Three and half million year history of moisture availability of South West Africa: Evidence from ODP site 1085 biomarker records

Ocean Drilling Program Site 1085 provides a continuous marine sediment record off southern South West Africa for at least the last three and half million years. The n-alkane ∂13 C record from this site records changes in past vegetation and provides an indication of the moisture availability of SW Africa during this time period. Very little variation, and no apparent trend, is observed in the n-alkane δ13C record, suggesting stable long-term conditions despite significant changes in East African tectonics and global climate. Slightly higher n-alkane δ13C values occur between 3.5 and 2.7 Ma suggesting slightly drier conditions than today. Between 2.5 and 2.7 Ma there is a shift to more negative n-alkane δ13C values suggesting slightly wetter conditions during a ~ 0.2 Ma episode that coincides with the intensification of Northern Hemisphere Glaciation (iNHG). From 2.5 to 0.4 Ma the n-alkane δ13C values are very consistent, varying by less than ± 0.5‰ and suggesting little or no long-term change in the moisture availability of South West Africa over the last 2.5 million years. This is in contrast to the long-term drying trend observed further north offshore from the Namib Desert and in East Africa. A comparison of the climate history of these regions suggests that Southern Africa may have been an area of long-term stability over the last 3.5 Myrs

Discours III.

This is the author accepted manuscript. The final version is available from Elsevier via the DOI in this record.Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are increasingly used to reconstruct past terrestrial temperature and soil pH. Here we compare all available modern soil brGDGT data (n=350) to a wide range of environmental parameters to obtain new global temperature calibrations. We show that soil moisture index (MI), a modeled parameter that also takes potential evapotranspiration into account, is correlated to the 6-methyl brGDGT distribution but does not significantly control the distribution of 5-methyl brGDGTs. Instead, temperature remains the primary control on 5-methyl brGDGTs. We propose the following global calibrations: MAAT soil = 40.01 x MBT’5me − 15.25 (n=350, R2 22 = 23 0.60, RMSE = 5.3 °C) and growing degree days above freezing (GDD0 soil) = 14344.3 x MBT’5me - 4997.5 (n=350, R2 24 = 0.63, RMSE = 1779 °C). Recent studies have suggested that factors other than temperature can impact arid and/or alkaline soils dominated by 6-methyl brGDGTs. As such, we develop new global temperature calibrations using samples dominated by 5-methyl brGDGTs only (IR6me<0.5). These new calibrations have significantly improved correlation coefficients and lower root mean square errors (RMSE) compared to the global calibrations: MAATsoil’ = 39.09 x !"#!!" ! − 14.50 (n=177, R2 30 = 0.76, RMSE = 4.1 °C) and GDD0 soil’ = 13498.8 x !"#!!" ! − 4444.5 (n=177, R2 31 = 0.78, RMSE = 1326). We suggest that these new calibrations should be used to reconstruct terrestrial climate in the geological past; however, care should be taken when employing these calibrations outside the modern calibration rangThis research was funded through the advanced ERC grant `The greenhouse earth 412 system' (T-GRES, project reference 340923). R.D.P. acknowledges the Royal Society 413 Wolfson Research Merit Award

Distributions of geohopanoids in peat: Implications for the use of hopanoid-based proxies in natural archives

