Lipid Biomarker Analysis Research Articles

Warming and Carbon Injection at the Paleocene‐Eocene Boundary: Bayesian Modeling Supports Synchroneity

AbstractWe evaluate lead‐lag relationships between warming associated with the Paleocene‐Eocene thermal maximum (PETM) and the attendant carbon isotope excursion (CIE) recorded in sedimentary archives from the mid‐Atlantic continental margin. Cores from the New Jersey coastal plain (NJCP) provide thick (up to 15 m), rapidly deposited shelf PETM sections recording a 6–8°C warming based on the TEX86 paleothermometer. Updip cores from Medford, NJ provide the most expanded CIE onset, associated with a gradual lithologic change from uppermost Paleocene glauconitic sands to the lowermost Eocene kaolinitic Marlboro Clay. The relative thickness of these transitional sediments and the CIE onset allow for high‐resolution stable isotopic (bulk sediment, foraminifera, and organic carbon) and lipid biomarker analyses. The TEXH86‐derived temperature records from Medford cores show no warming prior to the CIE onset, with the carbon isotopic decrease in phase with temperature. Previous studies of more downdip PETM sections on the NJCP suggested that warming preceded the CIE, consistent with a thermal trigger for carbon release. Re‐evaluation of published records and Bayesian analysis of TEXH86‐derived temperature and δ13C from five NJCP sites do not indicate a statistically discernible lead or lag of carbon injection and warming. Though we can not preclude that a lead or lag exists, our analysis suggests that a synchronous CIE onset and warming is the most likely scenario on the NJ paleoshelf.

Sedimentary organic matter signature hints at the phytoplankton-driven biological carbon pump in the central Arabian Sea

Abstract. The central Arabian Sea, a unique tropical basin, is profoundly impacted by monsoon wind reversal affecting its surface circulation and biogeochemistry. Phytoplankton blooms associated with high biological productivity and particle flux occur in the northern part of the central Arabian Sea due to summer-monsoon-induced open-ocean upwelling and winter convection. The core oxygen minimum zone (OMZ) at intermediate water depths is another important feature of the northern central Arabian Sea and fades southward. In this study, we attempt to interlink how these factors collectively impact phytodetrital export to the sediment. Short sediment core-top (1 cm) samples representing the recent particle flux signatures were analysed from five locations (21 to 11° N; 64° E) in the central Arabian Sea. Previously, we used core-top (0–0.5 cm) samples and observed a trend between diatom frustule abundance and diversity with bulk sedimentary parameters indicating a spatial variability in phytodetrital export to the sediment. To verify this observation further, lipid biomarkers of key phytoplankton groups and a sea surface temperature (SST) proxy have been analysed in addition to diatom frustules. The C37 alkenone-based SST proxy indicated cooler SST (27.6 ± 0.25 °C) in the north (21–15° N) mostly due to upwelling (summer) and convective mixing (winter). Warmer SSTs (+0.4 °C) are measured in the south, which usually remains nutrient-poor. This trend was consistent with satellite-derived average SST values (2017–2020). Lipid biomarker analysis suggests that dinoflagellates were likely to be the highest contributor, as indicated by dinosterol and its degradative product dinostanol, followed by brassicasterol and C37 alkenone, likely representing diatoms and coccolithophores, respectively. The north, which largely experiences periodic phytoplankton blooms and is influenced by the thick OMZ, revealed the highest contents of organic matter, diatom frustules (diversity and abundance), dominated by large, thickly silicified cells (e.g. Coscinodiscus and Rhizosolenia) and phytoplankton lipid biomarkers, as well as lower contents of zooplankton biomarkers (cholesterol and cholestanol). In contrast, relatively smaller chain-forming centric (e.g. Thalassiosira) and pennate (e.g. Pseudo-nitzschia, Nitzschia, Thalassionema) diatom frustules along with lower phytoplankton lipid biomarker contents were found in the south, where zooplankton biomarkers and silicious radiolarians were more abundant. The possible impacts of the OMZ on particle flux related to the phytoplankton community, including zooplankton grazing and other factors, have been discussed.

Relevance of combined influence of nutritional and inflammatory status on non-alcoholic fatty liver disease and advanced fibrosis: A mediation analysis of lipid biomarkers.

