A revised chronology of the lowest occupation layer of Pedra Furada Rock Shelter,Piauı́, Brazil: the Pleistocene peopling of the Americas

The present work revisits the chronology of the archaeologically controversial Pedra Furada Rock Shelter of Southeast Piauı́, Brazil, using an improved radiocarbon laboratory pre-treatment and measurements on charcoal samples. The procedure, known as ABOX-SC (acid–base–wet oxidation followed by stepped combustion), has previously been used to secure radiocarbon dates of >40 ka for the antiquity of human occupation of Australia and South Africa, and now has been applied to charcoal from the previously dated oldest occupation layer of the Pedra Furada site. Previous radiocarbon dating had obtained only lower limits of 40–45 ka BP for the Pedra Furada basal layer. Nine charcoal samples from well-structured hearths were subjected to the ABOX-SC procedure and their radiocarbon content determined by accelerator mass spectrometry. Measurements on five of the samples returned ages of greater than 56 ka BP, from graphites produced from ABOX pre-treated charcoal combusted at 910°C. Two other samples were greater than 50 ka BP. The remaining two samples were essentially completely combusted at 650°C, with no material surviving to make a 910°C CO₂ fraction. Their ages were 41.3 and 47.2 ka BP. Ages obtained from graphites generated from the 650°C combusted fraction are considered minimum ages.     

Geochemistry,radiocarbon ages,and paleorecharge conditions along a transect in the central High Plains aquifer,southwestern Kansas,USA

Water samples from short-screen monitoring wells installed along a 90-km transect in southwestern Kansas were analyzed for major ions, trace elements, isotopes (H, B, C, N, O, S, Sr), and dissolved gases (He, Ne, N₂, Ar, O₂, CH₄) to evaluate the geochemistry, radiocarbon ages, and paleorecharge conditions in the unconfined central High Plains aquifer. The primary reactions controlling water chemistry were dedolomitization, cation exchange, feldspar weathering, and O₂ reduction and denitrification. Radiocarbon ages adjusted for C mass transfers ranged from <2.6 ka (¹⁴C) B.P. near the water table to 12.8 ± 0.9 ka (¹⁴C) B.P. at the base of the aquifer, indicating the unconfined central High Plains aquifer contained a stratified sequence of ground water spanning Holocene time. A cross-sectional model of steady-state ground-water flow, calibrated using radiocarbon ages, is consistent with recharge rates ranging from 0.8 mm/a in areas overlain by loess to 8 mm/a in areas overlain by dune sand. Paleorecharge temperatures ranged from an average of 15.2 ± 0.7 °C for the most recently recharged waters to 11.6 ± 0.4 °C for the oldest waters. The temperature difference between Early and Late Holocene recharge was estimated to be 2.4 ± 0.7 °C, after taking into account variable recharge elevations. Nitrogen isotope data indicate NO₃ in paleorecharge (average concentration=193 μM) was derived from a relatively uniform source such as soil N, whereas NO₃ in recent recharge (average concentration=885 μM) contained N from varying proportions of fertilizer, manure, and soil N. Deep water samples contained components of N₂ derived from atmospheric, denitrification, and deep natural gas sources. Denitrification rates in the aquifer were slow (5 ± 2× 10⁻³ μmol N L⁻¹ a⁻¹), indicating this process would require >10 ka to reduce the average NO₃ concentration in recent recharge to the Holocene background concentration.     

Quantifying pyrogenic carbon from thermosequences of wood and grass using hydrogen pyrolysis