This is the final version of the article. Available from Elsevier via the DOI in this record.Hopanoids are pentacyclic triterpenoids produced by a wide range of bacteria. Within modern settings, hopanoids mostly occur in the biological 17β,21β(H) configuration. However, in some modern peatlands, the C31 hopane is present as the ‘thermally-mature’ 17α,21β(H) stereoisomer. This has traditionally been ascribed to isomerisation at the C-17 position catalysed by the acidic environment. However, recent work has argued that temperature and/or hydrology also exert a control upon hopane isomerisation. Such findings complicate the application of geohopanoids as palaeoenvironmental proxies. However, due to the small number of peats that have been studied, as well as the lack of peatland diversity sampled, the environmental controls regulating geohopanoid isomerisation remain poorly constrained. Here, we undertake a global approach to investigate the occurrence, distribution and diagenesis of geohopanoids within peat, combining previously published and newly generated data (n = 395) from peatlands with a wide temperature (−1 to 27 °C) and pH (3–8) range. Our results indicate that peats are characterised by a wide range of geohopanoids. However, the C31 hopane and C32 hopanoic acid (and occasionally the C32 hopanol) typically dominate. C32 hopanoic acids occur as αβ- and ββ-stereoisomers, with the ββ-isomer typically dominating. In contrast, C31 hopanes occur predominantly as the αβ-stereoisomer. These two observations collectively suggest that isomerisation is not inherited from an original biological precursor (i.e. biohopanoids). Using geohopanoid ββ/(αβ + ββ) indices, we demonstrate that the abundance of αβ-hopanoids is strongly influenced by the acidic environment, and we observe a significant positive correlation between C31 hopane isomerisation and pH (n = 94, r2 = 0.64, p 1 pH unit) and longer-term (>1 kyr) variation. Overall, our findings demonstrate the potential of geohopanoids to provide unique new insights into understanding depositional environments and interpreting terrestrial organic matter sources in the geological record.This research was funded through the advanced ERC grant ‘The Greenhouse Earth System’ (T-GRES. Project reference: 340923). RDP acknowledges the Royal Society Wolfson Research Merit Award. YZ thanks the National Natural Science Foundation of China (Project reference: 41372033). ELM acknowledges the Philip Leverhulme Prize. We also thank the NERC Life Sciences Mass Spectrometry Facility (Bristol) for analytical support and D. Atkinson for help with the sample preparation. GNI thanks Janet Dehmer and Philippe Schaeffer for helpful discussions. Members of the T-GRES Peat Database collaborators are M.J. Amesbury, H. Biester, R. Bindler, J. Blewett, M.A. Burrows, D. del Castillo Torres, F.M. Chambers, A.D. Cohen, S.J. Feakins, M. Gałka, A. Gallego-Sala, L. Gandois, D.M. Gray, P.G. Hatcher, E.N. Honorio Coronado, P.D.M. Hughes, A. Huguet, M. Könönen, F. Laggoun-Défarge O. Lähteenoja, M. Lamentowicz, R. Marchant, X. Pontevedra-Pombal, C. Ponton, A. Pourmand, A.M. Rizzuti, L. Rochefort, J. Schellekens, F. De Vleeschouwer. Finally, we thank Darci Rush, Phil Meyers and an anonymous reviewer for their comments and thoughtful suggestions which greatly improved this manuscript

Major changes in glacial and Holocene terrestrial temperatures and sources of organic carbon recorded in the Amazon fan by tetraether lipids

The Amazon basin is a major component of the global carbon and hydrological cycles, a significant natural source of methane, and home to remarkable biodiversity and endemism. Reconstructing past climate changes in the Amazon basin is important for a better understanding of the effect of such changes on these critical functions of the basin. Using a novel biomarker proxy, based on the membrane lipids of soil bacteria with a new regional calibration, we present a reconstruction of changes in mean annual air temperatures for the Amazon catchment during the last 37 kyr B. P. Biomarkers were extracted from Ocean Drilling Program sediment core ODP942 recovered from the Amazon fan. The Amazon fan is a major depository for terrestrial sediments, with the advantage that the terrestrial material captured reflects a regional integration of the whole river catchment. The reconstructed tropical Amazonian temperatures were similar to 5 degrees C cooler at the Last Glacial Maximum (similar to 21 degrees C) compared to modern values (similar to 26 degrees C). This is in agreement with previous estimates of tropical continental temperatures in the tropical Amazon basin and tropical Africa during the Last Glacial Maximum. Moreover, we also illustrate how the soil bacterial membrane lipid record reveals major changes in basin dynamics and sediment provenance during the glacial-Holocene transition, impacting the biomarker reconstructions from similar to 11 kyr onward

Effects of temperature and pH on archaeal membrane lipid distributions in freshwater wetlands