This study aimed to investigate the relationship between advanced lung cancer inflammation index (ALI) and non-alcoholic fatty liver disease (NAFLD) and advanced liver fibrosis (AF). A total of 5642 individuals from the National Health and Nutrition Examination Survey (NHANES) between 2017 and 2020 were examined. Limited cubic spline regression model, and weighted logistic regression were employed to determine if ALI levels were related to the prevalence of NAFLD and AF. Additionally, a mediating analysis was conducted to investigate the role of lipid biomarkers, such as total cholesterol (TC) and high-density lipoprotein cholesterol (HDL-C), in the effects of ALI on the prevalence of NAFLD and AF. After adjusting for potential confounders, a significant positive association was found between ALI with NAFLD and AF prevalence. Compared with those in ALI Tertile 1, participants in Tertile 3 had higher odds of NAFLD prevalence (odds ratio [OR]: 3.16; 95% confidence interval [CI]: 2.52-3.97) and AF (OR: 3.17; 95% CI: 2.30-4.36). Participants in both Tertile 2 and Tertile 3 had lower odds of developing AF (P for trend=0.005). Moreover, we discovered a nonlinear association between ALI and NAFLD. An inflection point of 74.25 for NAFLD was identified through a two-segment linear regression model. Moreover, TC and HDL-C levels mediated the association between ALI and NAFLD by 10.2% and 4.2%, respectively (both P<0.001). Our findings suggest that higher ALI levels are positively associated with an increased prevalence of NAFLD and AF, partly mediated by lipid biomarkers.

Hyperexpansion of genetic diversity and metabolic capacity of extremophilic bacteria and archaea in ancient Andean lake sediments

BackgroundThe Andean Altiplano hosts a repertoire of high-altitude lakes with harsh conditions for life. These lakes are undergoing a process of desiccation caused by the current climate, leaving terraces exposed to extreme atmospheric conditions and serving as analogs to Martian paleolake basins. Microbiomes in Altiplano lake terraces have been poorly studied, enclosing uncultured lineages and a great opportunity to understand environmental adaptation and the limits of life on Earth. Here we examine the microbial diversity and function in ancient sediments (10.3–11 kyr BP (before present)) from a terrace profile of Laguna Lejía, a sulfur- and metal/metalloid-rich saline lake in the Chilean Altiplano. We also evaluate the physical and chemical changes of the lake over time by studying the mineralogy and geochemistry of the terrace profile.ResultsThe mineralogy and geochemistry of the terrace profile revealed large water level fluctuations in the lake, scarcity of organic carbon, and high concentration of SO42--S, Na, Cl and Mg. Lipid biomarker analysis indicated the presence of aquatic/terrestrial plant remnants preserved in the ancient sediments, and genome-resolved metagenomics unveiled a diverse prokaryotic community with still active microorganisms based on in silico growth predictions. We reconstructed 591 bacterial and archaeal metagenome-assembled genomes (MAGs), of which 98.8% belonged to previously unreported species. The most abundant and widespread metabolisms among MAGs were the reduction and oxidation of S, N, As, and halogenated compounds, as well as aerobic CO oxidation, possibly as a key metabolic trait in the organic carbon-depleted sediments. The broad redox and CO2 fixation pathways among phylogenetically distant bacteria and archaea extended the knowledge of metabolic capacities to previously unknown taxa. For instance, we identified genomic potential for dissimilatory sulfate reduction in Bacteroidota and α- and γ-Proteobacteria, predicted an enzyme for ammonia oxidation in a novel Actinobacteriota, and predicted enzymes of the Calvin–Benson–Bassham cycle in Planctomycetota, Gemmatimonadota, and Nanoarchaeota.ConclusionsThe high number of novel bacterial and archaeal MAGs in the Laguna Lejía indicates the wide prokaryotic diversity discovered. In addition, the detection of genes in unexpected taxonomic groups has significant implications for the expansion of microorganisms involved in the biogeochemical cycles of carbon, nitrogen, and sulfur.EPcqnK6xUD66cr6MUL2q3UVideo

A matter of extraction – Extraction yields and ratios of faecal lipid biomarker from archaeological soils using Soxhlet, microwave-assisted and accelerated-solvent extraction

