be taken into account for organic carbon sequestration and the validity of GDGT-based paleo-proxies in mangrove wetlands. Full article

Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are promising molecular biomarkers widely applied in paleoenvironmental reconstructions, including temperature and pH. However, knowledge of the microorganisms responsible for brGDGT production in marine environments remains limited, which constrains the further development and application of brGDGT-based proxies for reconstructing past marine conditions. In this study, both ‘living’ intact polar lipid-derived brGDGTs (IPL-brGDGTs) and ‘fossil’ core brGDGTs (CL-brGDGTs), together with bacterial community compositions, were analysed in multiple sediment cores collected along a nearshore-to-offshore transect in the East China Sea (ECS). The potential correlations between brGDGT distributions and bacterial community compositions at varying sediment depths across an environmental gradient were also explored. Results revealed that IPL-brGDGTs were predominantly biosynthesised in situ, whereas CL-brGDGTs reflected a mixture of marine autochthonous production and terrestrial inputs. Potential brGDGT-producing bacteria in nearshore environments were primarily composed of chemolithoautotrophic taxa (e.g., Gammaproteobacteria and Dehalococcoidia) and chemoheterotrophic taxa (e.g., Alphaproteobacteria, Bacilli, and Actinobacteria). In contrast, offshore regions were dominated by chemoheterotrophic hypoxic bacteria (e.g., Anaerolineae and Phycisphaerae) and facultatively anaerobic chemolithoautotrophic bacteria (e.g., Gammaproteobacteria and Desulfobacteria). A significant difference in bacterial community composition and IPL-brGDGT distribution was observed at a depth of 17 cm, likely due to physical disturbance in near-surface sediments, such as wave action, tidal forces, and storm events. Variance partitioning analysis (VPA) revealed that the bacterial community composition alone accounted for 14.1% of the variation in IPL-brGDGTs and 6.5% in CL-brGDGTs, further suggesting that the distribution of brGDGTs is primarily influenced by the composition of the bacterial community in the nearshore-to-offshore sedimentary ecosystems of the ECS. These findings regarding the potential biosynthesis of brGDGTs in coastal habitats advance our understanding of the microbial mechanisms that regulate brGDGT distribution in marine ecosystems. Moreover, they emphasise the importance of considering physical disturbance effects when interpreting sedimentary brGDGT records for paleoenvironmental reconstructions in marginal seas, such as the ECS. Full article

Archaeal lipids, defining a primordial life domain alongside Bacteria and Eukarya, are distinguished by their unique glycerol-1-phosphate backbone and ether-linked isoprenoid chains. Serving as critical geochemical biomarkers, archaeal lipids like glycerol dialkyl glycerol tetraethers (GDGTs) underpin paleoclimate proxies, while their phylum-specific distributions illuminate phylogenetic divergence. Despite the maturity of Mass Spectrometry-based quantitative biomarkers—predominantly those with established structures—becoming well-established in geochemical research, systematic investigation of archaeal lipids as natural products has notably lagged. This deficit manifests across three key dimensions: (1) Extraction methodology lacks universal protocols adapted to diverse archaeal taxa and sample matrices. While comparative studies exist, theoretical frameworks guiding method selection remain underexplored. (2) Purification challenges persist due to the unique structures and complex isomerization profiles of archaeal lipids, hindering standardized separation protocols. (3) Most critically, structural characterization predominantly depends on decades-old foundational studies. However, the existing reviews prioritize chemical structural, biosynthetic, and applied aspects of archaeal lipids over analytical workflows. This review addresses this gap by adopting a natural product chemistry perspective, integrating three key aspects: (1) the clarification of applicable objects, scopes, and methodological mechanisms of various extraction technologies for archaeal lipids, encompassing both cultured and environmental samples; (2) the elucidation of separation principles underlying polar-gradient lipid fractionation processes, leveraging advanced chromatographic technologies; (3) the detailed exploration of applications for NMR in resolving complex lipid structures, with specialized emphasis on determining the stereochemical configuration. By synthesizing six decades of methodological evolution, we establish a comprehensive analytical framework, from lipids extraction to structural identification. This integrated approach constructs a systematic methodological paradigm for archaeal lipid analysis, bridging theoretical principles with practical implementation. Full article

