Abstract not available

Ionizing radiation of organic matter (OM) is ubiquitous on the surface and in the subsurface of rocky planets such as Earth and Mars, and is associated with chemical changes in the elemental, isotopic, bulk and molecular compositions of OM over geological time scales. Plentiful efforts have been made in the last decade that contribute to growing understanding of subsurface OM irradiation and insights into perplexing petroleum system dynamics worldwide. This review opens with a brief introduction of recent progress in the technical application of OM radiolysis in multiple scientific areas to elucidate basic radiolysis principles that also govern both artificial and natural irradiation of OM. In light of these considerations, four major topics covering radiolysis in geological systems are addressed: (1) radiation of kerogen in radioactive shales and changes in OM chemical compositions, (2) radiolytic alteration of crude oil and its potential application in tracing oil residence time, (3) characteristics of radiolytic natural gases and geochemical templates for distinguishing natural gases of various origins, and (4) radiolytic synthesis of simple precursors into larger OM molecules. Highlights are the exploration of proxies using radiolytic changes in OM as geochronometers for oil residence time dating under topic (2), and the novel interpretation of obscured natural gas formations worldwide based on the newly proposed geochemical template for natural gas origins under topic (3). This review wraps up with a brief discussion of the radiation environment on Mars and an analogy between Mars and Earth, which bears valuable information on the preservation of OM on both planets in response to irradiation and may shed light on the origin of life and evidence for life on extraterrestrial planets.

Lichens are found in a wide range of terrestrial habitats and have important roles in terrestrial ecosystems. However, because lichens are easily decomposed and are rarely preserved as fossils, their paleoenvironmental ecology and evolutionary history remain a mystery. We performed lipid analyses on 29 lichen samples belonging to Lecanoromycetes, the largest class of lichens, from several locations in Japan, to determine their potential for use as taxonomic tools and biomarkers. We found that the lichens contained aliphatic hydrocarbons, including n-alkanes, alkenes, and long-chain branched alkanes, fernenes, diploptene, and hop-21-ene. Lichens with a green algal photobiont (photosynthetic symbiotic algae) contained 1,8-heptadecadiene or 6,9-heptadecadiene and 8- and 7-heptadecene, whereas lichens with cyanobacteria as a photobiont did not contain the heptadecadienes but did contain octadecene, nonadecene and nonadecadiene. These differences in characteristics could be attributed to phylogenetic differences in the photobionts that comprised the lichens, indicating that the alkene composition could be used for lichen chemotaxonomy. Although additional research is needed to confirm that this signal gets preserved in sedimentary archives, our results suggest a previously unknown origin for the C17–C19 alkenes in sediments and imply that these components could be used to reconstruct the past composition of lichens.

Concentrations of particulate organic carbon (POC) and total hydrolyzable amino sugars (THAS) were measured along a transect of the dynamic South Yellow Sea (SYS) to investigate the bioreactivity and bacterial reworking of particulate organic matter (POM). Results showed that POM bioavailability was linked with primary production, as revealed by the significant correlation between chlorophyll-a concentrations and the diagenetic indicator glucosamine/galactosamine (GlcN/GalN). Production of bioavailable POM could rapidly stimulate microbial activity, generating hot spots of heterotrophic alteration. Lower GlcN/GalN ratios (<3) observed in the entire SYS indicate that POM underwent extensive microbial alteration. In particular, extremely low GlcN/GalN ratios (∼0.7) were found in the Yellow Sea Cold Water Mass, reflecting high bacterial alteration of POM. Estimates based on the bacterial biomarker muramic acid showed that on average ∼13% of POM in the SYS was of bacterial origin. Elevated bacterial contributions were found in both nearshore and offshore areas. Strong mixing in the nearshore and the presence of cyclonic eddies in offshore waters may increase the residence time of POM in the water column and thus promote bacterial transformation of POM. Overall, our findings indicate that bacterial reworking of POM varies with productivity and that the extensive bacterial transformation of the remaining POM observed in the water column probably enhances long-term carbon sequestration.