The performance of Soxhlet (SOX), microwave-assisted (MAE) and accelerated-solvent extraction (ASE) in the analysis of faecal lipid biomarkers (FLB, Δ5-sterols, stanols, stanones) from archaeological soils was investigated to assess effectiveness and reproducibility of the extraction methods. Results from two Anthrosols that were analysed in six replicates show that SOX achieves significantly higher extraction yields for individual substances and steroid sums than MAE, while ASE produces the lowest lipid yields. Regarding the FLB ratios, which are used for sourcing of faeces, the three extraction methods show comparable values with three out of five ratios differing significantly between different soil samples. The reproducibility of extraction yields decreases with SOX > ASE > MAE, as well as for concentrations <100 ngg−1 sediment. Analyses of six different soils indicate a weak influence of soil properties (pH, texture, total organic carbon and cation exchange capacity) on the effectiveness of extraction methods. From our study we conclude that the classical SOX is still the preferred extraction approach when reliably higher FLB yields are of foremost interest or low concentrations are expected, as it is most effective and reproducible. However, considering the drawbacks of SOX (high extraction times and high solvent consumption), MAE and ASE appear to be comparably attractive for extracting FLBs in archaeological contexts. In addition to comparable FLB ratios, MAE and ASE are economically more efficient, as they reach a higher sample throughput and waste lower amounts of extractant.

Disentangling influences of climate variability and lake-system evolution on climate proxies derived from isoprenoid and branched glycerol dialkyl glycerol tetraethers (GDGTs): the 250 kyr Lake Chala record

Abstract. High-resolution paleoclimate records from tropical continental settings are greatly needed to advance understanding of global climate dynamics. The International Continental Scientific Drilling Program (ICDP) project DeepCHALLA recovered a 214.8 m long sediment sequence from Lake Chala, a deep and permanently stratified (meromictic) crater lake in eastern equatorial Africa, covering the past ca. 250 000 years (250 kyr) of continuous lacustrine deposition since the earliest phase of lake-basin development. Lipid biomarker analyses on the sediments of Lake Chala can provide quantitative records of past variation in temperature and moisture balance from this poorly documented region. However, the degree to which climate proxies derived from aquatically produced biomarkers are affected by aspects of lake developmental history is rarely considered, even though it may critically influence their ability to consistently register a particular climate variable through time. Modern-system studies of Lake Chala revealed crucial information about the mechanisms underpinning relationships between proxies based on isoprenoid (iso-) and branched (br-) glycerol dialkyl glycerol tetraethers (GDGTs) and the targeted climate variables, but the persistence of these relationships in the past remains unclear. Here we assess the reliability of long-term climate signals registered in the sediments of Lake Chala by comparing downcore variations in GDGT distributions with major phases in lake-system evolution as reflected by independent proxies of lake depth, mixing regime and nutrient dynamics: seismic reflection data, lithology and fossil diatom assemblages. Together, these records suggest that during early lake history (before ca. 180–200 ka) the distinct mixing-related depth zones with which specific GDGT producers are associated in the modern-day lake were not yet formed, likely due to more open lake hydrology and absence of chemical water-column stratification. Consequently absolute GDGT concentrations dating to this period are relatively low, proxies sensitive to water-column stratification (e.g., branched versus isoprenoid tetraether (BIT) index) display highly irregular temporal variability, and correlations between proxies are dissimilar to expectations based on modern-system understanding. A sequence of lake-system changes between ca. 180–200 and ca. 80 ka first established and then strengthened the chemical density gradient, promoting meromictic conditions despite the overall decrease in lake depth due to the basin gradually being filled up with sediments. From ca. 180 ka onward some GDGTs and derived proxies (e.g., crenarchaeol concentration, BIT index and IR6Me) display strong ∼ 23 kyr periodicity, likely reflecting the predominantly precession-driven insolation forcing of Quaternary climate variability in low-latitude regions. Our results suggest that GDGT-based temperature and moisture-balance proxies in Lake Chala sediments reflect the climate history of eastern equatorial Africa from at least ca. 160 ka onwards, i.e., covering the complete last glacial–interglacial cycle and the penultimate glacial maximum. This work confirms the potential of lacustrine GDGTs for elucidating the climate history of tropical regions at Quaternary timescales, provided they are applied to suitably high-quality sediment archives. Additionally, their interpretation should incorporate a broader understanding of the extent to which lake-system evolution limits the extrapolation back in time of proxy-climate relationships established in the modern system.

