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Rationale: Helium (He) and energy shortages have caused price increases and reduced their availability. Using three combustion reactions per acquisition of carbon and nitrogen isotope ratios saves 50% He and energy during the elemental analysis/isotope ratio mass spectrometry (EA/IRMS). This approach needs to be tested for sulfur isotope (δ34S) analyses. Methods: A new method to measure δ34S in three sequential combustion reactions within one EA/IRMS acquisition was developed. The same material or blank samples could be used in the three reactions. After SO2 was used, a N2 purging method was employed to prolong the lifetime of the valves in the EA/IRMS interface. The 3×EA/IRMS was applied to measure δ34S in precious samples, such as Ag2S from acid‐volatile and chromium‐reducible sulfur extracted with a multiple‐port setup. Results: The 3×EA/IRMS‐δ34S method was validated with replicate analyses of international reference materials and laboratory standards with a wide range of mineralogical compositions and δ34S values. The method provided a strategic advantage for the δ34S measurements of small precious samples (measured between blanks). The accuracy and precision of the 3×EA/IRMS values effectively matched those obtained using conventional EA/IRMS, with good agreement between the mean ± SD values and the recommended values with their uncertainties. Conclusions: Compared with the conventional EA/IRMS, the proposed method provides accurate and precise δ34S measurements of the sulfate and sulfide samples while saving approximately 50% of He, energy, SO2 reference gas, O2, analysis time, and cost. Notably, 3×EA/IRMS can provide up to three δ34S values unaffected by memory effects. [ABSTRACT FROM AUTHOR]

This article discusses the global energy shortage crisis and the impact it has had on helium shortages and rising prices. It highlights the need for academic institutions and industries to find alternatives and reduce helium consumption. The focus is on excessive helium consumption in high-temperature combustion reactors used in isotope ratio mass spectrometers. The author presents a strategy to cope with helium shortages in elemental analysis and isotope ratio mass spectrometry by using three combustion reactions in a single acquisition. The article also provides a table of values for various reference materials used in isotopic analysis, along with their uncertainties. The document describes a modified method for analyzing carbon and nitrogen isotopes using an elemental analyzer/isotope ratio mass spectrometer. This method has been validated and found to be accurate and precise, while also reducing helium consumption, analysis time, and costs. It is suitable for high-throughput analysis in academia, industry, and research. [Extracted from the article]

In this study, we present evidence of a Paleocene-Eocene Thermal Maximum (PETM) record within a 543-m-thick (1780 ft) deep-marine section in the Gulf of Mexico (GoM) using organic carbon stable isotopes and biostratigraphic constraints. We suggest that climate and tectonic perturbations in the upstream North American catchments can induce a substantial response in the downstream sectors of the Gulf Coastal Plain and ultimately in the GoM. This relationship is illustrated in the deep-water basin by (1) a high accommodation and deposition of a shale interval when coarse-grained terrigenous material was trapped upstream at the onset of the PETM, and (2) a considerable increase in sediment supply during the PETM, which is archived as a particularly thick sedimentary section in the deep-sea fans of the GoM basin. Despite other thick PETM sections being observed elsewhere in the world, the one described in this study links with a continentalscale paleo-drainage, which makes it of particular interest for paleoclimate and source-to-sink reconstructions. [ABSTRACT FROM AUTHOR]

Tracing methods of non-European EVOOs commercialized worldwide are becoming crucial for effective authenticity controls. Limited analytical studies of these oils are available on a global scale, similar to those of European EVOOs. We report for the first time the fatty acid concentrations, bulk-oil 2H/1H, 13C/12C, and 18O/16O ratios and fatty acid 13C/12C ratios of 43 authentic monovarietal EVOOs from different geographical regions in Argentina and Uruguay. The samples were obtained from a wide range of latitudes and altitudes along an E–W profile, from lowlands near the Atlantic Ocean to the pre-Andean highlands near the Pacific Ocean. Principal component scores were used to cluster EVOOs into three groups— central-western Argentina, central Argentina, and Uruguay—based on nine stable isotope ratios and the oleic-linoleic acid concentration ratio. The bulk 2H/1H and 18O/16O values and 13C/12C of palmitoleic and linoleic acids provide good tools for differentiating these oils via linear discriminant analysis. • Characterization of authentic EVOOs from regions in Argentina and Uruguay. • Argentinian and Uruguayan EVOOs differ in stable isotopes (SI, δ2H, δ13C, δ18O). • Minor differences were noted for fatty acid profiles, more for oleic/linoleic. • PCA and LDA allows discrimination of the oils according to geographical origin. • Suitability of SI for authenticity and traceability of EVOO is confirmed. [ABSTRACT FROM AUTHOR]