Previously studied thermosequences of wood (chestnut) and grass (rice straw) biochar were subjected to hydrogen pyrolysis (hypy) to evaluate the efficacy of the technique for determining pyrogenic carbon (C_P) abundance. As expected, biochar from both wood and grass produced at higher temperature had higher C_P amount. However, the trend was not linear, but more sigmoidal. C_P/C_T ratio values (C_T = total organic carbon) for the wood thermosequence were ⩽0.03 at biochar production temperature (T_CHAR) ⩽ 300 °C. They increased dramatically until 600 °C and remained relatively constant and near unity at higher biochar production temperature. Grass biochar was similar in profile, but C_P/C_T values rose dramatically after 400 °C. The findings are consistent with the hypothesis that hypy residues contain polycyclic aromatic hydrocarbons (PAHs) with a degree of condensation above at least 7–14 fused rings, with labile organic matter and pyrogenic PAHs below this degree of condensation removed by hypy.Both wood and grass thermosequences displayed δ¹³C_P values that decreased with increased T_CHAR, indicating that recalcitrant carbon compounds (pyrogenic aromatic PAHs with a relatively high degree of condensation) were first formed from structural components with relatively high δ¹³C values (e.g. cellulose). Relatively constant δ¹³C values at T_CHAR ⩾ 500 °C suggested the dominant pyrolysis reaction was condensation of PAHs with no additional fractionation. Comparison of hypy with benzene polycarboxylic acid (BPCA), ‘ring current’ NMR and pyrolysis gas chromatography–mass spectrometry (GC–MS) results from the same suite of samples indicated a consistent overview of the structure of C_P, but provided unique and complimentary information.     

Radiolytic alteration of biopolymers in the Mulga Rock (Australia) uranium deposit

We investigated the effect of ionizing radiation on organic matter (OM) in the carbonaceous uranium (U) mineralization at the Mulga Rock deposit, Western Australia. Samples were collected from mineralized layers between 53 and 58.5 m depths in the Ambassador prospect, containing <5300 ppm U. Uranium bears a close spatial relationship with OM, mostly finely interspersed in the attrinite matrix and via enrichments within liptinitic phytoclasts (mainly sporinite and liptodetrinite). Geochemical analyses were conducted to: (i) identify the natural sources of molecular markers, (ii) recognize relationships between molecular markers and U concentrations and (iii) detect radiolysis effects on molecular marker distributions. Carbon to nitrogen ratios between 82 and 153, and Rock–Eval pyrolysis yields of 316–577 mg hydrocarbon/g TOC (HI) and 70–102 mg CO₂/g TOC (OI) indicate a predominantly lipid-rich terrigenous plant OM source deposited in a complex shallow swampy wetland or lacustrine environment. Saturated hydrocarbon and ketone fractions reveal molecular distributions co-varying with U concentration. In samples with <1700 ppm U concentrations, long-chain n-alkanes and alkanones (C₂₇–C₃₁) reveal an odd/even carbon preference indicative of extant lipids. Samples with ⩾1700 ppm concentrations contain intermediate-length n-alkanes and alkanones, bearing a keto-group in position 2–10, with no carbon number preference. Such changes in molecular distributions are inconsistent with diagenetic degradation of terrigenous OM in oxic depositional environments and cannot be associated with thermal breakdown due to the relatively low thermal maturity of the deposits (R_r = 0.26%). It is assumed that the intimate spatial association of high U concentrations resulted in breakdown via radiolytic cracking of recalcitrant polyaliphatic macromolecules (spores, pollen, cuticles, or algal cysts) yielding medium chain length n-alkanes (C₁₃–C₂₄). Reactions of n-alkenes with OH⁻ radicals from water hydrolysis produced alcohols that dehydrogenated to alkanones or through carbonylation formed alkanones. Rapid reactions with hydroxyl radicals likely decreased the isomerization of n-alkenes and decreased alkanone diversity, such that the alkan-2-one isomer is predominant. This specific distribution of components generated by natural radiolysis enables their application as “radiolytic molecular markers”. Breaking of C–C bonds through radiolytic cracking at temperatures much lower than the oil window (<50 °C) can have profound implications on initiation of petroleum formation, paleoenvironmental reconstructions, mineral exploration and in tracking radiolysis of OM.     

One-year spatial and temporal monitoring of concentration and carbon isotopic composition of atmospheric CO2 in a Wrocław (SW Poland) city area

The main aim of this study was to assess the natural and anthropogenic contributions of CO₂ in the urban atmosphere of Wrocław City (SW Poland) using combined quantitative (CO₂ concentrations) and qualitative analysis (δ¹³C of CO₂). Between 21 January 2011 and 22 December 2011, 17 sampling campaigns were performed at 3-week intervals and in total 255 samples were collected. The mean CO₂ concentration was 469 ± 71 ppm and the mean δ¹³C(CO₂) was −10.8 ± 1‰.The measured δ¹³C(CO₂) values of major end-members for two winter heating seasons (−25.7‰ in January–March of 2011 and −27.6 ‰ in October–December of 2011) and for one vegetative season (−20.4‰ in April–September of 2011) suggest soil respiration as a main source of atmospheric CO₂ during the vegetative season, and a very significant impact of fossil fuel combustion during the winter heating seasons. There were significant increases of CO₂ concentrations at many sampling locations after the opening of a new motorway on 31 August 2011. The authors hypothesise that the new motorway contributes to the increase of CO₂ across the city.     