High-throughput surface epitope immunoaffinity isolation of extracellular vesicles and downstream analysis.

Extracellular vesicles (EVs), including exosomes, have significant potential for diagnostic and therapeutic applications. The lack of standardized methods for efficient and high-throughput isolation and analysis of EVs, however, has limited their widespread use in clinical practice. Surface epitope immunoaffinity (SEI) isolation utilizes affinity ligands, including antibodies, aptamers, or lectins, that target specific surface proteins present on EVs. Paramagnetic bead-SEI isolation represents a fit-for-purpose solution for the reproducible, high-throughput isolation of EVs from biofluids and downstream analysis of RNA, protein, and lipid biomarkers that is compatible with clinical laboratory workflows. This study evaluates a new SEI isolation method for enriching subpopulations of EVs. EVs were isolated from human plasma using a bead-based SEI method designed for on-bead and downstream analysis of EV-associated RNA and protein biomarkers. Western blot analysis confirmed the presence of EV markers in the captured nanoparticles. Mass spectrometry analysis of the SEI lysate identified over 1500 proteins, with the top 100 including known EV-associated proteins. microRNA (miRNA) sequencing followed by RT-qPCR analysis identified EV-associated miRNA transcripts. Using SEI, EVs were isolated using automated high-throughput particle moving instruments, demonstrating equal or higher protein and miRNA yield and recovery compared to manual processing. SEI is a rapid, efficient, and high-throughput method for isolating enriched populations of EVs; effectively reducing contamination and enabling the isolation of a specific subpopulation of EVs. In this study, high-throughput EV isolation and RNA extraction have been successfully implemented. This technology holds great promise for advancing the field of EV research and facilitating their application for biomarker discovery and clinical research.

Authigenic carbonate and native sulfur formation in Messinian (upper Miocene) marine sediments: Sedimentological, petrographical and geochemical constraints

Carbonate concretions accompanied by elemental sulfur were found in an early Messinian (Late Miocene) marine succession of NW Italy. The rocks were studied with an integrated approach including sedimentological, petrographical, stable isotope (carbon, oxygen, and multiple sulfur isotopes), and lipid biomarker analyses. Unlike other examples from Messinian strata of the Mediterranean area, the studied carbonate and sulfur concretions did not derive from the diagenetic replacement of sulfate minerals. Three lithofacies were distinguished: a) laminated lithofacies representing aphotic carbonate stromatolites enclosing fossils of filamentous sulfide-oxidizing bacteria; b) brecciated lithofacies deriving from the brecciation of carbonate stromatolites by mud injections; c) sulfur-bearing lithofacies deriving from the precipitation of thin laminae of elemental sulfur at or close to the sediment-water interface. The carbon and oxygen stable isotope composition of authigenic carbonate minerals and lipid biomarkers indicate that the initial formation of the laminated lithofacies was favored by organoclastic sulfate reduction in the shallow subsurface close to the sediment-water interface, producing sulfide that sustained dense microbial mats of sulfide-oxidizing bacteria at the seafloor. Calcification of the mats and consequent formation of stromatolites were possibly favored by nitrate-driven sulfide oxidation at the seafloor. The subsequent brecciation of the stromatolites was apparently the consequence of sulfate-driven anaerobic oxidation of methane (SD-AOM) in an underlying sulfate-methane transition zone (SMTZ). Focused fluid flow from below, possibly resulting from destabilization of gas hydrates, was not only responsible for the brecciation of the stromatolites, but also for the delivery of bicarbonate ions and the consequent precipitation of additional, 13C-depleted calcite (δ13C values as low as −52‰). Along with bicarbonate, also hydrogen sulfide was produced by SD-AOM at the SMTZ and was transported upwards. The oxidation of hydrogen sulfide at or close to the seafloor promoted the formation of elemental sulfur characterized by δ34S values and Δ33S values close to coeval seawater sulfate.

Electrochemical detection of extracellular vesicles for early diagnosis: a focus on disease biomarker analysis.

