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The fate of leaf lipids upon early diagenesis was monitored in a two year litterbag experiment in a soil and at the water-sediment interface of an adjacent pond. The biomarker content of degrading leaves exhibited substantial variability among litterbags, even for a given time step within a given environmental condition, likely reflecting natural microenvironmental variability. Due to this variability and the oxic conditions in the pond, no substantial difference between the soil and the pond could be evidenced in the biomarker degradation pattern. An occasional increase in the abundance of several biomarkers (β- sitosterol, oleanolic acid, C 16 phytyl ester, C 27 n -alkane) was also noted during the experiment, which was attributed to release of bound compounds and/or an external contribution. Nevertheless, absolute quantification showed that the concentration of all lipid constituents was reduced, but they exhibited different decay profiles: (i) rapid extensive degradation (phytyl ester), (ii) exponential-like decrease (fatty lipids) and (iii) variable degradation profile (polycyclic triterpenoids). However, all the main constituents initially present in the senescent leaves were still detected after two years of degradation in both environments. Fatty lipids abundances generally decreased to < 10% of the initial content but the main distribution features (carbon number maximum and predominance) remained unchanged. The results thus tend to validate their use as proxy for source and environment in ancient organic matter. They also suggest that, on a mid-term basis, a plant biomarker signature is not substantially affected by differential degradation in soil and at the water-sediment interface, at least for a qualitative approach. [ABSTRACT FROM AUTHOR]

• 3-OH FAs and brGDGTs analyzed in soils from an altitudinal transect in the French Alps. • Investigation of the environmental factors controlling the distribution of bacterial lipids. • Influence of soil traits predominant over MAAT. • Statistical identification of the individual bacterial lipids influenced by MAAT/pH required. • Development of local calibrations with MAAT and pH based on such identification. Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are a family of bacterial lipids widely used for temperature and pH reconstructions in terrestrial settings. 3-hydroxy fatty acids (3-OH FAs) with 10–18 carbon atoms, produced by Gram-negative bacteria, have been recently proposed as independent and complementary proxies of temperature and pH in terrestrial environments. Nevertheless, the correlations between mean annual air temperature (MAAT)/pH and bacterial lipid (brGDGTs/3-OH FAs) distributions show a large degree of scatter, as the relative abundance of these lipids is influenced by factors other than temperature and pH. A full understanding of the environmental parameters influencing bacterial lipid distribution in soils is required to increase the reliability of the temperature and pH proxies based on these compounds in terrestrial environments. The aim of this work was to determine and quantify the cumulative effect of environmental parameters on the distribution of both brGDGTs and 3-OH FAs along a well-documented composite altitudinal transect in the French Alps (234–2748 m). Redundancy analysis revealed that the influence of local parameters (pH and to a lesser extent, soil moisture and grain size, related to vegetation and soil types) on brGDGT and 3-OH FA distributions amounted to 48.1% and 26.1%, respectively, and was predominant over MAAT. This likely explained the weak or lack of relationships between MAAT and brGDGT-/3-OH FA-based indices in this region. The identification of lipids whose fractional abundance is correlated with MAAT or pH allowed the development of local calibrations with MAAT/pH applicable in the French Alps, which are representative of highly contrasted microenvironments, reflecting different types of soil and vegetation. The present study highlighted the importance of constraining the environmental factors affecting the distribution of 3-OH FAs and brGDGTs in terrestrial settings prior to any paleoenvironmental reconstruction. Such an approach should be reproduced in other sites, where local factors could also strongly influence the bacterial lipid distribution. [ABSTRACT FROM AUTHOR]

Highlights • 3-hydroxy fatty acids analysed in soils from two contrasting altitudinal transects. • Distribution of 3-hydroxy fatty acids correlated with air temperature and soil pH. • Promising pH and temperature proxies in terrestrial environments. Abstract Three hydroxy (3-OH) fatty acids (FAs), containing 10 to 18 C and a hydroxyl group in third position are characteristic components of Gram-negative bacteria. These compounds were used previously to detect and quantify Gram-negative bacterial communities in various types of samples, from terrestrial, aquatic and atmospheric environments. The relative abundance of 3-OH FAs in soils was recently shown to vary with mean annual air temperature (MAAT) and pH in soils from Mt. Shennongjia (China). In the current study, the concentrations and abundances of 3-OH FAs were determined in soils from altitudinal transects under tropical and temperate climates: Mt. Rungwe (SW Tanzania) and Mt. Majella (Central Italy), respectively. The aim was to (i) examine and compare the distributions of 3-OH FAs in soils from different climatic zones and (ii) to investigate the potential of 3-OH FAs as temperature and pH proxies. When combined with previously published data, a moderate correlation (R2 0.62) between the summed iso and anteiso to the total amount of normal 3-OH FAs (RIAN index) and pH was obtained. We show that Gram-negative bacteria respond in the same way to temperature variations in soils from different latitudes, with a relative increase of the anteiso to normal 3-OH FA ratios of the C 15 and C 17 compounds (RAN 15 and RAN 17 indices, respectively) with decreasing temperature. Nevertheless, the intercepts of the relationships between RAN 15 and MAAT are mountain-dependent, suggesting that regional calibrations may be required to use RAN 15 as a temperature proxy. In contrast with RAN 15 , the statistical similarity of the local relationships between RAN 17 and MAAT leads to a combined calibration (R2 0.60, residual mean error 5.1 °C) covering a wide range of temperature (ca. 0–25 °C). As 3-OH FAs seem well-preserved in sedimentary archives, this strengthens the potential of these compounds as a temperature and pH proxy for paleoreconstructions in terrestrial settings. [ABSTRACT FROM AUTHOR]