Glycerol dialkyl glycerol tetraethers (GDGTs) have been widely applied to coastal marine sediments to reconstruct past temperature variability. However, coastal environments are characterised by variability in the source, age and/or thermal maturity of different organic carbon (OC) pools and may bias various GDGT-based proxies. Here we analyse TEX86 and MBT5ME values within a shallow marine sediment core (South Dover Bridge, Maryland) from the Paleocene-Eocene Thermal Maximum (PETM; 56 million years ago (Ma)) to explore how changes in OC reworking influence GDGT-derived sea surface and terrestrial temperature estimates, respectively. We demonstrate that TEX86 values are unaffected by an increase in soil- and fossil organic carbon during the PETM. In contrast, we find large and unexpected variations in MBT5ME-derived temperature estimates (∼6 to 25 °C) during the onset and core of the PETM at some sites. This coincides with input of reworked terrestrial OC from the Cenomanian-aged Raritan Formation. However, there is also an increase in the degree of cyclisation of tetramethylated branched GDGTs, suggesting that branched GDGTs are also derived from marine in-situ production. These factors preclude terrestrial temperature reconstructions at this site. We explored whether OC reworking is problematic in other PETM-aged coastal environments. Using GDGT metrics and the Branched and Isoprenoid GDGT Machine learning Classification algorithm (BIGMaC), we demonstrate that TEX86 values are mostly unaffected by changes in OC sources. However, MBT5ME values are affected by marine and/or freshwater overprints, especially in environments with low terrestrial OC input. Taken together, this study highlights the importance of constraining the provenance of different GDGTs in marine and lacustrine environments.

Knowledge of the formation and enrichment mechanisms of shale oil is essential to understanding its mobility and hence a critical aspect for evaluating shale oil exploration and production. Semi-open hydrous pyrolysis experiments were performed on an organic-rich shale to simulate the petroleum generation and expulsion processes of Type II kerogen. The residual rocks matured to different levels (Easy%Ro = 0.50–1.37) were thereafter treated with stepwise extraction to obtain free and bound bitumen fractions. This study focuses on the structural characteristics of kerogen, bitumen fractions, and expelled oil during shale maturation using Fourier transform infrared (FTIR) spectroscopy and quantitative flash pyrolysis–gas chromatography (Py–GC). The results reveal that the composition of expelled oils changes with increasing maturity, whereas an opposite trend in structural composition was observed for kerogen after significant oil expulsion from the shale occurs, beginning at Easy%Ro = 0.79. A notable change is that aliphatic carbon chains of kerogen became shorter and/or more branched while those of expelled oil appeared to be more aliphatic with longer carbon chains at this stage. However, the overall compositional structures of shale bitumen fractions, both in free and bound phases, show only slight changes within the oil window stage. The bound bitumen is generally enriched in oxygenated functional groups as compared to free bitumen, indicating that the bound bitumen is related mainly to the interaction between the mineral surface and the bitumen–kerogen matrix. During maturation, the cracking (including defunctionalization) and condensation of kerogen and bitumen fractions, as well as a compositional fractionation due to oil expulsion, are likely to be the main factors influencing the opposite trend observed in structural compositions between kerogen and expelled oil. These processes may control the quality and content of expelled oil and bitumen in a petroleum system. Nevertheless, kerogen, expelled oil and bitumen show a gradual trend of decarboxylation during shale maturation in general.

