Description: In ocean margin sediments both marine and terrestrial organic matter (OM) are buried but the factors governing their relative preservation and degradation are not well understood. In this study, we analysed the degree of preservation of marine isoprenoidal and soil-derived branched glycerol dialkyl glycerol tetraethers (GDGTs) upon long-term oxygen exposure in OM-rich turbidites from the Madeira Abyssal Plain by analyzing GDGT concentrations across oxidation fronts. Relative to the anoxic part of the turbidites ca. 7-20% of the soil-derived branched GDGTs were preserved in the oxidized part while only 0.2-3% of the marine isoprenoid GDGT crenarchaeol was preserved. Due to these different preservation factors the Branched Isoprenoid Tetraether (BIT) index, a ratio between crenarchaeol and the major branched GDGTs that is used as a tracer for soil-derived organic matter, substantially increases from 0.02 to 0.4. Split Flow Thin Cell (SPLITT) separation of turbidite sediments showed that the enhanced preservation of soil-derived carbon was a general phenomenon across the fine particle size ranges (〈38 mm). Calculations reveal that, despite their relatively similar chemical structures, degradation rates of crenarchaeol are 2-fold higher than those of soil-derived branched GDGTs, suggesting preferential soil OM preservation possibly due to matrix protection.

Description: One of the primary prerequisites for the application of organic proxies is that they should not be substantially affected by diagenesis. However, studies have shown that oxic degradation of biomarker lipids can affect their relative distribution. We tested the diagenetic stability of the UK'37 and TEX86 palaeothermometers upon long term oxygen exposure. For this purpose, we studied the distributions of alkenones and glycerol dialkyl glycerol tetraethers (GDGTs) in different sections of turbidites at the Madeira Abyssal Plain (MAP) that experienced different degrees of oxygen exposure. Sediments were deposited anoxically on the shelf and then transported by turbidity currents to the MAP, which has oxic bottom water. This resulted in partial degradation of the turbidite organic matter as a result of long term exposure to oxic bottom water. Concentrations of GDGTs and alkenones were reduced by one to two orders of magnitude in the oxidized parts of the turbidites compared to the unoxidized parts, indicating substantial degradation. High-resolution analysis of the Pleistocene F-turbidite showed that the UK'37 index of long chain alkenones increased only slightly (0.01, corresponding to 〈0.5 °C) in the oxidized part of the turbidite, suggesting minor preferential degradation of the C37:3 alkenone, in agreement with previous studies. TEX86 values showed a small increase (0.02, corresponding to ~2 °C) in the F-turbidite, like UK'37 , while for other Pliocene/Miocene turbidites it either remained unchanged or decreased substantially (up to 0.06, corresponding to ~6 °C). Previous observations showed that the BIT index, a proxy for the contribution of soil organic matter to total organic carbon, was always substantially higher in the oxidized part in all the turbidites, as a result of preferential degradation of marine-derived GDGTs. This relative increase in soil-derived GDGTs affects TEX86, as the isoprenoid GDGT distribution on the continent can be quite different from that in the marine environment. Our results indicate that the organic proxies are affected by long term oxic degradation to different extents; this should be taken into account when applying these proxies in palaeoceanographic studies of sediments which have been exposed to prolonged oxic degradation.

Description: The TEX86H temperature proxy is a relatively new proxy based on crenarchaeotal lipids and has rarely been applied together with other temperature proxies. In this study, we applied the TEX86H on a sediment core from the Alboran Sea (western Mediterranean, core ODP-977A) covering the penultimate climate cycle, that is, from 244 to 130 ka, and compared this with previously published sea surface temperatures derived from the Uk'37 of alkenones of haptophyta and Mg/Ca records of planktonic foraminifera. The TEX86H temperature record shows remarkably similar stadial-interstadial patterns and abrupt temperature changes to those observed with the Uk'37 palaeothermometer. Absolute TEX86H temperature estimates are generally higher than those of Uk'37, though this difference (〈3°C in 81% of the data points) is mainly within the temperature calibration error for both proxies, suggesting that crenarchaeota and haptophyta experienced similar temperature variations. During occasional events (〈5% of the analyzed time span), however, the TEX86H exhibits considerably higher absolute temperature estimates than the Uk'37. Comparison with Mg/Ca records of planktonic foraminifera as well as other Mediterranean TEX86 and Uk'37 records suggests that part of this divergence may be attributed to seasonal differences, that is, with TEX86H reflecting mainly the warm summer season while Uk'37 would show annual mean. Biases in the global calibration of both proxies or specific biases in the Mediterranean are an alternative, though less likely, explanation. Despite differences between absolute TEX86H and Uk'37 temperatures, the correlation between the two proxies (r**2 = 0.59, 95% significance) provides support for the occurrence of abrupt temperature variations in the western Mediterranean during the penultimate interglacial-to-glacial cycle.