The stable isotope ratios of sulfur (δ34S relative to Vienna Cañon Diablo Troilite) in sulfates and sulfides determined by elemental analysis and isotope ratio mass spectrometry (EA/IRMS) have been proven to be a remarkable tool for studies of the (bio)geochemical sulfur cycles in modern and ancient environments. However, the use of EA/IRMS to measure δ34S in arsenides and sulfarsenides may not be straightforward. This difficulty can lead to potential health and environmental hazards in the workplace and analytical problems such as instrument contamination, memory effects, and a non-matrix-matched standardization of δ34S measurements with suitable reference materials. To overcome these practical and analytical challenges, we developed a procedure for sulfur isotope analysis of arsenides, which can also be safely used for EA/IRMS analysis of arsenic sulfides (i.e., realgar, orpiment, arsenopyrite, and arsenian pyrite), and mercury sulfides (cinnabar). The sulfur dioxide produced from off-line EA combustion was trapped in an aqueous barium chloride solution in a leak-free system and precipitated as barium sulfate after quantitative oxidation of hydrogen sulfite by hydrogen peroxide. The derived barium sulfate was analyzed by conventional EA/IRMS, which bracketed the δ34S values of the samples with three international sulfate reference materials. The protocol (BaSO4-EA/IRMS) was validated by analyses of reference materials and laboratory standards of sulfate and sulfides and achieved accuracy and precision comparable with those of direct EA/IRMS. The δ34S values determined by BaSO4-EA/IRMS in sulfides (arsenopyrite, arsenic, and mercury sulfides) samples from different origins were comparable to those obtained by EA/IRMS, and no sulfur isotope fractionations were introduced during sample preparation. We report the first sulfur isotope data of arsenides obtained by BaSO4-EA/IRMS. [ABSTRACT FROM AUTHOR]

We investigated the within- and between-leaf variability in the carbon and nitrogen isotope composition (δ 13C and δ 15N) and total nitrogen (TN) content in two grapevine cultivars (Vitis vinifera cv. Chasselas and Pinot noir) field-grown under rain-fed conditions. The within-leaf variability was studied in discs sampled from base-to-tip and left and right regions from the margin to midrib. The intra- and interplant variability was studied by comparing leaves at different positions along the shoot (basal, median, apical). In leaves from both cultivars, a decrease in δ 13C from base to tip was observed, which is in line with an upward gradient of stomatal density and chlorophyll concentration. Less important, but still significant differences were observed between the right and left discs. The leaf TN and δ 15N values differed between cultivars, showed smaller variations than the δ 13C values, and no systematic spatial trends. The intraleaf variations in δ 13C, δ 15N, and TN suggest that stomatal behavior, CO 2 fixation, chlorophyll concentrations, and the chemical composition of leaf components were heterogeneous in the leaves. At the canopy scale, the apical leaves had less 13C and more 15N and TN than the basal leaves, indicating differences in their photosynthetic capacity and remobilizations from old, senescing leaves to younger leaves. Overall, this study demonstrates patchiness in the δ 13C and δ 15N values of grapevine leaves and species-specificity of the nitrogen assimilation and 15N fractionation. These findings suggest that care must be taken not to overinterpret foliar δ 13C and δ 15N values in studies based on fragmented material as markers of physiological and biochemical responses to environmental factors. [Display omitted] • Potential patchiness of δ 13C, δ 15N, and nitrogen content in leaves is explored. • Within-leaf δ 13C and δ 15N values varied up to 1.5 mUr. • Young apical leaves had lower δ 13C, higher N content, and δ 15N than old basal leaves. • Significant interspecific differences were found in leaf N content and δ 15N values. [ABSTRACT FROM AUTHOR]