The formation mechanism for thermogenic gas remains unresolved. Disputes are focused on: (1) stability barrier for decomposition of oil to gas and wet gas to methane, and (2) inconsistence in dryness ratio (C1/ΣC1–5) between gases produced in pyrolysis experiments and in natural reservoirs. Here, we demonstrate the variation trend of dryness ratio (C1/ΣC1–5) with temperatures and thermal stress levels, and the correlation of dryness ratios with the yields of liquid components (ΣC8+) in confined pyrolysis experiments (gold capsules) of twenty coals. At both heating rates of 2 and 20 °C/h, dryness ratios of gaseous hydrocarbons at first decrease, and then increase with increasing temperatures and thermal stress levels. Dryness ratios of produced gases can be very high in the range of 66.3–95.7 wt% at initial temperature about 334 °C and heating rate of 20 °C/h, corresponding to EASY%Ro 0.56. We suggest that these gases are not the original products released from kerogen, but have been altered via wet gas incorporation to kerogen. Larger oil molecules (C8+) are more competitive in incorporating to kerogen compared with wet gases, and therefore, prohibit wet gas incorporation, leading to the observed trend of gas dryness ratios with increasing temperature and maturity and the negative correlation between dryness ratios and the yields of liquid components (ΣC8+). The conflicting results between the yields and carbon isotopes of wet gases produced in the isothermal confined pyrolysis experiments for coal plus oil can be well interpreted using the reaction mechanism that wet gases incorporate to kerogen while oil components retard this incorporation. Once free oil and wet gas molecules are reincorporated to kerogen, the bound molecules can easily decompose to smaller molecules due to substantial reduction of activation energy for carbon-carbon bond rupture. Petroleum formation from kerogen can be a recycling process: kerogen first releases oil compounds, and then free molecules reincorporate to kerogen and further decompose to smaller molecules, and finally to methane.

Organic solvent extracted bitumen (EB) and microscopically observed solid bitumen (SB) carry many geological implications in unconventional source-rock reservoirs. EB is a commonly used term in organic geochemistry, and SB is normally used in organic petrology. Although both EB and SB are secondary organic matter initially formed from kerogen degradation and partially describe the same components, they are defined by different physical and chemical criteria and have specific applications, and thus are rarely comparatively investigated. In this study, by taking the shale of the seventh member of the Upper Triassic Yanchang Formation in the Ordos Basin, China, as a case study, we performed an integrated characterization on the two types of bitumen. The characterization was carried out on source rocks and reservoir assemblages at two scales: lamina-scale (organic-rich lamina and silty lamina) and lithofacies-scale (shale and sandstone). Programmed temperature pyrolysis (Rock-Eval 7 pyrolysis), gas chromatography–mass spectrometry (GC–MS), and Raman spectroscopy were used in this study. The samples are distributed within a 12 m interval and therefore should have experienced the same degree of thermal stress. However, maturity parameters derived from GC–MS for EB and Raman spectroscopy for SB exhibit a different inferred thermal maturity between source rocks and reservoirs at both lithofacies- and lamina-scales. The side-chain scission reactions related (non-)biomarker parameters such as Ts/C30H, ΣnC21−/ΣnC22+ alkanes, relative C21 + C22 sterane content and TA(I)/TA(I + II) suggest higher thermal maturity in source rocks (shale and organic-rich lamina) than the corresponding reservoirs (sandstone and silty lamina), while Raman-derived parameters RBS and G-FWHM indicate higher maturity in reservoirs than the corresponding source rocks. It is speculated that the EB measured by GC–MS comprises saturated and aromatic components corresponding to relatively mobile hydrocarbons. The maturation of the source rock exerts greater control over this component than that of the reservoir. In comparison, the SB measured using Raman spectroscopy mainly consists of solid residue left behind after migration and/or decomposition of a once-liquid oil phase that is less readily able to move. It is more intensely altered by the organic–inorganic interactions (mineral dissolution–precipitation processes) in the reservoir than that in the source rock, resulting in a consolidated SB with higher aromaticity. The storage ability of silty lamina in shale may complicate the data interpretation of geochemical differences in EB- and SB-derived parameters. On a practical note, when assessing thermal maturity, taking into the account the lithology or rock texture, which affects the organic–inorganic interactions, as well as specific components detected by different techniques may provide helpful clues to explain some contradictory results.