Mineralisation and structural changes during the initial phase of microbial degradation of pyrogenic plant residues in soil

The microbial recalcitrance of char accumulated after vegetation fires was studied using pyrogenic organic material (PyOM) with increasing degrees of charring, produced from rye grass (Lolium perenne) and pine wood (Pinus sylvestris) at 350 °C under oxic conditions. Solid state ¹³C and ¹⁵N nuclear magnetic resonance (NMR) spectroscopy confirmed increasing aromaticity and the formation of heterocyclic N with prolonged charring. After mixing with a mineral soil, the PyOM was aerobically incubated for 48 days at 30 °C. To account for the input of fresh litter after a fire event, unburnt rye grass residue was added as a co-substrate. The grass-derived PyOM showed the greatest extent of C mineralisation. After 48 days incubation, up to 3.2% of the organic C (OC) was converted to CO₂. More severe thermal alteration resulted in a decrease in the total C mineralisation to 2.5% of OC. In the pine-derived PyOM, only 0.7% and 0.5% of the initial C were mineralised. The co-substrate additions did not enhance PyOM mineralisation during initial degradation. ¹³C NMR spectroscopic analysis indicated structural changes during microbial degradation of the PyOM. Concomitant with a decrease in O-alkyl/alkyl-C, carboxyl/carbonyl C content increased, pointing to oxidation. Only the strongly thermally altered pine PyOM showed a reduction in aromaticity. The small C losses during the experiment indicated conversion of aryl C into other C groups. As revealed by the increase in carboxyl/carbonyl C, this conversion must have included the opening and partial oxidation of aromatic ring structures. Our study demonstrates that plant PyOM can be microbially attacked and mineralised at rates comparable to those for soil organic matter (SOM), so its role as a highly refractory SOM constituent may need re-evaluation.     

Tracking the fate of dung-derived carbohydrates in a temperate grassland soil using compound-specific stable isotope analysis

Carbohydrates are major organic components of dung and are likely to contribute substantially to increased carbon stocks in manured soils. To investigate this hypothesis, a field-scale experiment was conducted on a temperate grassland site in Devon, UK. C₄ dung (bulk δ¹³C value ?12.6‰) was applied to a temperate grassland C₃ soil (bulk δ¹³C value ?30.3‰) in April and the surface soil beneath cow pats sampled at seven dates over a year. Total carbohydrates were extracted as their monosaccharide components and analysed as the alditol acetates using gas chromatography. The δ¹³C values of the major monosaccharides glucose (?11.5 ±0.6‰), xylose (?10.4 ±0.4‰), arabinose (?10.4 ±0.5‰) and galactose (?8.3 ±1.6‰) extracted from the C₄ dung via acid hydrolysis were indicative of their source. Their weighted mean δ¹³C value was ?10.8‰, 1.8‰ more ¹³C-enriched than the bulk dung value. The δ¹³C values of individual monosaccharides recovered by acid hydrolysis in the 0–1 cm and 1–5 cm soil horizons beneath C₄ cow pats, compared with control soils determined over 372 days, allowed assessment of the extent of incorporation and fluxes of dung-derived monosaccharides. A maximum of 60% of the dung C in soil was derived from carbohydrates after 56 days, declining to around 20% after 372 days. Incorporation dynamics varied between monosaccharide species. Glucose, xylose and arabinose behaved in a similar manner because of their predominantly plant cell wall derived provenance in the dung, whilst dung-derived galactose and mannose appeared to have a microbial source in the soil. The dynamics of total dung-derived monosaccharides in the top 5 cm was comparable to incorporation and flux of bulk dung C, previously estimated using bulk δ¹³C values. The movement of dung-derived carbohydrates into the soil was inequivalent between the 0–1 cm and 1–5 cm horizons. The lack of a significant difference in concentration, but the evidence for the persistence of dung-derived monosaccharides in soil based on δ¹³C values, indicated replacement of existing pools in the soil, suggesting that the ability of this particular soil to sequester further C derived from carbohydrates was limited.     