• Forest management practices can lead to distinct compositions of topsoil OM. • Thermal stability is likely constrained by mineral interactions. • Thermal analysis and Py-GC/MS highlight forest management impacts on OM. 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. [ABSTRACT FROM AUTHOR]

[Display omitted] • Lipid biomarkers from loess-paleosol sequences inform on palaeoenvironmental changes. • Shrub versus grass cover shifts suggested by n -alkyl compounds and triterpenoids. • Regional temperature variations suggested by bacterial membrane lipids. • Distinction between anthropogenic and climate impacts on local vegetation cover. • Significant impacts of reindeer herders on vegetation in sub-Arctic environment. Arctic reindeer herders demonstrate resilience to climate fluctuations by adjusting their pastoral practices to changing environments. The multiple phases of occupation at one of the oldest identified reindeer-herding sites, I A ^ rte 6 on the I A ^ mal peninsula, northwest Siberia, are thought to be linked to its local vegetation cover. Here we provide information on local palaeovegetation and climate shifts which occurred between the 7th and the 11th century CE based on lipid biomarkers. Aliphatic compounds, pentacyclic triterpenoids, branched glycerol dialkyl glycerol tetraethers (brGDGTs) and other lipids were analysed in four separate palaeosols from two loess-palaeosol sequences at the site. Based on different indices, the impact of human- or root-derived lipids and post-depositional microbial degradation on the signature of the studied pedosequences seem limited, which indicates that palaeobiomarkers are well preserved and representative of the analysed compounds. n -Alkanes, n -carboxylic acids, n -aldehydes and pentacyclic triterpenoids point to the progressive colonization of grasses, sedges and herbs at the site, which can be attributed to the regional decrease in temperature suggested by bacterial-derived brGDGTs. During the last phase of occupation, however, when proxies point to increasing temperatures, and shrubs would normally be expected to return, the shrub cover continued to decrease, probably due to the impact of camping and holding reindeer at the site. The decoupling trends observed for particular pentacyclic triterpenoids as potential dwarf birch biomarkers could suggest a preferential shift of species within shrubs, probably influenced by human activities. Multi-family lipid biomarker analysis therefore made it possible to distinguish anthropogenic impacts on the local vegetation cover from regional climatic changes, and show how significant the impacts of humans on local vegetation can be, even in extreme environments where such activities are limited. [ABSTRACT FROM AUTHOR]

Isoprenoid and branched glycerol dialkanol diethers (iso GDDs and br GDDs) have recently been detected in various environments, including sediment, soil and peat deposits. Their structures strongly resemble those of glycerol dialkyl glycerol tetraethers (GDGTs). Nevertheless, the origin of GDDs and their link to GDGTs remain unclear. Here we examined the concentration and distribution of iso GDDs and br GDDs, together with those of iso GDGTs and br GDGTs along a 4 m peat core from Tanzania. Whereas br GDDs have only been detected to date in their core lipid (CL) form, we report here, for the first time, br GDDs in both CL and intact polar lipid (IPL) forms, suggesting a biosynthetic origin for br GDDs. Concentrations of br GDGTs and br GDDs on one hand and of iso GDGTs and iso GDDs on the other hand, were observed to significantly co-vary ( R 2 0.49–0.58; p < 0.05), both for the CL and IPL fractions. Moreover, the fractional abundance of each GDD correlated significantly with that of its GDGT analogue ( R 2 0.33–0.97; p < 0.05). Taken together, the data show that GDDs and GDGTs are closely related and likely take part in common metabolic pathways, although the hypothesis of GDDs being degradation products of GDGTs cannot be excluded. [ABSTRACT FROM AUTHOR]

• %Corg and %N reflect significant inputs of OM in sediments during fireplace operation. • Lipids and bulk OM mark the use of wood as fuel and the involvement of animal OM. • Distinction between meat-cooking and bone-fueled fireplaces is possible. • N-compounds are characteristic of culinary use. A better understanding of the operation and use of prehistoric fires is fundamental to interpreting the organization of living spaces. Following a previous study that focused on the organic signatures of fireplaces fueled with wood and/or bones, this study targeted the completion of an experimental reference database through the addition of a wood-fueled fireplace dedicated to the cooking of meat. Different sedimentary features of this experimental fireplace were visually identified (e.g. darkening, reddening), sampled, and subjected to geochemical analysis. Corg and N contents were quantified, samples were extracted with organic solvents and analyzed through GC–MS and bulk organic matter was characterized through py(TMAH)-GC–MS. Five different samples were studied and compared with a control sample, representative of the local background. A significant increase of Corg and N contents was measured for the three samples presenting darkened or charred caracteristics. The meat-cooking fireplace seems to be characterized by the strong contribution of nitrogen, which was visible in elementary analyses as well as in the molecular composition of solvent extracts, and bulk organic matter. More specifically, compounds containing nitrile functions, amides, N-heterocyclic and N-aromatic compounds could be detected in solvent extracts. Amines, amides, N-heterocyclic and N-aromatic compounds could be identified in py(TMAH)-GC–MS. Some of these compounds present a relative stability in soils and could therefore aid in our comprehension and functional interpretations of archaeological fireplaces, and may, more particularly, make it possible to highlight the use of fireplaces for the cooking of meat. [ABSTRACT FROM AUTHOR]