Organic compounds are widely used for paleoclimatic and paleoenvironmental reconstructions. Bulk organic proxies, however, are more complicated to interpret due to the multiple causes of variation in climatic and environmental conditions and the degree of diagenetic alteration. As labile compounds, rich in easily degradable function and generally richer in heteroatoms such as oxygen and nitrogen, decompose, the remaining organic matter becomes progressively richer in refractory carbon and its carbon content increases. Thus, in a peat deposit composed almost entirely of organic matter, total organic carbon (TOC) is expected to increase with time and depth, which could mask the paleoclimatic signal. We propose a simple model for peat sediments to remove the decomposition signal based on a logarithmic function fitted with a partial dataset where decomposition is the main parameter. The subtraction of the obtained logarithmic function to the raw data (i.e., measured data) leads to “residual” data. We discuss the influence of different parameters (water table depth, vegetation, microbial community) on the “residual” data and their possible link to paleoclimatic and paleoenvironmental variations. This method is tested on bulk elemental and isotopic data obtained from a new peat core from the Adamawa Plateau (North-East Cameroon) covering nearly 10 ka cal BP. Comparison with Rock-Eval® parameters highlights similar variations between the Hydrogen Index and residual TOC variations, supporting the interpretation based on residual TOC. Our approach allows to extract paleoenvironmental information from decomposition-prone bulk organic proxies and can be generalized to peat deposits where decomposition plays a major role in controlling bulk data.

The effect of forest management practices on carbon quality is poorly documented. To assess changes in the quality and stability of soil organic carbon (SOC) of a temperate forest upon human activities, we investigated soil from forests (i) developed following natural regeneration after clearcutting 20 and 40 years ago, (ii) developed following afforestation on an abandoned crop area 40 years ago and (iii) in an area where regular clear-cut (with wood residues input) was conducted 40 years ago. Topsoil and subsoil layers were collected (0–20 cm and 50–80 cm). Soil organic matter (OM) was characterized by elemental analysis (total carbon and total nitrogen), thermal analysis (Rock-Eval®) and thermochemolysis (i.e., Py-GC/MS in the presence of tetramethylammonium hydroxide (TMAH)). In addition, a size fractionation to separate the labile coarse fraction (50–2000 μm) from the fine fraction (<50 µm) was performed. These fractions were analyzed by thermal analysis.Despite no measurable differences in carbon and nitrogen contents, the characterization of the OM by thermal analysis, and the relative quantification of OM compounds revealed differences in the composition in OM for the topsoil layers. The thermal analysis clearly distinguished sites with inputs of woody residues (higher HI) with a higher relative contribution of lignin and cutin/suberin compounds. However, the OM thermal stability seems mainly controlled by the organo-mineral interactions rather than chemical composition. Combination of Rock-Eval® thermal analysis and Py-GC/MS suggests that thermal stability cannot be used as an indicator of stability in specific contexts where pedogenetic processes are deeply modified by regular and extensive anthropogenic inputs of woody residues.

The Middle Permian Qixia and Maokou formations (Fms), are important targets for current gas exploration in the Sichuan Basin. In recent years, high-yield industrial gas flow has been obtained in different structural zones of the basin. Based on the molecular and isotopic compositions of natural gas and reservoir bitumen, biomarker composition, and geological conditions, the genetic types, maturity, and sources of natural gas reservoired in the Qixia and Maokou Fms in different structural zones in the basin were analyzed. The following conclusions can be drawn: (1) the molecular and isotopic compositions of natural gas reservoired in the Middle Permian Qixia and Maokou Fms from different areas in the Sichuan Basin differ considerably; (2) the Middle Permian natural gas is oil-type gas, which is mainly generated by oil cracking; (3) most of the natural gas reservoired in the Qixia and Maokou Fms in the Sichuan Basin has reached the over-mature stage. The maturity of the natural gas from the northwestern Sichuan Basin is the highest, followed by gas from eastern and southern Sichuan, and part of natural gas in Southern Sichuan is high-maturity; (4) except for the slight thermochemical sulfate reduction (TSR) secondary alteration in the central Sichuan Basin, an effect of TSR was not observed in other areas; and (5) natural gas is controlled by the regional hydrocarbon kitchen. Gas in the eastern and southern Sichuan areas mainly originates from the Lower Silurian Longmaxi Fm shale, with a small contribution from marl in the Maokou Fm. The gas of the first member of the Maokou Fm has self-generation and self-storage characteristics, with a small contribution of the Longmaxi Fm shale. The Middle Permian gas in northwestern Sichuan is a mixture of gas generated from source rocks of the Lower Cambrian Qiongzhusi and Maokou Fms, whereas that in central Sichuan mainly originates from source rocks of the Qiongzhusi Fm. The Middle Permian gas in southwestern Sichuan mainly originates from its own source rock, and the natural gas reservoired in Permian volcanic rocks in the Chengdu–Jianyang area was generated by the mudstone of the Qiongzhusi Fm.

