Gram-negative bacteria produce specific membrane lipids, i.e. 3-hydroxy fatty acids with 10 to 18 C atoms. They have been recently proposed as temperature and pH proxies in terrestrial settings. Nevertheless, the existing correlations between pH or temperature and indices derived from 3-OH FA distribution are based on a small soil dataset (ca. 70 samples) and only applicable regionally. The aim of this study was to investigate the applicability of 3-OH FAs as mean annual air temperature (MAAT) and pH proxies at the global level. This was achieved using an extended soil dataset of 168 topsoils distributed worldwide, covering a wide range of temperatures (5 to 30 ∘C) and pH (3 to 8). The response of 3-OH FAs to temperature and pH was compared to that of established branched glycerol dialkyl glycerol tetraether (GDGT)-based proxies (MBT'5Me/CBT). Strong linear relationships between 3-OH-FA-derived indices (RAN15, RAN17 and RIAN) and MAAT or pH could only be obtained locally for some of the individual transects. This suggests that these indices cannot be used as palaeoproxies at the global scale using simple linear regression models, in contrast with the MBT'5Me and CBT. However, strong global correlations between 3-OH FA relative abundances and MAAT or pH were shown by using other algorithms (multiple linear regression, k-NN and random forest models). The applicability of the three aforementioned models for palaeotemperature reconstruction was tested and compared with the MAAT record from a Chinese speleothem. The calibration based on the random forest model appeared to be the most robust. It generally showed similar trends with previously available records and highlighted known climatic events poorly visible when using local 3-OH FA calibrations. Altogether, these results demonstrate the potential of 3-OH FAs as palaeoproxies in terrestrial settings.
19 July 2024 in Geochemistry, Geophysics, Geosystems
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.
In the hyperarid Atacama Desert, water availability plays a crucial role in allowing plant survival. Along with scant rainfall, marine advective fog frequently occurs along the coastal escarpment fueling isolated mono-specific patches of Tillandsia vegetation. In this study, we investigate the lipid biomarker composition of the bromeliad Tillandsia landbeckii (CAM plant) to assess structural adaptations at the molecular level as a response to extremely arid conditions. We analyzed long-chain n-alkanes and fatty acids in living specimens (n = 59) collected from the main Tillandsia dune ecosystems across a 350 km coastal transect. We found that the leaf wax composition was dominated by n-alkanes with concentrations (total average 160.8 ± 91.4 µg/g) up to three times higher than fatty acids (66.7 ± 40.7 µg/g), likely as an adaptation to the hyperarid environment. Significant differences were found in leaf wax distribution (Average Chain Length [ACL] and Carbon Preference Index [CPI]) in the northern zone relative to the central and southern zones. We found strong negative correlations between fatty acid CPI and n-alkane ACL with precipitation and surface evaporation pointing at fine-scale adaptations to low moisture availability along the coastal transect. Moreover, our data indicate that the predominance of n-alkanes is reflecting the function of the wax in preventing water loss from the leaves. The hyperarid conditions and good preservation potential of both n-alkanes and fatty acids make them ideal tracers to study late Holocene climate change in the Atacama Desert.
Quantitative reconstructions of past continental climates are vital for understanding contemporary and past climate change. Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are unique bacterial lipids that have been proposed as universal paleothermometers due to their correlation with temperature in modern settings. Thus, brGDGTs may serve as a crucial paleotemperature proxy for understanding past climate variations and improving regional climate projections, especially in critical but under constrained regions. That said, complications can arise in their application due to varying source contributions (e.g., soils vs. peats vs. lacustrine). As such, this study investigates brGDGT distributions in Chilean lake surface sediments and corresponding watershed soils to determine the source of brGDGTs to lake sediments. Global datasets of brGDGTs in lake sediments and soils were additionally compiled for comparison. Distinct brGDGT distributions in Chilean lakes and soils indicate minimal bias from soil inputs to the lacustrine sediments as well as in situ lacustrine production of brGDGTs, which supports the use of brGDGTs in lake sediments as reliable paleotemperature proxies in the region. The ΣIIIa/ΣIIa ratio, initially promising as a brGDGT source indicator in marine settings, shows global complexities in lacustrine settings, challenging the establishment of universal thresholds for source apportionment. That said, we show that the ratio can be successfully applied in Chilean lake surface sediments. Direct comparisons with watershed soils and further research are crucial for discerning brGDGT sources in lake sediments and improving paleotemperature reconstructions on regional and global scales moving forward. Overall, this study contributes valuable insights into brGDGT variability, essential for accurate paleoreconstructions.