This review article presents a detailed examination of the integral role that electrochemical detection of extracellular vesicles (EVs) plays, particularly focusing on the potential application for early disease diagnostics through EVs biomarker analysis. Through an exploration of the benefits and challenges presented by electrochemical detection vetted for protein, lipid, and nucleic acid biomarker analysis, we underscore the significance of these techniques. Evidence from recent studies renders this detection modality imperative in identifying diverse biomarkers from EVs, leading to early diagnosis of diseases such as cancer and neurodegenerative disorders. Recent advancements that have led to enhanced sensitivity, specificity and point-of-care testing (POCT) potential are elucidated, along with equipment deployed for electrochemical detection. The review concludes with a contemplation of future perspectives, recognizing the potential shifts in disease diagnostics and prognosis, necessary advances for broad adoption, and potential areas of ongoing research. The objective is to propel further investigation into this rapidly burgeoning field, thereby facilitating a potential paradigm shift in disease detection, monitoring, and treatment toward human health management.

Quantifying Global Origin-Diagnostic Features and Patterns in Biotic and Abiotic Acyclic Lipids for Life Detection.

Lipids are a geologically robust class of organics ubiquitous to life as we know it. Lipid-like soluble organics are synthesized abiotically and have been identified in carbonaceous meteorites and on Mars. Ascertaining the origin of lipids on Mars would be a profound astrobiological achievement. We enumerate origin-diagnostic features and patterns in two acyclic lipid classes, fatty acids (i.e., carboxylic acids) and acyclic hydrocarbons, by collecting and analyzing molecular data reported in over 1500 samples from previously published studies of terrestrial and meteoritic organics. We identify 27 combined (15 for fatty acids, 12 for acyclic hydrocarbons) molecular patterns and structural features that can aid in distinguishing biotic from abiotic synthesis. Principal component analysis (PCA) demonstrates that multivariate analyses of molecular features (16 for fatty acids, 14 for acyclic hydrocarbons) can potentially indicate sample origin. Terrestrial lipids are dominated by longer straight-chain molecules (C4-C34 fatty acids, C14-C46 acyclic hydrocarbons), with predominance for specific branched and unsaturated isomers. Lipid-like meteoritic soluble organics are shorter, with random configurations. Organic solvent-extraction techniques are most commonly reported, motivating the design of our novel instrument, the Extractor for Chemical Analysis of Lipid Biomarkers in Regolith (ExCALiBR), which extracts lipids while preserving origin-diagnostic features that can indicate biogenicity.

Molecular fossils in reefal carbonates and sponges of the deep fore reef of Mayotte and Mohéli, Comoro Islands, western Indian Ocean

Microbial carbonates are common components of Quaternary tropical coral reefs. Previous studies revealed that sulfate-reducing bacteria trigger microbial carbonate precipitation in supposedly cryptic reef environments. Here, using petrography, lipid biomarker analysis, and stable isotope data, we aim to understand the formation mechanism of microbial carbonate enclosed in deep fore reef limestones from Mayotte and Mohéli, Comoro Islands, which differ from other reefal microbial carbonates in that they contain less microbial carbonate and are dominated by numerous sponges. To discern sponge-derived lipids from lipids enclosed in microbial carbonate, lipid biomarker inventories of diverse sponges from the Mayotte and Mohéli reef systems were examined. Abundant peloidal, laminated, and clotted textures point to a microbial origin of the authigenic carbonates, which is supported by ample amounts of mono-O-alkyl glycerol monoethers (MAGEs) and terminally branched fatty acids; both groups of compounds are attributed to sulfate-reducing bacteria. Sponges revealed a greater variety of alkyl chains in MAGEs, including new, previously unknown, mid-chain monomethyl- and dimethyl-branched MAGEs, suggesting a diverse community of sulfate reducers different from the sulfate-reducers favoring microbialite formation. Aside from biomarkers specific for sulfate-reducing bacteria, lipids attributed to demosponges (i.e., demospongic acids) are also present in some of the sponges and the reefal carbonates. Fatty acids attributed to demosponges show a higher diversity and a higher proportion in microbial carbonate compared to sponge tissue. Such pattern reflects significant taphonomic bias associated with the preservation of demospongic acids, with preservation apparently favored by carbonate authigenesis.