Endospore distributions in marine sediments are influenced by geological conduits providing routes for subsurface to surface microbial dispersal. To examine this phenomenon in more detail, endospore abundance was determined by quantifying dipicolinic acid (DPA) in 16 deep sea sediment cores from hydrocarbon prospective areas in the NW Atlantic Ocean. DPA concentrations were compared with measurements of over 250 different gaseous and liquid hydrocarbon compounds used to assess for the presence of thermogenic hydrocarbons. This revealed significantly higher levels of endospores at hydrocarbon seep sites than at most hydrocarbon-negative sites. In one exceptional case, a hydrocarbon-negative core in close proximity to adjacent thermogenic seep sites exhibited high endospore abundance, indicating either deposition of endospores emitted from the subsurface via nearby seepage, or alternatively a historical thermogenic hydrocarbon seep where hydrocarbons can no longer be detected by standard geochemistry approaches. This work expands the application of DPA as a proxy for quantifying dormant endospore biogeography of both recent and paleoenvironmental hydrocarbon seep sites.

Lipid biomarkers, such as the various bacteriohopanetetrol (BHT) isomers studied here, are useful tools in tracing bacterially mediated nitrogen and carbon cycle processes affecting greenhouse gas emissions, including the anaerobic oxidation of ammonia. Three BHT isomers occur commonly in the environment. By gas chromatography, BHT-34S elutes first; it is produced by numerous bacteria. The two later eluting isomers are more constrained in their origin. The marine anammox bacteria ‘Ca. Scalindua’ is the only known producer of a BHT isomer of unknown stereochemistry (BHT-x), making BHT-x a diagnostic biomarker in anoxic marine settings. The BHT-34R isomer is produced by three freshwater aerobic heterotrophic producers (Frankia spp., Acetobacter pasteurianus, and Komagataeibacter xylinus), a freshwater serine-cycle (Type II) methanotroph (Methylocella palustris), and the freshwater anammox ‘Ca. Brocadia’, which makes the detection of freshwater anammox using BHT-34R more complicated. We investigated whether the source of BHT-34R in freshwater environments could be ascertained via its δ13C value. We used conventional on-column gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) (as opposed to high temperature GC-C-IRMS) to determine the δ13C composition of acetylated BHT isomers in cultured bacteria and bacterial enrichments. We combined these with bulk biomass and substrate δ13C compositions to establish carbon isotopic fractionation factors. The two anammox genera had large fractionation factors from dissolved inorganic carbon (DIC) to biomass (Δ13Cbiomass – DIC = –43.8 to –26.4 ‰) and to BHTs (Δ13CBHT – DIC = –53.8 to –38.2 ‰), which clearly distinguished them from the freshwater aerobic heterotrophic producers (Δ13Cbiomass – substrate = –2.3 to –0.1 ‰; Δ13CBHT – substrate = –12.8 to 5.2 ‰). Methylocella assimilated mainly carbon from DIC, rather than from methane, into its biomass and BHT, and previous work suggested this assimilation comes with relatively small fractionation. Thus, in peatlands, the BHT δ13C values of Methylocella would not reflect the low δ13C values of biogenic methane. Consequently, the presence of BHT-34R with low δ13C values relates to ‘Ca. Brocadia’ and presents a novel tool to trace anammox in freshwater environments.