The sulfur (S) isotope composition of carbonate associated sulfate (CAS) in carbonate rocks has been used to assess variations in paleo-oceanographic redox conditions and its relationship to biotic changes in Earth's history, including the Smithian – Spathian transition. However, previous CAS studies of the Olenekian are mostly based on nearshore continental shelf sections and report highly variable δ34S values mostly offset from those of contemporaneous evaporites, casting doubt on the utility of the CAS proxy during this interval. The current study presents new CAS isotopic data from three well-dated carbonate successions which were deposited in continental shelf (Qiakong) and offshore marine (Wadi Musjah and Jebel Aweri) environments during the Olenekian (Smithian – Spathian). The aim of the study was to constrain the temporal and spatial variations in sulfur cycling and its relation to marine redox and faunal changes across the Smithian – Spathian transition (ca. 250.5–248.8 Ma). The CAS dataset is complemented by rare earth element (REE) concentration data and thin section petrography. Using a suite of optical and geochemical techniques, the preservation of near-primary CAS isotopic information in the studied samples is evaluated. Results indicate that of the three sections investigated, the offshore sections mostly preserve near-primary marine sulfate S-isotope compositions while the continental shelf Qiakong section suffers from post-depositional alteration of CAS. Comparisons of our new, as well as previously published CAS δ34S data, with the evaporite δ34S record suggests that although Olenekian CAS δ34S values may have been modified by diagenetic processes, a global and primary seawater δ34S trend can be delineated as follows: seawater δ34S values increased across the middle Smithian and Smithian – Spathian boundary (SSB). Based on our new CAS data, this increase was in the order of 9 ‰ over ca. 1.14 million years. Other short-term variability in the CAS δ34S record most likely reflects diagenetic processes. The middle Smithian to SSB δ34S increase is attributed to a global increase in microbial sulfate reduction and pyrite burial associated with decreasing ocean dissolved oxygen during this time. Calculations of the rate of sulfur cycling and box modeling constraints indicate that Olenekian marine sulfur cycle perturbations occurred while the seawater sulfate reservoir only had between 10 and 25% of the modern marine sulfate inventory. Furthermore, results from the current study suggest that variations in ocean dissolved oxygen levels, inferred from the δ34S and REE data, are not consistently correlated with nektonic faunal changes during the Olenekian in the studied sections. As such, faunal turnover during the Olenekian is unlikely to be explained exclusively by abiotic factors such as ocean-atmosphere oxygenation levels. • Global CAS records preserve primary long-term marine δ34S trends in the Olenekian. • Global δ34S records support increased MSR and pyrite burial across the SSB. • Olenekian δ34S trends support decreasing ocean dissolved oxygen across the SSB. • Olenekian seawater sulfate concentration was 10–25% of modern seawater inventory. • No consistent link between ocean dissolved oxygen levels and conodont diversity. [ABSTRACT FROM AUTHOR]

Nitrogen deficit affects both crop production and composition, particularly in crops requiring an optimal fruit N content for aroma development. The adaptation of cultural practices to improve N use efficiency (NUE) (i.e. N uptake, assimilation and partitioning) is a priority for the sustainable production of high-quality crops. A trial was set on potted grapevines (Vitis vinifera L. cv. Chasselas) to investigate the potential of crop limitation (via bunch thinning) to control plant NUE and ultimately fruit N composition at harvest. A large crop load gradient was imposed by bunch thinning (0.5–2.5 kg m–2) and N traceability in the plant was realised with an isotope-labelling method (10 atom % 15N foliar urea). The results indicate that the mobilisation of root reserves plays a major role in the balance of fruit N content. Fertiliser N uptake and assimilation appeared to be strongly stimulated by high-yielding conditions. Fertilisation largely contributed to fulfilling the high fruit N demand while limiting the mobilisation of root reserves under high yield conditions. Plants were able to modulate root N reserve mobilisation and fertiliser N uptake in function of the crop load, thus maintaining a uniform N concentration in fruits. However, the fruit free amino N profile was modified, which potentially altered the fruit aromas. These findings highlight the great capacity of plants to adapt their N metabolism to constraints, crop thinning in this case. This confirms the possibility of monitoring NUE by adapting cultural practices. Without fertilisation, plant nutrition can be enhanced to some extent through the optimisation of agricultural practices. In a 15N-labelling experiment, we demonstrate that grapevine has a strong ability to regulate N uptake and reserve mobilisation to maintain a constant fruit N concentration despite changes in crop load. Nitrogen uptake and root N mobilisation were positively correlated with crop load. This result is essential for improving perennial fruit crop production through higher fertilisation efficiency and lower environmental impact. [ABSTRACT FROM AUTHOR]

Successful reproductive output and recruitment is crucial to coral persistence and recovery following anthropogenic stress. Feeding is known to alter coral physiology and increase resilience to bleaching.The goal of the study was to address the knowledge gap of the influence of feeding on reproductive output and offspring phenotype.Colonies of Stylophora pistillata from the Northern Gulf of Aqaba (Red Sea) were fed an Artemia diet or unfed for 5 months during gametogenesis, fertilization, and brooding. In addition, time to settlement and mortality of planulae were assessed at water temperatures ranging from winter temperature (22°C) to three degrees above average peak summer temperature (31°C). A range of physiological parameters was measured in parents and offspring.In brooding parents, feeding significantly increased protein concentration and more than tripled the number of released planulae. Planulae from unfed colonies had higher chlorophyll per symbiont concentration and concomitantly higher photosynthetic efficiency compared to planulae from fed parents. In settlement assays, planulae showed a similar thermal resistance as known for this Red Sea adult population. Mortality was greater in planulae from unfed parents at ambient and 3°C above ambient temperature despite higher per offspring investment in terms of total fatty acid content. Fatty acid profiles and relative abundances were generally conserved between different fed and unfed colonies but planulae were enriched in monounsaturated fatty acids relative to adults, that is, 16:1, 18:1, 20:1, 22:1, and 24:1 isomers.Ultimately the availability of zooplankton could influence population physiology and recruitment in corals. [ABSTRACT FROM AUTHOR]