Searching for traces of human activity in earthen floor sequences: high-resolution geoarchaeological analyses at an Early Iron Age village in Central Iberia

The Northern Iberian Plateau during the Early Iron Age witnessed the proliferation of villages, showcasing well-preserved earthen architectural remains that offer valuable insights into past daily life practices. However, the application of high-resolution geoarchaeological approaches to these contexts has been largely overlooked, despite their significance in assessing complex sedimentary sequences predominantly composed of earth-based construction materials. This paper presents the outcomes of a microcontextual geoarchaeological study conducted on earthen dwellings from the Early Iron Age village of Cerro de San Vicente (Salamanca, Northern Iberia). Our study employed soil micromorphology, lipid biomarker analysis, XRD, and XRF analyses to investigate site formation processes, characterize construction materials and techniques, and explore aspects of daily life practices, functionality, and dwelling life histories. Our results have enabled the identification of three distinct construction layers within the dwellings, shedding light on recurrent events of floor use, maintenance, and repaving. Additionally, we have detected periods of abandonment and decay of the earth-based construction material that inform on the dynamics of abandonment and reuse within the village. Furthermore, our analysis has revealed the presence of well-preserved lipid biomarkers throughout the sequences, possibly associated with the past functionality of the dwellings. Ongoing and future analyses will further contribute to our understanding of ancient construction practices and the utilization of domestic spaces at Cerro de San Vicente. This study significantly enhances the limited availability of high-resolution, microcontextual data sets concerning Iron Age contexts in Iberia, underscoring the potential of our approach for future consolidation and advancement. By combining different geoarchaeological methodologies, we demonstrate the importance of integrating diverse analytical techniques to gain comprehensive insights into the socio-cultural dynamics of the Early Iron Age settlements.

Modern Sedimentation Patterns in Lake Issyk Kul (Kyrgyzstan), Derived From Surface Sediment and Inlet Stream Samples

AbstractThis study provides a descriptive characterization of the modern sedimentary processes in Lake Issyk Kul, Kyrgyzstan, important for the selection of a suitable coring or deep‐drilling site, interpretation of future core data and applicability of proxies. The quasi‐equidistant sampling grid of 66 sediment surface samples covers the entirety of the lake basin and is complemented by 10 samples from the major inflows. The methodological approach includes geochemical, granulometric, lipid biomarker, diatom, and statistical analyses. The quantitative and qualitative changes in sediment composition yield information on its generic origin and prevailing transport and depositional environments. The composition of the surface sediments in Issyk Kul is highly heterogenous. Nearshore deposition is mainly controlled by wave action and by fluvial sediment supply with highest quantities of detrital input coming from the high‐energetic, eastern tributaries. Sediments in the deep central basin are mainly produced in situ and dominated by authigenic calcite. Biogenic accumulation is overall low, except for the western extremity of the lake, where the nearshore, shallow‐water, and low‐energetic environment favors aquatic productivity and subsequent preservation of organic material and diatoms. Redeposition of sediments is a dominant process along the slopes across the southern and western basin floor, where run‐out distances of mass movement deposits are up to 5 km. Directional sediment transport by lake currents appears to be less important, except for the transport of very fine‐grained organic matter. Biomarker‐inferred temperature reconstructions suggest lake surface temperatures of ∼15°C in the western littoral zone and in Tyup Bay and a decrease to ∼13°C basinward.

Distinguishing between sheep and goat in archaeological fumiers through faecal lipid biomarkers: The case of Belmaco Cave (Canary Islands, Spain)

Lipid biomarker analysis focused on steroids has shown to have great potential for discriminating between animal faecal inputs in archaeology. This is particularly interesting when applied to stabling deposits to assess herding strategies and livestock composition. Here we present the results of a sedimentary faecal biomarker study conducted at Belmaco Cave, a pre-European archaeological site in La Palma (Canary Islands). The site was occupied by indigenous pastoralist groups over the course of five centuries prior to the first arrival of the Europeans in the 15th century. Previous soil micromorphological data indicates recurrent sheep and/or goat penning and periodic burning of the pen in the central area of the cave. We selected bulk sediment samples from unburned, charred and ashed dung layers and carried out sterol, stanol and bile acid analysis. Our results suggest that the main source of faecal matter is sheep. We also found that even though charred and dung ash layers contained lower concentrations of the biomarker compounds, these were still sufficient to provide information on the origin of the faecal remains. These data add to our current knowledge of the aboriginal Canary Island pastoralist economy.