Major extractable lipid biomarkers (hydrocarbons, sterols and fatty acids) were assessed in Lake Seeburg, a shallow eutrophic lake that has increasingly been suffering from cyanobacterial blooms due to continued anthropogenic nutrient inputs over the last decades. Over the course of one year (2018/19), the distributions of these compounds were analyzed in the inflow, the lake water, and the topmost sediments (0–2 cm) to assess their origin and transfer into the lake deposits. Principal component analysis (PCA) was used to cluster the studied biomarkers into 5 groups with similar characteristics. These groups were comprised of (i) compounds delivered from external sources via the inflow, (ii) autochthonous compounds formed in the lake by eukaryotes or (iii) bacteria, (iv) compounds accumulating in the surface sediment, and (v) C27 to C29 stenols together with their degradation products, C27 to C29 5α(H)-stanols. Their seasonal partition clearly revealed that C27 stenols mainly derived from autochthonous sources within the lake, whereas C29 stenols largely reflect allochthonous material reaching the lake via the inflow. Analysis of stenol plus stanol concentrations with depth in two lake sediment cores (≈30 and 50 cm) found highest C27 to C29 ratios in surface sediments with lowest ratios at depth. These signals are interpreted to reflect the increasing trend of eutrophication of Lake Seeburg and, thus, enhanced autochthonous organic matter production in the lake over the last decades. The abundances of C27 vs. C29 stenols, summed with their respective degradation products, 5α(H)-stanols, are considered as suitable molecular indicators to qualitatively reconstruct historical eutrophication trends.

Methane stored in marine sediments can form by microbial and thermal decomposition of organic matter. Identifying the source of methane allows us to assess the potential of natural gas reservoirs and the limits of subsurface microbial life. However, such assessments are complicated by the burial and transport of methane, which can produce mixtures from multiple sources. We measured the abundances of stable isotopes (13C/12C and D/H), clumped isotopologue 13CH3D, and n-alkanes (C1/C2+3, methane over ethane plus propane) for gas samples collected by mud-logging to investigate how 13CH3D can be used to constrain sources of methane. Two kilometer-scale depth profiles representing the transition between microbial and thermal methanogenic zones were analyzed from the northeastern Gulf of Mexico and the western Black Sea. We found that Δ13CH3D values of methane do not follow conservative two-component mixing between shallow microbial methane and deep thermogenic methane transported by advection. Rather, methane isotopologues indicate re-equilibration along geothermal gradients following burial, which continues up to apparent temperatures of 100 ± 15 °C. The re-equilibration is likely microbially catalyzed, although this apparent temperature is ca. 20 °C higher than the putative upper-temperature limit of microbial methanogenesis in marine sediments. Above 150 °C, methane isotopologues are expected to equilibrate along geothermal gradients because the rate of abiotic D/H exchange becomes comparable to that of temperature increase with burial. This study provides novel kilometer-scale profiles of clumped methane isotopologues as a means to trace the upper-temperature limits of microbial activity in hydrocarbon-rich marine sedimentary environments.