Isotope geochemistry of Swan Lake Basin in the Nebraska Sandhills,USA: Large 13C enrichment in sediment-calcite records

This study presents isotope geochemical analyses conducted on water column samples and core sediments collected from the Swan Lake Basin. Water analyses include the dissolved methane (CH₄) content and the ratio of carbon-13 to carbon-12 (δ¹³C) in dissolved inorganic carbon (DIC). The core sediments – sandy muds containing inorganic calcite, organic matter, and opal phases ± ostracods – were examined by X-ray diffraction, dated by radiocarbon (¹⁴C), analyzed for wt% organic carbon, wt% organic nitrogen, wt% organic matter, wt% calcite, δ¹³C of bulk-sediment insoluble organic matter (kerogen), ¹⁸O:¹⁶O ratio (δ¹⁸O) and δ¹³C of bulk and ostracod calcite. Of particular significance is the large enrichment in carbon-13 (δ¹³C = +4.5 to +20.4‰ V-PDB) in the calcite of these sediments. The ¹³C-enriched calcite is primarily formed from DIC in the water column of the lake as a result of the following combined processes: (i) the incorporation of ¹³C enriched residual carbon dioxide (CO₂) after partial reduction to CH₄ in the sediments and its migration into the water column-DIC pool; (ii) the preferential assimilation of ¹²C by phytoplankton during photosynthesis; (iii) the removal of ¹³C-depleted CH₄ by ebullition and of organic matter by sedimentation and burial. The ¹³C enrichment was low between 3624 and 2470 yr BP; high between 2470 and 1299 yr BP; and moderate since 1299 yr BP. Low ¹³C enrichment was formed under low water-column carbon levels while higher ones were formed under elevated rates of biomass and calcite deposition. These associations seem to imply that biological productivity is the main reason for carbon-13 enrichments.     

Organic geochemistry of the Vindhyan sediments: Implications for hydrocarbons

The organic geochemical methods of hydrocarbon prospecting involve the characterization of sedimentary organic matter in terms of its abundance, source and thermal maturity, which are essential prerequisites for a hydrocarbon source rock. In the present study, evaluation of organic matter in the outcrop shale samples from the Semri and Kaimur Groups of Vindhyan basin was carried out using Rock Eval pyrolysis. Also, the adsorbed low molecular weight hydrocarbons, methane, ethane, propane and butane, were investigated in the near surface soils to infer the generation of hydrocarbons in the Vindhyan basin. The Total Organic Carbon (TOC) content in shales ranges between 0.04% and 1.43%. The S₁ (thermally liberated free hydrocarbons) values range between 0.01–0.09 mgHC/gRock (milligram hydrocarbon per gram of rock sample), whereas the S₂ (hydrocarbons from cracking of kerogen) show the values between 0.01 and 0.14 mgHC/gRock. Based on the T_max (temperature at highest yield of S₂) and the hydrogen index (HI) correlations, the organic matter is characterized by Type III kerogen. The adsorbed soil gas, CH₄ (C₁), C₂H₆ (C₂), C₃H₈ (C₃) and nC₄H₁₀, (nC4), concentrations measured in the soil samples from the eastern part of Vindhyan basin (Son Valley) vary from 0 to 186 ppb, 0 to 4 ppb, 0 to 5 ppb, and 0 to 1 ppb, respectively. The stable carbon isotope values for the desorbed methane (δ¹³C₁) and ethane (δ¹³C₂) range between −45.7‰ to −25.2‰ and −35.3‰ to −20.19‰ (VPDB), respectively suggesting a thermogenic source for these hydrocarbons. High concentrations of thermogenic hydrocarbons are characteristic of areas around Sagar, Narsinghpur, Katni and Satna in the Son Valley. The light hydrocarbon concentrations (C₁–C₄) in near surface soils of the western Vindhyan basin around Chambal Valley have been reported to vary between 1–2547 ppb, 1–558 ppb, 1–181 ppb, 1–37 ppb and 1–32 ppb, respectively with high concentrations around Baran-Jhalawar-Bhanpur-Garot regions (Kumar et al., 2006). The light gaseous hydrocarbon anomalies are coincident with the wrench faults (Kota – Dholpur, Ratlam – Shivpuri, Kannod – Damoh, Son Banspur – Rewa wrench) in the Vindhyan basin, which may provide conducive pathways for the migration of the hydrocarbons towards the near surface soils.     