This is the author accepted manuscript. The final version is available from Elsevier via the DOI in this record.  Freshwater wetlands harbour diverse archaeal communities and associated membrane lipid assemblages, but the effect of environmental factors (e.g. pH and temperature) on the distribution of these lipids is relatively poorly constrained. Here we explore the effects of temperature and pH on archaeal core-lipid and intact polar lipid (IPL) derived core lipid distributions in a range of wetlands. We focus not only on the commonly studied isoprenoidal glycerol dialkyl glycerol tetraethers (isoGDGTs), but also widen our analyses to include more recently identified but relatively widespread archaeal lipids such as isoGDGT isomers, methylated isoGDGTs (Me-GDGTs), and butanetriol and pentanetriol tetraethers (BDGTs and PDGTs). Based on multivariate analysis and a globally distributed set of wetlands, we find that the degree of isoGDGT cyclisation does increase along with temperature and pH in wetlands; however and unlike in some other settings, this relationship is obscured in simple scatterplots due to the incorporation of isoGDGTs from highly diverse archaeal sources with multiple ring-temperature or ring-pH relationships. We further show that the relative abundance of early eluting to later eluting isoGDGT isomers increases with pH, representing a previously unknown and seemingly widespread archaeal membrane homeostasis mechanism or taxonomic signal. The distribution and abundance of crenarchaeol, a marker for Thaumarchaeota, demonstrates that in wetlands these Archaea, likely involved in ammonia oxidation, are restricted primarily to the generally dryer, soil/sediment surface and typically are more abundant in circumneutral pH settings. We identify Me-GDGTs and Me-isoGMGTs (homologs of isoGDGTs and isoGMGTs, but with additional methylation on the biphytanyl chain) as being ubiquitous in wetlands, but variation in their abundance and distribution suggests changing source communities and/or membrane adaptation. The high relative abundance of BDGTs and PDGTs in the perennially anoxic part of the peat profile (catotelm) as well as their elevated abundance in a circumneutral pH wetland is consistent with an important input from their only known culture source, the methanogenic Methanomassiliicoccales. Our results underline the diversity of archaeal membrane lipids preserved in wetlands and provide a baseline for the use of archaeal lipid distributions in wetlands as tracers of recent or ancient climate and biogeochemistry.NERCRoyal SocietyER

The tropical peatland archaeal lipidome – influence of vegetation and redox on diversity

This is the final version. Available from the European Association of Geoscientists & Engineers via the DOI in this record. The nature, variability, and diversity of environmental microbiomes and lipidomes are vital to understanding soil health, biogeochemical processes and reconstructing past climates. Such research on peatlands – especially tropical peatlands – is limited, despite their importance to the global carbon cycle through the sequestration of organic matter (OM) and production of methane. Here, we explore the distribution of archaea and their isoprenoidal glycerol dialkyl glycerol tetraether lipids (isoGDGTs) across a range of wetlands, in order to ascertain the controls on their distribution. We focus specifically on vegetation and OM composition to explore the relationships between archaeal ecology and carbon cycling in tropical contexts. Through international collaboration, we created a database of core archaeal and bacteria lipid distributions of hundreds of peats from globally widespread sites (the TGRES Peat Database, Naafs et al., 2017). This formed the basis for peat-specific temperature and pH proxies based on the distribution of bacterial branched GDGTs as initially pioneered for mineral soils. However, clear environmental controls and patterns in the distribution of archaeal lipids are ambiguous (Naafs et al., 2018). For example, isoGDGT-5 is restricted to high temperature and low pH settings, but other isoGDGT and overly methylated isoprenoidal GDGT (Me-GDGTs) ring indices are poorly correlated with temperature and pH (Blewett et al., 2020). This suggests that in comparison to previously established GDGT-based environmental proxies the archaeal GDGTs of peatlands derive from an ecologically diverse group of organisms that confound simple environmental comparisons. Given the increased recognition of archaeal metabolic diversity, including a range of heterotrophic, methanotrophic and methanogen ecologies, it seems likely that changes in vegetation, peat OM composition and water level depth will impose significant controls on the archaeal community – and that of the lipids they produce

Archaeal and bacterial glycerol dialkyl glycerol tetraether (GDGT) lipids in environmental samples by high temperature-gas chromatography with flame ionisation and time-of-flight mass spectrometry detection