One gravity core retrieved from the Niger Delta was used to explore the origin of deposited organic matter (OM) and the paleo-climatic and environmental conditions over the Holocene in equatorial West Africa. The geochemical properties of sediments including glycerol dialkyl glycerol tetraethers (GDGTs) and elemental (%OC, %N, C/N) and isotopic (δ¹³C_org, δ¹⁵N) signatures were determined. The determination constrained the age of the column and revealed that the sediment OM was mainly derived from a marine source. The isoprenoid (iso)GDGTs were the dominant GDGTs, with a small amount of branched (br)GDGTs, which led to a low-branched and isoprenoid tetraether index (BIT, 0.02–0.21) and represented a low terrestrial input. Most isoGDGTs and OH-GDGTs were produced in situ by Marine Group I (MG-I) Thaumarchaeota, while the brGDGTs were mainly transported from land. A two-endmember model quantified the contribution of terrestrial OM, as 0.9–19.9% by BIT and 1.1–32.6% by δ¹³C. Accordingly, the millennium-scale sea surface temperatures (SSTs) were reconstructed based on the cyclopentane ring distribution (${\mathrm{T}\mathrm{E}\mathrm{X}}_{86}^{\mathrm{H}}$) and the ring index of OH-GDGTs (RI-OH). The top core SSTs were lower than the modern mean annual SST due to the growth season and habitat depth of Thaumarchaeota. The reconstructed SSTs clearly revealed the four stages of paleoclimate change, in particular, the drought episode of 8.2 kyr and the following humid period. The above research has enhanced our understanding of the paleoclimate change in river outflow during the Holocene at the millennium scale. Full article

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. Full article

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. Full article

Bipolar tetraether lipids (BTL) have been long thought to play a critical role in allowing thermoacidophiles to thrive under extreme conditions. In the present study, we demonstrated that not all BTLs from the thermoacidophilic archaeon Sulfolobus acidocaldarius exhibit the same membrane behaviors. We found that free-standing planar membranes (i.e., black lipid membranes, BLM) made of the polar lipid fraction E (PLFE) isolated from S. acidocaldarius formed over a pinhole on a cellulose acetate partition in a dual-chamber Teflon device exhibited remarkable stability showing a virtually constant capacitance (~28 pF) for at least 11 days. PLFE contains exclusively tetraethers. The dominating hydrophobic core of PLFE lipids is glycerol dialky calditol tetraether (GDNT, ~90%), whereas glycerol dialkyl glycerol tetraether (GDGT) is a minor component (~10%). In sharp contrast, BLM made of BTL extracted from microvesicles (Sa-MVs) released from the same cells exhibited a capacitance between 36 and 39 pF lasting for only 8 h before membrane dielectric breakdown. Lipids in Sa-MVs are also exclusively tetraethers; however, the dominating lipid species in Sa-MVs is GDGT (>99%), not GDNT. The remarkable stability of BLM_PLFE can be attributed to strong PLFE–PLFE and PLFE–substrate interactions. In addition, we compare voltage-dependent channel activity of calcium-gated potassium channels (MthK) in BLM_PLFE to values recorded in BLM_Sa-MV. MthK is an ion channel isolated from a methanogenic that has been extensively characterized in diester lipid membranes and has been used as a model for calcium-gated potassium channels. We found that MthK can insert into BLM_PLFE and exhibit channel activity, but not in BLM_Sa-MV. Additionally, the opening/closing of the MthK in BLM_PLFE is detectable at calcium concentrations as low as 0.1 mM; conversely, in diester lipid membranes at such a low calcium concentration, no MthK channel activity is detectable. The differential effect of membrane stability and MthK channel activity between BLM_PLFE and BLM_Sa-MV may be attributed to their lipid structural differences and thus their abilities to interact with the substrate and membrane protein. Since Sa-MVs that bud off from the plasma membrane are exclusively tetraether lipids but do not contain the main tetraether lipid component GDNT of the plasma membrane, domain segregation must occur in S. acidocaldarius. The implication of this study is that lipid domain formation is existent and functionally essential in all kinds of cells, but domain formation may be even more prevalent and pronounced in hyperthermophiles, as strong domain formation with distinct membrane behaviors is necessary to counteract randomization due to high growth temperatures while BTL in general make archaea cell membranes stable in high temperature and low pH environments whereas different BTL domains play different functional roles. Full article