Radiocarbon analysis of halophilic microbial lipids from an Australian salt lake

Assigning accurate dates to hypersaline sediments opens important terrestrial records of local and regional paleoecologies and paleoclimatology. However, as of yet no conventional method of dating hypersaline systems has been widely adopted. Biomarker, mineralogical, and radiocarbon analyses of sediments and organic extracts from a shallow (13 cm) core from a hypersaline playa, Lake Tyrrell, southeastern Australia, produce a coherent age-depth curve beginning with modern microbial mats and extending to ~ 7500 cal yr BP. These analyses are furthermore used to identify and constrain the timing of the most recent change in hydrological regime at Lake Tyrrell, a shift from a clay deposit to the precipitation of evaporitic sands occurring at some time between ~ 4500 and 7000 yr. These analyses show the potential for widespread dating of hypersaline systems integrating the biomarker approach, reinforce the value of the radiocarbon content of biomarkers in understanding the flow of carbon in modern ecologies, and validate the temporal dimension of data provided by biomarkers when dating late Quaternary sediments.     

Greenhouse gas emissions from soils—A review

Soils act as sources and sinks for greenhouse gases (GHG) such as carbon dioxide (CO₂), methane (CH₄), and nitrous oxide (N₂O). Since both storage and emission capacities may be large, precise quantifications are needed to obtain reliable global budgets that are necessary for land-use management (agriculture, forestry), global change and for climate research. This paper discusses exclusively the soil emission-related processes and their influencing parameters. It reviews soil emission studies involving the most important land-cover types and climate zones and introduces important measuring systems for soil emissions. It addresses current shortcomings and the obvious bias towards northern hemispheric data.When using a conservative average of 300 mg CO₂e m⁻² h⁻¹ (based on our literature review), this leads to global annual net soil emissions of ≥350 Pg CO₂e (CO₂e = CO₂ equivalents = total effect of all GHG normalized to CO₂). This corresponds to roughly 21% of the global soil C and N pools. For comparison, 33.4 Pg CO₂ are being emitted annually by fossil fuel combustion and the cement industry.     

Stable isotopic signatures of the modern land snail Eremina desertorum from a low-latitude (hot) dry desert—A study from the Petrified Forest,New Cairo,Egypt

This study was conducted on recent desert samples—including (1) soils, (2) plants, (3) the shell, and (4) organic matter from modern specimens of the land snail Eremina desertorum—which were collected at several altitudes (316–360 m above sea level) from a site in the New Cairo Petrified Forest. The soils and shell_{E. desertorum} were analyzed for carbonate composition and isotopic composition (δ¹⁸O, δ¹³C). The plants and organic matter_{E. desertorum} were analyzed for organic carbon content and δ¹³C. The soil carbonate, consisting of calcite plus minor dolomite, has δ¹⁸O values from −3.19 to −1.78‰ and δ¹³C values −1.79 to −0.27‰; covariance between the two values accords with arid climatic conditions. The local plants include C3 and C4 types, with the latter being dominant. Each type has distinctive bulk organic carbon δ¹³C values: −26.51 to −25.36‰ for C3-type, and −13.74 to −12.43‰ for C4-type plants.The carbonate of the shell_{E. desertorum} is composed of aragonite plus minor calcite, with relatively homogenous isotopic compositions (δ¹⁸O_mean = −0.28 ± 0.22‰; δ¹³C_mean = −4.46 ± 0.58‰). Most of the δ¹⁸O values (based on a model for oxygen isotope fractionation in an aragonite-water system) are consistent with evaporated water signatures. The organic matter_{E. desertorum} varies only slightly in bulk organic carbon δ¹³C values (−21.78 ± 1.20‰) and these values suggest that the snail consumed more of C3-type than C4-type plants. The overall offset in δ¹³C values (−17.32‰) observed between shell_{E. desertorum} carbonate and organic matter_{E. desertorum} exceeds the value expected for vegetation input, and implies that 30% of carbon in the shell_{E. desertorum} carbonate comes from the consumption of limestone material.     