Archaeal isoprenoidal glycerol dibiphytanyl glycerol tetraether lipids (iGDGTs) and their non-isoprenoidal branched bacterial analogues (brGDGTs) have widespread applications in biogeochemistry and paleothermometry. Analysis of GDGTs usually involves separation using high performance liquid chromatography, typically coupled via atmospheric pressure chemical ionisation to mass spectrometric detection in selected ion-monitoring mode (HPLC–APCI-MS). However, reliable determination of ratios and, in particular, quantification by this technique, can be challenging due to differences in ionisation efficiencies of the various compounds. Quantification of GDGTs also relies on external calibration of the relative response to an internal standard with authenticated GDGTs, which are often not readily accessible. Here, we tested the suitability of high temperature gas chromatography with flame ionisation detection (HTGC-FID) for the determination of concentrations and tetraether lipid-based ratios in marine and terrestrial samples. For this, we identified GDGTs in environmental samples using HTGC coupled to time-of-flight mass spectrometry (HTGC–MS). Using a purified GDGT standard, we show we can quantify GDGT-0 in environmental samples by GC-FID. Some GDGT-based ratios measured by HTGC-FID exhibited a linear correlation (1:1) with ratios derived from HPLC–MS and weight-based ratios of mixtures of purified standards. However, ratios relying on minor isomers, such as TEX86 and MBT/CBT have many unresolved challenges for determination by HTGC. Detection limits were higher than for HPLC–MS. However, the advantages of employing HTGC-based methods include: (1) the independence from MS tuning-related differences in ionisation energies; (2) the potential for direct comparison with other, non-GDGT based biomarkers; and (3) a more complete insight into biomarker distributions in environmental samples by the extension of the temperature range. Quantitative elution of GDGTs from a HTGC column as demonstrated herein, will also enable their analysis by compound-specific isotope ratio mass spectrometry

Use of 16S rRNA Gene Based Clone Libraries to Assess Microbial Communities Potentially Involved in Anaerobic Methane Oxidation in a Mediterranean Cold Seep

This study provides data on the diversities of bacterial and archaeal communities in an active methane seep at the Kazan mud volcano in the deep Eastern Mediterranean sea. Layers of varying depths in the Kazan sediments were investigated in terms of (1) chemical parameters and (2) DNA-based microbial population structures. The latter was accomplished by analyzing the sequences of directly amplified 16S rRNA genes, resulting in the phylogenetic analysis of the prokaryotic communities. Sequences of organisms potentially associated with processes such as anaerobic methane oxidation and sulfate reduction were thus identified. Overall, the sediment layers revealed the presence of sequences of quite diverse bacterial and archaeal communities, which varied considerably with depth. Dominant types revealed in these communities are known as key organisms involved in the following processes: (1) anaerobic methane oxidation and sulfate reduction, (2) sulfide oxidation, and (3) a range of (aerobic) heterotrophic processes. In the communities in the lowest sediment layer sampled (22–34 cm), sulfate-reducing bacteria and archaea of the ANME-2 cluster (likely involved in anaerobic methane oxidation) were prevalent, whereas heterotrophic organisms abounded in the top sediment layer (0–6 cm). Communities in the middle layer (6–22 cm) contained organisms that could be linked to either of the aforementioned processes. We discuss how these phylogeny (sequence)-based findings can support the ongoing molecular work aimed at unraveling both the functioning and the functional diversities of the communities under study

Steady decline in mean annual air temperatures in the first 30 k.y. after the Cretaceous-Paleogene boundary

The Cretaceous-Paleogene (K-Pg) boundary marks one of the five major mass extinctions of the Phanerozoic. The ways in which the climate system responded to a bolide impact and extensive volcanism at this time over different time scales are highly debated. We used the distribution of branched tetraether lipids (brGDGT) from fossil peats at two sites in Saskatchewan, Canada (paleolatitude ~55°N), to generate a high-resolution (millennial) record of mean annual air temperature (MAAT) spanning the last ~4 k.y. of the Cretaceous and the first ~30 k.y. of the Paleogene. Our study shows that MAATs ranged from 16 to 29 °C, with the highest value in the first millennia of the Paleogene. The earliest Paleogene averaged ~25 °C—maintaining or enhancing warmth from the latest Cretaceous—followed by a general cooling to ~20 °C over the following ~30 k.y. No abrupt postboundary cooling (e.g., an “impact winter”) or abrupt warming is evident in our data, implying that if such phenomena occurred, their duration was relatively short-lived (i.e., sub-millennial-scale). Further, no long-term impactor volcanism-driven warming is evident. The range of temperature change observed is considerably greater than that derived from marine proxy records over the same time interval. Our findings therefore more properly place bounds on the magnitude and duration of temperature change on land during this critical interval—the main setting for the demise of nonavian dinosaurs and the rise of mammals