Reconstructing formation processes at the Canary Islands indigenous site of Belmaco Cave (La Palma, Spain) through a multiproxy geoarchaeological approach

AbstractThe indigenous populations of La Palma (Canary Islands), who arrived on the island from Northwest Africa ca. 2000 years B.P., were predominantly pastoralists. Yet, many aspects of their subsistence economy such as the procurement, management, and use of wild plant resources remain largely unknown. To explore this, we studied the 600–1100‐year‐old archaeological site of Belmaco Cave, which comprises a stratified sedimentary deposit representative of a fumier. Here, we present a high‐resolution, multiproxy geoarchaeological study combining soil micromorphology, lipid biomarker analysis, X‐ray diffraction, μ‐X‐ray diffraction, μ‐X‐ray fluorescence, Fourier transform infrared spectroscopy, and μ‐Fourier transform infrared spectroscopy, to characterize formation processes and explore plant sources. Recurrent goat/sheep habitation and maintenance activities are represented by interstratified layers of unburned dung, charcoal‐rich sediment, and dung ash. Lipid biomarker data show a herd diet mainly composed of herbaceous plants, which is key to understanding the mobility of indigenous shepherds. Our results also revealed an unusual suite of authigenic minerals including hazenite, aragonite, and sylvite, possibly formed through diagenetic processes involving interaction between ash, dung, urine, volcanogenic components, and bacterial activity, coupled with arid and alkaline conditions. Our study shows the potential of a multiproxy approach to a fumier deposit in a volcanogenic sedimentary context.

The Determination of the Spatial Distribution of Indigenous Lipid Biomarkers in an Immature Jurassic Sediment Using Time-of-Flight-Secondary Ion Mass Spectrometry.

The ability to detect and map lipids, including potential lipid biomarkers, within a sedimentary matrix using mass spectrometry (MS) imaging may be critical to determine whether potential lipids detected in samples returned from Mars are indigenous to Mars or are contaminants. Here, we use gas chromatography-mass spectrometry (GC-MS) and time-of-flight-secondary ion mass spectrometry (ToF-SIMS) datasets collected from an organic-rich, thermally immature Jurassic geologic sample to constrain MS imaging analysis of indigenous lipid biomarkers in geologic samples. GC-MS data show that the extractable fractions are dominated by C27-C30 steranes and sterenes as well as isorenieratene derivatives. ToF-SIMS spectra from organic matter-rich laminae contain a strong, spatially restricted signal for ions m/z 370.3, m/z 372.3, and m/z 386.3, which we assign to C27 sterenes, cholestane (C27), and 4- or 24-methyl steranes (C28), respectively, as well as characteristic fragment ions of isorenieratene derivatives, including m/z 133.1, m/z 171.1, and m/z 237.1. We observed individual steroid spatial heterogeneity at the scale of tens to hundreds of microns. The fine-scale heterogeneity observed implies that indigenous lipid biomarkers concentrated within specific regions may be detectable via ToF-SIMS in samples with even low amounts of organic carbon, including in samples returned from Mars.

What about nitrogen? Using nitrogen as a carrier gas during the analysis of petroleum biomarkers by gas chromatography mass spectrometry

Gas chromatography mass spectrometry (GC–MS) is a commonly used method for organic geochemistry for both academic research and applications such as petroleum analysis. Gas chromatography requires a carrier gas, which needs to be both volatile and stable and in most organic geochemical applications helium or hydrogen have been used, with helium predominating for gas chromatography mass spectrometry. Helium, however, is becoming an increasingly scarce resource and is not sustainable. Hydrogen is the most commonly considered alternative carrier gas to helium but has characteristics that in certain respects make its use less practical, foremost is that hydrogen is flammable and explosive. But as hydrogen is increasingly used as a fuel, higher demand may also make its use less desirable. Here we show that nitrogen can be used for the GC–MS analysis of fossil lipid biomarkers. Using nitrogen, chromatographic separation of isomers and homologues can be achieved, but sensitivity is orders of magnitude less than for helium. It is reasonable to use nitrogen as a carrier gas in applications where low levels of detection are not needed, such as the characterization of samples of crude oil or foodstuffs, or potentially as part of a gas-mixture seeking to reduce helium-demand but maintain a level of chromatographic separation sufficient to support proxy-based characterizations of petroleum.