Revised 14C dating of ice wedge growth in interior Alaska (USA) to MIS 2 reveals cold paleoclimate and carbon recycling in ancient permafrost terrain

Establishing firm radiocarbon chronologies for Quaternary permafrost sequences remains a challenge because of the persistence of old carbon in younger deposits. To investigate carbon dynamics and establish ice wedge formation ages in Interior Alaska, we dated a late Pleistocene ice wedge, formerly assigned to Marine Isotope Stage (MIS) 3, and host sediments near Fairbanks, Alaska, with 24 radiocarbon analyses on wood, particulate organic carbon (POC), air-bubble CO₂, and dissolved organic carbon (DOC). Our new CO₂ and DOC ages are up to 11,170 yr younger than ice wedge POC ages, indicating that POC is detrital in origin. We conclude an ice wedge formation age between 28 and 22 cal ka BP during cold stadial conditions of MIS 2 and solar insolation minimum, possibly associated with Heinrich event 2 or the last glacial maximum. A DOC age for an ice lens in a thaw unconformity above the ice wedge returned a maximum age of 21,470 ± 200 cal yr BP. Our variable ¹⁴C data indicate recycling of older carbon in ancient permafrost terrain, resulting in radiocarbon ages significantly older than the period of ice-wedge activity. Release of ancient carbon with climatic warming will therefore affect the global ¹⁴C budget.     

Variability of Indian monsoonal rainfall over the past 100 ka and its implication for C3–C4 vegetational change

Oxygen and carbon isotope ratios of soil carbonate and carbon isotope ratios of soil organic matter (SOM) separated from three cores, Kalpi, IITK and Firozpur, of the Ganga Plain, India are used to reconstruct past rainfall variations and their effect on ambient vegetation. The δ¹⁸O values of soil carbonate (δ¹⁸O_SC) analyzed from the cores range from ? 8.2 to ? 4.1‰. Using these variations in δ¹⁸O_SC values we are able, for the first time, to show periodic change in rainfall amount between 100 and 18 ka with three peaks of higher monsoon at about 100, 40 and 25 ka. The estimation of rainfall variations using δ¹⁸O value of rainwater-amount effect suggests maximum decrease in rainfall intensity (~ 20%) during the last glacial maximum. The δ¹³C values of soil carbonate (δ¹³C_SC) and SOM (δ¹³C_SOM) range from ? 6.3 to + 1.6‰ and ? 28.9 to ? 19.4‰, respectively, implying varying proportions of C₃ and C₄ vegetations over the Ganga Plain during the last 100 ka. The comparison between monsoonal rainfall and atmospheric CO₂ with vegetation for the time period 84 to 18 ka indicate that relative abundances of C₃ and C₄ vegetations were mainly driven by variations in monsoonal rainfall.     

The onset of dune formation in the Strzelecki Desert,South Australia

This study is concerned with the Late Quaternary climatic chronology of the Strzelecki Desert dunefields in central Australia. The sand ridges comprise layers of quartz sand, some of which include palaeosol horizons with carbonated rootlets providing excellent opportunity for dating of alternations of dune building and stability by using optically stimulated luminescence (OSL). Deduced from the OSL age of the oldest aeolian layer dated, we conclude that the onset of aridity dates back to at least ∼65 ka. Older phases of aeolian activity though, following a fluvial depositional phase 160 ka ago, cannot be excluded, although no aeolian layers giving evidence for this have been found in the two dunes dated here. Unconsolidated dune sands in the upper part of one section with Late Holocene (4 ka to modern) depositional ages indicate a reactivation of the dunefield in recent times.From the crosscheck of ¹⁴C ages of the carbonated rootlets with OSL results it is concluded that under the given environmental conditions radiocarbon dating of the calcareous rootlets is not able to provide reliable ages for the phase of soil development.     

