TEXPRESS v1.0: A MATLAB toolbox for efficient processing of GDGT LC–MS data

Liquid chromatography–mass spectrometry (LC–MS) analysis of glycerol dialkyl glycerol tetraethers (GDGTs) from sediment and soil samples has become a widely adopted approach for reconstructing past ocean and continental climate variables such as temperature and pH. The LC–MS data used for constructing these GDGT climate proxies are taken directly from the peak area values of individual GDGT [M+H]⁺ ions, often determined from manual peak integration due to unreliable computer integrators in commercial software, particularly in cases of complex baselines, asymmetric peak shapes and peak coelution. Manual integration is not only time consuming, but also prone to user induced inconsistency when individuals utilize different criteria for peak/baseline definition. To overcome these problems, we have developed a user friendly, graphical user interface (GUI) programmed in the MATLAB environment, allowing users to efficiently and reproducibly perform batch processing and peak integration of LC–MS data. The program, “TEXPRESS” v1.0 (“tetraether index express”), incorporates modern chemometric based techniques for baseline definition and deconvolution of complex chromatographic peaks and we show that LC–MS data processed using the TEXPRESS toolbox are in strong agreement with results obtained from manual peak integration. We provide a general overview of the concepts and architecture of the TEXPRESS toolbox and discuss the advantages of chemometric based peak integration methods for processing branched and isoprenoid GDGT LC–MS data.     

Glacial and Holocene terrestrial temperature variability in subtropical east Australia as inferred from branched GDGT distributions in a sediment core from Lake McKenzie

Branched glycerol dialkyl glycerol tetraether (GDGT) distributions observed in a sediment core from Lake McKenzie were utilized to quantitatively reconstruct the pattern of mean annual air temperature (MAAT) from coastal subtropical eastern Australia between 37 and 18.3 cal ka BP and 14.0 cal ka BP to present. Both the reconstructed trend and amplitude of MAAT changes from the top of the sediment core were nearly identical to a local instrumental MAAT record from Fraser Island, providing confidence that in this sediment core branched GDGTs could be used to produce a quantitative record of past MAAT. The reconstructed trend of MAAT during 37 to 18.3 cal ka BP and timing of the Last Glacial Maximum (LGM) in the Lake McKenzie record were in agreement with previously published nearby marine climate records. The amplitude of lower-than-present MAAT during the LGM potentially provides information on the latitude of separation of the Tasman Front from the East Australian current in the subtropical western Pacific. The Lake McKenzie record shows an earlier onset of near modern day warm temperatures in the early Holocene compared to marine records and the presence of a warmer than present day period during the mid-Holocene.     

Distribution of glycerol ether lipids in halophilic,methanogenic and hyperthermophilic archaea

Four representatives of methanogenic Euryarchaeota (Methanosarcina mazei strain Gö1, Methanosphaera stadtmanae, Methanobrevibacter smithii and Methanosaeta thermophila), the hyperthermophilic euryarchaeon Thermococcus kodakarensis and the halophilic euryarchaeon Haloferax volcanii were studied for their glycerol ether lipid composition. The predominant core membrane lipid in all of them was archaeol, which was accompanied by variable quantities of sn-2-hydroxyarchaeol in the methanogens M. mazei (Methanosarcinales) and M. stadtmanae (Methanobacteriales). All methanogenic and hyperthermophilic Euryarchaeota also contained comparatively high abundances of the glycerol dialkyl glycerol tetraether without a cyclopentane moiety (GDGT-0). The methanoarchaeon M. stadtmanae, in addition to GDGT-0, contained GDGT core lipid structures with 1–4 cyclopentane moieties (GDGTs 1–4). We also found minor amounts of a glycerol trialkyl glycerol tetraether (GTGT) and a glycerol dialkanol diether (GDD), both of which did not contain cyclopentane moieties, as well as methylated and dimethylated GDGT-0 in all the archaea with the exception of H. volcanii. Like its GDGT distribution, M. stadtmanae showed an extended range of GDD structures with up to two cyclopentane ring systems. Our results thus indicate that both methanogenic and hyperthermophilic Euryarchaeota may represent source organisms of GTGT-0, GDDs and methylated-GDGTs in natural environments. All the latter components have recently been reported to be ubiquitously distributed in marine sediments but their biological origin is largely unknown. Moreover, a suite of unsaturated GDGTs without a cyclopentane moiety and up to four double bonds in the hyperthermophile T. kodakarensis was tentatively assigned.     

Altitudinal shift in stable hydrogen isotopes and microbial tetraether distribution in soils from the Southern Alps,NZ: Implications for paleoclimatology and paleoaltimetry

The Southern Alps are an ideal locality for studying patterns of isotopic fractionation associated with orographic precipitation. We have evaluated whether altitudinal change is reflected in the stable hydrogen isotopic composition (δ²H) of stream water, plant stem water and leaf wax lipids (n-alkanes) from living plants and soils, as well as in soil temperature. Samples were collected along an altitudinal transect from the windward side of the Southern Alps to Lake Hawea in the rain shadow. The results indicate that δ²H values of stem water overlap with stream water, demonstrating a gradual decrease with elevation that complied with modeled Rayleigh distillation, reflecting an isotopic lapse rate of −18.0 (± 1.1, 1σ)‰/km. Leaf and soil n-alkanes shared similar δ²H values and were ²H depleted relative to stem/stream waters. The values for soil n-alkanes indicated an isotopic lapse rate of −21.8 (± 2.0, 1σ)‰/km, consistent with precipitation data and long term observations. MBT/CBT derived soil temperature values based on the relative distribution of microbial tetraether lipids were similar to midsummer temperature observations, displaying an elevational decrease rate of −5.6 (± 1.5, 1σ) °C/km, consistent with regional and global observations.The results indicate that sedimentary lipid δ²H and microbial tetraether temperature estimates captured altitudinal trends in the isotopic composition of precipitation and mean temperature and further support their application in the reconstruction of past climate and surface uplift histories. However, notable differences in isotopic composition and temperature estimates between in situ soils and those with downslope transport of material emphasize the importance of facies analysis when interpreting past systems.