Formation of authigenic carbonates contributed by sulfate- and metal-driven anaerobic oxidation of methane in the northern Okinawa Trough, East China Sea

Authigenic carbonates of the northern Okinawa Trough have been shown to be contributed by both sulfate- and Fe-driven anaerobic oxidation of methane (SD-AOM and Fe-AOM, respectively); however, the microorganisms involved remain poorly constrained. To better understand the types and roles of microorganisms in specific biological methane oxidation processes, authigenic carbonates collected from the northern Okinawa Trough at water depths between ∼540 m and 700 m were studied using petrographic, mineralogical, elemental, and lipid biomarker analyses. The carbonate minerals were primarily aragonite, high-magnesium calcite, low-magnesium calcite, or dolomite. The extremely low δ13C values of bulk carbonates (−59.2‰), molecular fossils of anaerobic methane oxidizing archaea (ANME; −131‰), and sulfate-reducing bacteria (SRB; −77‰) indicated that the authigenic carbonates formed as products of AOM. Biogenic methane was confirmed to be the main carbon source for all carbonates, whereas bio-degraded oil and hydrothermal input complemented carbon sources, as revealed by the occurrence of unresolved complex mixture, strongly enriched As and Sb, and their correlations with Fe/Al. Combined with enriched δ18O values (as high as +5‰), the methane fluids were suggested to derive from the dissociation of gas hydrates. ANME-2 and a mixture of ANME-1 and ANME-2 were identified for the two calcitic carbonates, respectively, as revealed by their specific biomarker patterns. The relatively higher contents of 13C-depeleted isoprenoids and SRB−related fatty acids, strong Mo enrichment, and biological debris in both calcite- and aragonite-dominated carbonates reflect precipitation driven by SD-AOM in a shallow sulfate-methane transition. For other seep carbonates, low amounts of 13C-depeleted isoprenoids and the near absence of crocetane suggest dominance of the ANME-1 assemblage. The extremely low amounts and non-13C-depleted iso-/anteiso-C15:0 fatty acids (−27‰) in the dolomite-containing carbonates indicate the decoupling of ANME and SRB. These carbonates were most likely formed below or at the bottom of the sulfate-methane transition and included contributions from Fe-AOM, as indicated by the low Mo content, occurrence of dolomite and siderite, and decreased δ56Fe values with increasing Fe/Al ratios.

New integrated molecular approaches for investigating lake settlements in north-western Europe

Lake settlements, particularly crannogs, pose several contradictions—visible yet inaccessible, widespread yet geographically restricted, persistent yet vulnerable. To further our understanding, we developed the integrated use of palaeolimnological (scanning XRF, pollen, spores, diatoms, chironomids, Cladocera, microcharcoal, biogenic silica, SEM-EDS, stable-isotopes) and biomolecular (faecal stanols, bile acids, sedaDNA) analyses of crannog cores in south-west Scotland and Ireland. Both can be effective methods sets for revealing occupation chronologies and identifying on-crannog activities and practices. Strong results from sedaDNA and lipid biomarker analyses demonstrate probable on-site animal slaughter, food storage and possible feasting, suggesting multi-period, elite site associations, and the storage and protection of valuable resources.

Fuel sources, natural vegetation and subsistence at a high-altitude aboriginal settlement in Tenerife, Canary Islands: Microcontextual geoarchaeological data from Roques de García Rockshelter

High-altitude island environments, with their characteristic strong seasonal contrast and limited resources, are challenging contexts for human subsistence. However, although archaeological contexts in this kind of setting hold great potential to explore the diversity of human biological and cultural adaptations, such sites are rare. In this paper, we present the results of a microcontextual geoarchaeological study carried out at Roques de García Rockshelter, the highest altitude cave archaeological site in the Canary Islands (Spain). The site was inhabited by the aboriginal population of the island and has yielded a rich archaeological context derived from combustion activity. We carried out soil micromorphology to characterize site function and lipid biomarker analysis to investigate the natural and anthropogenic organic record. Our data indicate that the aboriginal groups that occupied the site kept goats with them (in the rockshelter) and probably used Juniperus turbinata (sabina) wood, a current distant fuel source. These results suggest that the aboriginal societies of Tenerife occupied the highlands regularly, taking their herds and firewood with them. Further research is necessary to explore the use and exploitation of fuel sources, the seasonality of these occupations and their differences with lowland sites.