Generation of unusual branched long chain alkanes from hydrous pyrolysis of anammox bacterial biomass

Anammox, the microbial anaerobic oxidation of NH₄⁺ by NO₂⁻ to produce N₂, is recognised as a key process in the marine, freshwater and soil N cycles, and has been found to be a major sink for fixed inorganic N in the ocean. Ladderane lipids are unique anammox bacterial membrane lipids used as biomarkers for such bacteria in recent and past environmental settings. However, their fate during diagenesis and early catagenesis is not well constrained. In this study, hydrous pyrolysis experiments were performed on anammox bacterial biomass and the generated aliphatic hydrocarbons, present in oil generated at 220–365 °C, were analysed. A unique class of hydrocarbons was detected, and a representative component was isolated and rigorously identified using 2D nuclear magnetic resonance (NMR) spectroscopy. It consisted of C₂₄ to C₃₁ branched long chain alkanes with two internal ethyl and/or propyl substituents. The alkanes were generated above 260 °C, with maximum generation at 320 and 335 °C. Their stable carbon isotopic values were depleted in ¹³C, similar to carbon isotope values of the original anammox lipids, indicating that they were thermal products generated from lipids of anammox bacterial biomass. A range of sediments from different geological periods where anammox may have been an important process was screened for the presence of these compounds as possible catagenetic products. They were not detected, either because the concentration was too low, or the sediments screened were too immature for them to have been generated, or because the artificially produced products of anammox lipids may not reflect the natural diagenetic and catagenetic products of ladderane lipids.     

Diagenesis of organic matter in a 400 m organic rich sediment core from offshore Namibia using solid state 13C NMR and FTIR

Although rates and mechanisms of early diagenesis have been well studied, the effects of microbial metabolism on the molecular composition of the sedimentary organic matter (SOM) over long periods of time need more investigation. In this study, we characterize the early diagenesis of marine SOM from organic rich sediments of the Ocean Drilling Program site 1082 located off Namibia, in the vicinity of the Benguela coastal upwelling system. We used both Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (¹³C NMR) to assess the quantitative partitioning of the organic carbon into major compound classes (aliphatic, aromatic, ester, carboxylic, amide and carbons from carbohydrates). Then, we calculate the SOM composition in the main biomolecules (proteins, carbohydrates, lipids and lignin) on the basis of previous ¹³C NMR based estimates of the molecular composition of the organic mixtures. Results show that the SOM is still labile at 7 m below the seafloor (mbsf) and composed of about 25% proteins and 15% carbohydrates. With increasing depth, the protein content exponentially decreases to 13% at 367 mbsf, whereas the carbohydrate content decreases linearly to 11%. The lignin and lipid content consistently represent around 10% and 40% of the SOM, respectively, and show an increase with depth, due mostly to selective enrichment as the more labile components are lost by degradation. Thus, these components of the SOM are considered refractory at the depth scale considered. The calculated remineralization rates are extremely slow ranging from 5.6 mol C m⁻³ ky⁻¹ at the top of the core to 0.2 mol C m⁻³ ky⁻¹ according to the organic carbon flux to the seafloor. Knowing the labile carbon losses, we propose a method to calculate the initial TOC before the diagenesis took place.     

Soil organic carbon quantity,chemistry and thermal stability in a mountainous landscape: A Rock–Eval pyrolysis survey

Mountain soils store huge amounts of carbon which may be highly vulnerable to the strong land use and climate changes that mountain areas currently experience worldwide. Here, we tested the Rock–Eval (RE) pyrolysis as a proxy technique to (i) quantify soil organic carbon (SOC) stocks, (ii) bring insights into SOC bulk chemistry and (iii) investigate biogeochemical stability at the landscape scale in a mountain area of the French calcareous Prealps. A total of 109 soils from 11 eco-units representing the variety of ecosystems of the study area were analyzed with RE pyrolysis. RE pyrolysis showed an excellent predictive performance (R² = 0.99) for SOC content even in calcareous soils. The technique revealed specific chemical fingerprints for some eco-units and soil types, with decreasing hydrogen index values from Anthroposols (425 ± 62 mg HC/g SOC) to Umbrisols, Leptosols (311 ± 49 mg HC/g SOC) and to Cambisols (278 ± 35 mg HC/g SOC), associated with an increase in SOC maturation. Newly developed RE pyrolysis indices revealed the high stability of SOC in most eco-units developed on Cambisols (acidic grasslands, alpine meadows, bushy facies) and a significantly lower stability of SOC in mountain ridges, sheepfold areas and coniferous forest soils. The persistence of SOC in this mosaic of ecosystems may depend not only on its chemistry or thermal stability, but also on local environmental factors such as climatic conditions or pH, especially for high altitude soils. Overall, RE pyrolysis appears as an appropriate tool for landscape scale carbon inventories and could become a standardized proxy for assessing the vulnerability of SOC stocks.     

