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

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

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

The DeepMIP contribution to PMIP4: methodologies for selection, compilation and analysis of latest Paleocene and early Eocene climate proxy data, incorporating version 0.1 of the DeepMIP database

This is the final version of the article. Available from European Geosciences Union via the DOI in this record.Data availability. The data referenced in this manuscript are provided as Supplement Data Files 1 to 8. In the final version, these files will form DeepMIP database version 0.1 and will be accessible online via a citable DOI reference.The early Eocene (56 to 48 million years ago) is inferred to have been the most recent time that Earth's atmospheric CO2 concentrations exceeded 1000 ppm. Global mean temperatures were also substantially warmer than those of the present day. As such, the study of early Eocene climate provides insight into how a super-warm Earth system behaves and offers an opportunity to evaluate climate models under conditions of high greenhouse gas forcing. The Deep Time Model Intercomparison Project (DeepMIP) is a systematic model–model and model–data intercomparison of three early Paleogene time slices: latest Paleocene, Paleocene–Eocene thermal maximum (PETM) and early Eocene climatic optimum (EECO). A previous article outlined the model experimental design for climate model simulations. In this article, we outline the methodologies to be used for the compilation and analysis of climate proxy data, primarily proxies for temperature and CO2. This paper establishes the protocols for a concerted and coordinated effort to compile the climate proxy records across a wide geographic range. The resulting climate “atlas” will be used to constrain and evaluate climate models for the three selected time intervals and provide insights into the mechanisms that control these warm climate states. We provide version 0.1 of this database, in anticipation that this will be expanded in subsequent publications.Natural Environment Research Council (NERC)GNS Science Global Change through Time ProgrammeNational Science Foundation (NSF)KU Leuve

Introducing global peat-specific temperature and pH calibrations based on brGDGT bacterial lipids

Glycerol dialkyl glycerol tetraethers (GDGTs) are membrane-spanning lipids from Bacteria and Archaea that are ubiquitous in a range of natural archives and especially abundant in peat. Previous work demonstrated that the distribution of bacterial branched GDGTs (brGDGTs) in mineral soils is correlated to environmental factors such as mean annual air temperature (MAAT) and soil pH. However, the influence of these parameters on brGDGT distributions in peat is largely unknown. Here we investigate the distribution of brGDGTs in 470 samples from 96 peatlands around the world with a broad mean annual air temperature (-8 to 27 degrees C) and pH (3-8) range and present the first peat-specific brGDGT-based temperature and pH calibrations. Our results demonstrate that the degree of cyclisation of brGDGTs in peat is positively correlated with pH, pH = 2.49 x CBTpeat + 8.07 (n = 51, R-2 = 0.58, RMSE = 0.8) and the degree of methylation of brGDGTs is positively correlated with MAAT, MAAT(peat) (degrees C) = 52.18 x MBT'(5me) - 23.05 (n = 96, R-2 = 0.76, RMSE = 4.7 degrees C). These peat-specific calibrations are distinct from the available mineral soil calibrations. In light of the error in the temperature calibration (similar to 4.7 degrees C), we urge caution in any application to reconstruct late Holocene climate variability, where the climatic signals are relatively small, and the duration of excursions could be brief. Instead, these proxies are well-suited to reconstruct large amplitude, longer-term shifts in climate such as deglacial transitions. Indeed, when applied to a peat deposit spanning the late glacial period (similar to 15.2 kyr), we demonstrate that MAAT(peat) yields absolute temperatures and relative temperature changes that are consistent with those from other proxies. In addition, the application of MAAT(peat) to fossil peat (i.e. lignites) has the potential to reconstruct terrestrial climate during the Cenozoic. We conclude that there is clear potential to use brGDGTs in peats and lignites to reconstruct past terrestrial climate. (C) 2017 The Authors. Published by Elsevier Ltd

The DeepMIP contribution to PMIP4: methodologies for selection, compilation and analysis of latest Paleocene and early Eocene climate proxy data, incorporating version 0.1 of the DeepMIP database

The early Eocene (56 to 48 million years ago) is inferred to have been the most recent time that Earth's atmospheric CO₂ concentrations exceeded 1000 ppm. Global mean temperatures were also substantially warmer than those of the present day. As such, the study of early Eocene climate provides insight into how a super-warm Earth system behaves and offers an opportunity to evaluate climate models under conditions of high greenhouse gas forcing. The Deep Time Model Intercomparison Project (DeepMIP) is a systematic model–model and model–data intercomparison of three early Paleogene time slices: latest Paleocene, Paleocene–Eocene thermal maximum (PETM) and early Eocene climatic optimum (EECO). A previous article outlined the model experimental design for climate model simulations. In this article, we outline the methodologies to be used for the compilation and analysis of climate proxy data, primarily proxies for temperature and CO₂. This paper establishes the protocols for a concerted and coordinated effort to compile the climate proxy records across a wide geographic range. The resulting climate “atlas” will be used to constrain and evaluate climate models for the three selected time intervals and provide insights into the mechanisms that control these warm climate states. We provide version 0.1 of this database, in anticipation that this will be expanded in subsequent publications