An interlaboratory study of TEX86 and BIT analysis of sediments, extracts and standard mixtures.

Two commonly used proxies based on the distribution of glycerol dialkyl glycerol tetraethers (GDGTs) are the TEX86 (TetraEther indeX of 86 carbon atoms) paleothermometer for sea surface temperature reconstructions and the BIT (Branched Isoprenoid Tetraether) index for reconstructing soil organic matter input to the ocean. An initial round-robin study of two sediment extracts, in which 15 laboratories participated, showed relatively consistent TEX86 values (reproducibility ±3-4°C when translated to temperature) but a large spread in BIT measurements (reproducibility ±0.41 on a scale of 0-1). Here we report results of a second round-robin study with 35 laboratories in which three sediments, one sediment extract, and two mixtures of pure, isolated GDGTs were analyzed. The results for TEX86 and BIT index showed improvement compared to the previous round-robin study. The reproducibility, indicating interlaboratory variation, of TEX86 values ranged from 1.3 to 3.0°C when translated to temperature. These results are similar to those of other temperature proxies used in paleoceanography. Comparison of the results obtained from one of the three sediments showed that TEX86 and BIT indices are not significantly affected by interlaboratory differences in sediment extraction techniques. BIT values of the sediments and extracts were at the extremes of the index with values close to 0 or 1, and showed good reproducibility (ranging from 0.013 to 0.042). However, the measured BIT values for the two GDGT mixtures, with known molar ratios of crenarchaeol and branched GDGTs, had intermediate BIT values and showed poor reproducibility and a large overestimation of the "true" (i.e., molar-based) BIT index. The latter is likely due to, among other factors, the higher mass spectrometric response of branched GDGTs compared to crenarchaeol, which also varies among mass spectrometers. Correction for this different mass spectrometric response showed a considerable improvement in the reproducibility of BIT index measurements among laboratories, as well as a substantially improved estimation of molar-based BIT values. This suggests that standard mixtures should be used in order to obtain consistent, and molar-based, BIT values

Impact of riverine suspended particulate matter on the branched glycerol dialkyl glycerol tetraether composition of lakes : The outflow of the Selenga River in Lake Baikal (Russia)

Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are bacterial membrane lipids found in several environments, including soils, rivers and lakes, whose distribution varies with temperature and pH, although this dependence is apparently not the same for the different environments. Mixing of brGDGT sources may thus complicate palaeoenvironmental reconstruction. The extent to which brGDGTs in a lake outflow reflect the distribution delivered by upstream rivers was studied for Lake Baikal (Russia), one of the largest freshwater lakes worldwide. Fifteen brGDGTs in suspended particulate matter (SPM) of the Selenga River and its outflow from the lake were quantified. The river and lake SPM had rather different distributions. The riverine distribution was still apparent in the SPM of the lake surface water 5 km from the river mouth, but shifts in the distribution were already apparent in the SPM of the surface water after 1 km. Based on the brGDGT distributions of the SPM of the Selenga outflow and that of the lake, conservative mixing between the river and the lake brGDGT distributions could not fully explain the observed shifts in distributions. Both preferential degradation and in situ production of brGDGTs in the surface and, especially, bottom water of the river outflow were potentially responsible. This implies that a riverine lipid distribution delivered to a lake can be modified prior to being transported downstream. The lacustrine brGDGT distribution, that possibly could have reflected a mixture of mountainous and Selenga River SPM, was not recognized in downstream Yenisei River SPM. The watershed of Lake Baikal thus does not seem to contribute to the brGDGTs transported to the marine system. As many large rivers have major lakes in their watershed, this has implications for palaeoclimate reconstruction from river fan sediments globally

Using tetraether lipids archived in North Sea Basin sediments to extract North Western European Pliocene continental air temperatures