The subfossil tree deposits from the Garonne Valley and their implications on Holocene alluvial plain dynamics

Subfossil tree trunks deposits are common in large rivers, but their status as a source for dating alluvial sequences and palaeoenvironmental studies is still discussed. Particularly their origin and the process(es) of deposition as well as a possible remobilization were pointed as a limit to their use to document river alluvial changes. In this work we report the discovery of the largest subfossil trunks deposits in the Garonne valley. These new data are compared to the previous ones. A set of 17 tree trunks and more than 300 smaller wood fragments were collected. The xylologic study shows the prevalence of Quercus and a single occurrence of Ulmus. These two hardwood species are commonly associated with riparian forest. The ¹⁴C dating carried out on seven trunks and a single branch of Quercus on the outermost identified growth rings, indicates age ranging from 8400–8000 cal. BP for the oldest fragment (bough) to 4300–4000 cal. BP for the most recent tree trunk. Radiocarbon ages of the trunks are aggregated into two main periods: 5300–5600 cal. BP (four trunks) and 4300–4000 cal. BP (three trunks). The radiocarbon (charcoal) dating of the top of the alluvial sequence overlaying the trunks gives an age between 1965–1820 and 1570–1810 cal. BP, i.e. between the 2nd and the 5th c. AD. In addition, the discovery of two unpublished subfossil tree trunks deposits in Finhan are reported (six trunks). At the light of these results, we discuss previously proposed models for the Garonne floodplain building.     

Chemical and bioassay characterisation of nitrogen availability in biochar produced from dairy manure and biosolids

Biochar is charcoal made from waste biomass and intended to be added to soil to improve soil function and reduce emissions from the biomass caused by natural degradation to CO₂. Nitrogen (N) forms in biochar can be complex and their lability likely to be influenced by pyrolysis temperature which, together with the nature of carbon (C), will influence N mineralisation or immobilisation. These complex relationships are poorly understood, yet impact strongly on the potential agronomic value of biochar. In this study, N in different biochar samples produced from human and animal waste streams (biosolids and cow manure; each mixed with eucalyptus wood chips in a 1:1 dry wt. ratio) at different pyrolysis conditions (highest heating temperature 250, 350, 450 and 550 °C) was extracted with 6 M HCl. The acid hydrolysable, extractable N (THN) was fractionated into ammonia N (AN), amino acid N (AAN), amino sugar N (ASN) and uncharacterisable hydrolysable N (UHN). Biochar samples were also treated with 0.167 M K₂Cr₂O₇ acid to determine N potentially available in the long term. An incubation study of the different biochar samples mixed with acid washed sand was conducted at 32 °C for 81 days to study both C and N turnover. During incubation, the CO₂ released was trapped in NaOH and quantified. Hydrolysable N decreased as pyrolysis temperature increased from 250 to 550 °C. Fractionation into AN, AAN, ASN and UHN revealed progressive structural rearrangement of N with pyrolysis temperature. Based on HCl hydrolysis and dichromate oxidation results, C and N in biochar became more stable as pyrolysis temperature increased. The ratio of volatile C to THN was a useful indicator of whether net N mineralisation or immobilisation of N in biochar occurred. THN thus seems a sound estimate of the labile N fraction in biochar in the short term; however, dichromate-oxidisable N is probably more meaningful in the long run. Further studies using different types of biochar need to be conducted under more realistic conditions to obtain more information on N availability in biochar once in soil.