In Quaternary paleosciences, the rationale behind analogical inference presupposes that former processes can be explained by causes operating now, although their intensity and rates can vary through time. In this paper we synthesised the results of different modern analogue studies performed in a varved lake. We discuss their potential value to obtain best results from high resolution past records. Different biogeochemical contemporary processes revealed seasonality and year-to-year variability, e.g., calcite precipitation, lake oxygenation, production and deposition of pollen and phytoplankton growth. Fingerprints of the first two of these processes were clearly evidenced in the varve-sublayers and allow understanding related to past events. Pollen studies suggested the possibility of identifying and characterizing seasonal layers even in the absence of varves. Marker pigments in the water column were tightly associated with phytoplankton groups living today; most of them were identified in the sediment record as well. We observed that 50% of these marker pigments were destroyed between deposition and permanent burying. In another study, seasonality in the production/distribution of branched glycerol dialkyl glycerol tetraethers (brGDGTs) and derived temperature estimates were investigated in catchment soils and particles settling in the lake. The signatures of brGDGTs in depositional environments mainly were representative of stable conditions of soils in the catchment that last over decades; no brGDGTs seemed to be produced within the lake. The main contribution of this review is to show the advantages and limitations of a multiproxy modern-analogue approach in Lake Montcortès as a case study and proposing new working hypotheses for future research. Full article

In this study, we used optical spectroscopy to characterize the physical properties of microvesicles released from the thermoacidophilic archaeon Sulfolobus acidocaldarius (Sa-MVs). The most abundant proteins in Sa-MVs are the S-layer proteins, which self-assemble on the vesicle surface forming an array of crystalline structures. Lipids in Sa-MVs are exclusively bipolar tetraethers. We found that when excited at 275 nm, intrinsic protein fluorescence of Sa-MVs at 23 °C has an emission maximum at 303 nm (or 296 nm measured at 75 °C), which is unusually low for protein samples containing multiple tryptophans and tyrosines. In the presence of 10–11 mM of the surfactant n-tetradecyl-β-d-maltoside (TDM), Sa-MVs were disintegrated, the emission maximum of intrinsic protein fluorescence was shifted to 312 nm, and the excitation maximum was changed from 288 nm to 280.5 nm, in conjunction with a significant decrease (>2 times) in excitation band sharpness. These data suggest that most of the fluorescent amino acid residues in native Sa-MVs are in a tightly packed protein matrix and that the S-layer proteins may form J-aggregates. The membranes in Sa-MVs, as well as those of unilamellar vesicles (LUVs) made of the polar lipid fraction E (PLFE) tetraether lipids isolated from S. acidocaldarius (LUV_PLFE), LUVs reconstituted from the tetraether lipids extracted from Sa-MVs (LUV_MV) and LUVs made of the diester lipids, were investigated using the probe 6-dodecanoyl-2-dimethylaminonaphthalene (Laurdan). The generalized polarization (GP) values of Laurdan in tightly packed Sa-MVs, LUV_MV, and LUV_PLFE were found to be much lower than those obtained from less tightly packed DPPC gel state, which echoes the previous finding that the GP values from tetraether lipid membranes cannot be directly compared with the GP values from diester lipid membranes, due to differences in probe disposition. Laurdan’s GP and red-edge excitation shift (REES) values in Sa-MVs and LUV_MV decrease with increasing temperature monotonically with no sign for lipid phase transition. Laurdan’s REES values are high (9.3–18.9 nm) in the tetraether lipid membrane systems (i.e., Sa-MVs, LUV_MV and LUV_PLFE) and low (0.4–5.0 nm) in diester liposomes. The high REES and low GP values suggest that Laurdan in tetraether lipid membranes, especially in the membrane of Sa-MVs, is in a very motionally restricted environment, bound water molecules and the polar moieties in the tetraether lipid headgroups strongly interact with Laurdan’s excited state dipole moment, and “solvent” reorientation around Laurdan’s chromophore in tetraether lipid membranes occurs very slowly compared to Laurdan’s lifetime. Full article