Abstract not available

Abstract not available

Compound-specific carbon isotope ratios (CSIA) were measured for a suite of lipid biomarker compounds extracted from immature, late Ediacaran sedimentary rocks from drill cores sampled across Baltica. Using a newly developed picomolar‐scale CSIA (pico‐CSIA) method, we measured carbon isotope compositions of the abundant n-alkanes and hopanes, as well as C29 sterane, pristane, and phytane. Total organic carbon (TOC) of the Kotlin Regional Horizon in Baltica (Saint Petersburg area, Utkina Zavod drill core), from a low-salinity coastal environment, is consistently enriched in 13C by up to 10‰, compared to that for Redkino and Kotlin marine rocks from other locations in Baltica. This 13C enrichment is also recorded by the n-alkanes, hopanes, phytane, and C29 sterane. In all locations, the δ13C values of the C29 sterane are within 2‰ of the bacterial hopane δ13C values and within 0.7‰ of δ13CTOC, suggesting that the abundant hopanes within these sediments could be derived from RuBisCO Calvin-Benson-Bassham pathway-utilizing organisms, as well as from bacterial heterotrophs. Since δ13Clipid signature tracks δ13CTOC values for the Kotlin Regional Horizon samples from Utkina Zavod location, the significant 13C enrichments in this interval reflect either the δ13C composition of DIC used for autotrophy or a muted magnitude of carbon isotope fractionation during lipid biosynthesis, but are not due to enhanced preservation of organic compounds and geopolymers derived from 13C-enriched biochemicals. Pico-CSIA and biomarker data provide evidence for both regional environmental heterogeneity and secular changes in carbon cycling during deposition of sediments of the Kotlin and Redkino Regional Horizon intervals.

Soil water repellency (SWR) is an inability of soil to spontaneously absorb water. It affects the spatial distribution of soil moisture, may cause formation of preferential flow, increase surface runoff and the risk of water erosion, or affect nutrient availability for crops. Although there is a general agreement among published data that SWR is caused by hydrophobic components of soil organic matter (SOM), more comprehensive information is needed. Additionally, the link between SWR occurrence and SOM genesis has not been studied sufficiently. In this work, we analyzed SOM in water-repellent soils by pyrolysis combined with gas chromatography and mass spectrometry (Py-GC–MS). The samples were taken from two forest ecosystems in Slovakia: relatively dry pine–oak forest, located in the Záhorská nížina lowland (Záhorie), and spruce forest in the High Tatras with a colder and more humid climate. The results showed that the composition of SOM at both sites is dominated by partially decomposed residues of plant biomass. Whereas most compounds detected in the Záhorie samples were identified as pyrolysis products of lignin, the pyrolysates of the High Tatras soils originated mainly from polysaccharide-like substances. Although lauric (12:0), myristic (14:0) and palmitic (16:0) fatty acids were detected in pyrograms of water-repellent samples, the results suggest that the residues of lignin decomposition may contribute to SWR as well. Pyrolysates such as methylguaiacol, vinylguaiacol, dimethylphenol, or the methyl ester of vanillic acid are examples of less polar lignin-like moieties. Py-GC–MS data, as well as other soil properties, suggest that SWR at both sites is associated with the accumulation of certain SOM components in the topsoil. Acidic pH, higher C/N ratio and coarse soil texture prevent organic carbon stabilization in the studied soils. As a result, SOM is in great part composed of accumulated particulate residues with lignin-like origin and lipidic coatings, which contribute to SWR development during drier conditions.

Hydroxylated isoprenoid glycerol dialkyl glycerol tetraethers (OH-GDGTs), a class of lipids that widely occur in global marine and lacustrine environments, have been used as tools for temperature reconstruction. Reports on their occurrence in soils, however, are rare. Here, we report the downward variation in distribution and concentration of OH-GDGTs in three soil profiles (SP) from Mount Yujiashan in Wuhan, central China. The OH-GDGT concentrations show significant correlations with that of crenarchaeol and decreased with soil depth, likely in relation to the decreased oxygen availability of OH-GDGT-producing archaea with depth. Crenarchaeol was likely to be produced primarily by several thaumarchaeotal lineages, e.g. group I.1a, I.1b, and SAGMCG (South Africa Gold Mine Crenarchaeotal Group)-1, whereas OH-GDGTs were presumed to be contributed primarily by SAGMCG-1 and to a lesser extent, by group I.1a Thaumarchaeota based on 16S rRNA gene amplicon sequencing. OH-GDGTs were dominated by OH-GDGT-2, differing significantly from aquatic settings. This results in markedly higher RI-OH and RI-OH′ (both expressing the ring index of OH-GDGTs) values in soils than in marine sediments, suggesting a different response of terrestrial OH-GDGTs to temperature and (or) a significant bias towards summer temperature in RI-OH and RI-OH′ for soils.