The Pliocene is often regarded as a suitable analogue for future climate, due to an overall warmer climate (2–3 °C) coupled with atmospheric CO2 concentrations largely similar to present values (∼400 ppmv). Numerous Pliocene sea surface temperature (SST) records are available, however, little is known about climate in the terrestrial realm. Here we generated a Pliocene continental temperature record for Northwestern Europe based on branched glycerol dialkyl glycerol tetraether (brGDGT) membrane lipids stored in a marine sedimentary record from the western Netherlands. The total organic carbon (TOC) content of the sediments and its stable carbon isotopic composition () indicate a strong transition from primarily marine derived organic matter (OM) during the Pliocene, to predominantly terrestrially derived OM after the transition into the Pleistocene. This trend is supported by the ratio of branched and isoprenoid tetraethers (BIT index). The marine–terrestrial transition indicates a likely change in brGDGT sources in the core, which may complicate the applicability of the brGDGT paleotemperature proxy in this setting. Currently, the application of the brGDGT-based paleothermometer on coastal marine sediments has been hampered by a marine overprint. Here, we propose a method to disentangle terrestrial and marine sources based on the degree of cyclization of tetramethylated brGDGTs (#rings) using a linear mixing model based on the global soil calibration set and a newly developed coastal marine temperature transfer function. Application of this method on our brGDGT record resulted in a ‘corrected’ terrestrial temperature record (MATterr). This latter record indicates that continental temperatures were ∼12–14 °C during the Early Pliocene, and 10.5–12 °C during the Mid Pliocene, confirming other Pliocene pollen based terrestrial temperature estimates from Northern and Central Europe. Furthermore, two colder (Δ 5–7 °C) periods in the Pliocene MATterr record show that the influence of Pliocene glacials reached well into NW Europe

Distribution of glycerol dialkyl glycerol tetraether lipids in the water column of Lake Tanganyika

We studied the distribution of glycerol dialkyl glycerol tetraethers (GDGTs) in suspended particulate matter from the water column of Lake Tanganyika (East Africa), where sediment studies had shown the applicability of the TEX86 proxy for reconstructing surface lake water temperature. GDGTs, in particular crenarchaeol, showed maximum abundance within the suboxic zone (100–180 m), suggesting that this is the preferred niche of ammonia-oxidizing Thaumarchaeota. Despite evidence for anaerobic methane oxidation in deep anoxic water (300–1200 m) no unambiguous evidence for an imprint of methanotrophic archaea on GDGT distribution was found. Comparison of TEX86 and BIT indices with those of surface sediments suggests that the sedimentary GDGTs are derived predominantly from the oxic zone and suboxic zone of the lake

Aegean Sea as driver of hydrographic and ecological changes in the eastern Mediterranean

The eastern Mediterranean is undergoing a long-term increase in net evaporation, which may have preconditioned the profound changes that occurred in its deep-sea ventilation over the past two decades. We test the sensitivity of Aegean convective deep-water formation to forcing in the opposite sense, based on a last interglacial episode of enhanced freshwater injection into the eastern Mediterranean. We find that Aegean subsurface ventilation collapsed completely within 40 ± 20 yr, promoting euxinic conditions hostile to aerobic life that expanded toward the photic layer within 650 ± 250 yr. Similar conditions extended throughout the eastern Mediterranean 300 ± 120 yr later. These findings emphasize the exceptional sensitivity of Aegean deep-water formation to climate forcing, driving large-scale hydrographic adjustments throughout the eastern Mediterranean and beyond

Onset of long-term cooling of Greenland near the Eocene-Oligocene boundary as revealed by branched tetraether lipids

The Eocene-Oligocene (E-O) boundary interval is considered to be one of the major transitions in Earth's climate, witnessing the first major expansion of the East Antarctic Ice Sheet. However, the extent of the associated climatic cooling, especially for high northern latitude continental landmasses, is poorly constrained. In this study we reconstruct the first mean annual air temperature (MAAT) for the Greenland landmass during the late Eocene and early Oligocene by applying a new proxy based on the distribution of branched tetraether lipids derived from soil bacteria preserved in a marine sediment core from the Greenland Basin. The temperature estimates are compared with a composite continental temperature record based on bio-climatic analysis of pollen assemblages. Both proxies reveal comparable late Eocene MAATs of 13–15 °C and a gradual long-term cooling of 3–5 °C starting near the E-O boundary. These data are in agreement with other MAAT reconstructions from northern midlatitude continents and suggest a general cooling of the Northern Hemisphere during the E-O transition