Description: Two sediment cores from the western Arabian Sea, NIOP905 and 74KL, were analyzed to determine sea surface temperature (SST) variations over the last 23 kyr. Two organic molecular SST proxies were used, the well-established UK'37 based on long-chain unsaturated ketones synthesized by haptophyte algae and the newly proposed TEX86 derived from the membrane lipids of Crenarchaeota. Comparison of NIOP905 and 74KL core top data with present-day SST (0-10 m) values indicates that both proxies yield temperatures similar to local annual mean SSTs. However, TEX86 and UK'37 SST down-core records derived from the same cores differ in magnitude and phasing. The alkenone SST record of NIOP905 shows small changes in SST (~0.5°C) over the last 23 kyr, while that of core 74KL shows a ~2°C increase from the Last Glacial Maximum (LGM) (23-19 calendar (cal) kyr B.P.) through the Holocene (the last 11.5 cal kyr B.P.) synchronous with changes in the Northern Hemisphere. In contrast, the TEX86 records of both cores show a large increase in SST from 22°-23°C in the LGM to 28°-30°C during Termination I (19-11.5 cal kyr B.P.), decreasing to present-day annual means of ~26°C. A cold phase between 14.5 and 12 cal kyr B.P. that may correspond to the Antarctic cold reversal is also observed. This implies a Southern Hemisphere control on tropical SST reconstructed by the TEX86, possibly related to SW monsoon. Our results suggest that the application of both TEX86 and UK'37 give different but complementary information on SST developments in past marine environments.

Description: The TEX86H paleothermometer based on isoprenoid glycerol dialkyl glycerol tetraethers (isoGDGTs) has widely been applied in various marine settings to reconstruct past sea surface temperatures (SSTs). However, it still remains uncertain how well this proxy reconstructs annual mean SSTs. Here, we assess environmental factors governing the TEX86H paleothermometer in the Mediterranean Sea, by studying the distribution of isoGDGTs in surface sediments, suspended particulate matter (SPM), and two sediment cores. A redundancy analysis using the fractional abundance of the six major isoGDGTs indicates that the sedimentary isoGDGTs are mostly influenced by three environmental factors explaining a large part (74%) of the variance in isoGDGT distribution. In order of decreasing significance, these factors are annual mean SST, continental organic matter input as indicated by the BIT index, and water depth. However, when considering only the four isoGDGTs that are used for the TEX86H proxy, water depth is the most significant parameter, explaining 63% of the variance. Indeed, a strong positive relationship between water depth and TEX86H is observed in both surface sediments and SPM from the Mediterranean Sea. This is driven by an increase in fractional abundances of GDGT-2 and crenarchaeol regio-isomer and a decrease in the fractional abundances of GDGT-1 and GDGT-3 with increasing water depth, leading to a bias to higher temperatures of TEX86H in deep-water surface sediments. The fact that the water-depth trend is also apparent in SPM suggests that this change might be due to a change in thaumarchaeotal community thriving below surface mixed-layer waters and that this signal is, at least partly, incorporated into sedimentary isoGDGTs. Interestingly, surface-sediment TEX86H values from 〉1000 m water depth do not show a correlation with water depth anymore and instead are correlated to annual mean SSTs. A composite deep-water TEX86H dataset of surface sediments from both the Mediterranean Sea and the Red Sea, interconnected regional restricted basins with relatively high bottom-water temperatures and high salinity, forms a distinctive correlation line, statistically distinct from that of the general global correlation. Application of this correlation on two sedimentary records from the western Mediterranean Sea covering the last deglaciation yields SSTs nearly identical to those obtained with the UK'37 paleothermometer, whereas the global calibration substantially overestimates SSTs. Our results show that the warm bias of the TEX86H proxy in the Mediterranean Sea is not due to seasonality, as previously suggested. Further research is needed to elucidate the mechanism behind the strong water depth trend of TEX86H in the Mediterranean Sea which is not apparent in open ocean settings.