Recently, we reported that the carbon isotope composition of the solid residues obtained by freeze-drying white and red wines (δ13CWSR) could be used for tracing the water status of the vines whose grapes were used to produce them. Here, we compare different methods using δ13C values of other wine components, particularly those of whole wine (δ13CWW) obtained by elemental analysis and isotope ratio mass spectrometry (EA/IRMS) and of wine ethanol (δ13CWEtOH) obtained by gas chromatography/combustion/IRMS (GC/C/IRMS), for their suitability to assess the vine water status. The studied wines were obtained from field-grown cultivars (Vitis vinifera L. cv. Chasselas, Petite Arvine, and Pinot noir) under different water treatments during the 2009–2014 seasons and were the same wines in which the δ13CWSR was measured previously. The EA/IRMS method for whole wine used two successive EA analytical cycles in each acquisition period to reduce the residence time of the sample capsules in the autosampler. The sample aliquots for the EA/IRMS and GC/C/IRMS analyses were optimized for peak-size differences less than 10% between the sample and reference gas. For all wine varieties, the δ13CWW and δ13CWEtOH values were linearly correlated with the predawn leaf water potential (Ψpd) and therefore serve as reliable indicators of vine water status, as do the δ13C values for must sugars and wine solid residues. The strongest negative correlations with Ψpd were for δ13Csugars (r = −0.94, n = 54) and δ13CWEtOH (r = −0.91) and were lower but still highly significant (p < 0.00001) for δ13CWW (r = −0.71) and δ13CWSR (r = −0.70). An evaluation of the advantages and drawbacks of the different methods is presented, showing that the δ13C analysis of wine ethanol by GC/C/IRMS is the most appropriate. [ABSTRACT FROM AUTHOR]

The grapevine is one of the most important edible fruit plants cultivated worldwide, and it is highly sensitive to changes in the soil water content. We studied the total carbon and nitrogen contents and stable isotope compositions (C/N WSR , δ 13 C WSR and δ 15 N WSR values) of the solid residues obtained by freeze-drying wines produced from two white grapevine cultivars ( Vitis vinifera L. cv Chasselas and Petite Arvine) field grown under different soil water regimes while maintaining other climatic and ecopedological conditions identical. These experiments simulated the more frequent and extended climate change-induced periods of soil water shortage. The wines were from the 2009–2014 vintages, produced using the same vinification procedure. The plant water status, reflecting soil water availability, was assessed by the predawn leaf water potential ( Ψ pd ), monitored in the field during the growing seasons. For both wine varieties, the δ 13 C WSR values are highly correlated with Ψ pd values and record the soil water availability set by soil water holding capacity, rainfall and irrigation water supply. These relationships were the same as those observed for the carbon isotope composition of fruit sugars (i.e., must sugars) and plant water status. In Chasselas wines, the nitrogen content and δ 15 N WSR values decreased with soil water deficit, indicating control of the flux of soil-water soluble nutrients into plants by soil water availability. Such a correlation was not found for Petite Arvine, probably due to different N-metabolism processes in this genetically atypical cultivar. The results presented in this study confirm and generalize what was previously found for red wine (Pinot noir); the carbon isotope composition of wine solid residues is a reliable indicator of the soil and the plant water status and thus can be used to trace back local climatic conditions in the vineyard's region. In most wines (except Petite Arvine) the C/N WSR and δ 15 N WSR values are indicators of the origin of the nitrogen supplied to the plant's fruit (grape) that can be used to assess the N dynamics in the soil-water-plant system. [ABSTRACT FROM AUTHOR]

Soil water repellency (hydrophobicity) prevents water from wetting or infiltrating soils, triggering changes in the ecosystems. Fire may develop, enhance or destroy hydrophobicity in previously wettable or water-repellent soils. Soil water repellency is mostly influenced by the quality and quantity of soil organic matter, particularly the lipid fraction. Here we report the results of a study on the effect of fire on the distribution of soil lipids and their role in the hydrophobicity grade of six particle size fractions (2–1, 1–0.5, 0.5–0.25, 0.25–0.1, 0.1–0.05 and <0.05 mm) of an Arenosol under Quercus suber canopy at the Doñana National Park (SW-Spain). Hydrophobicity was determined using water drop penetration time test. Field emission scanning electron microscopy (FESEM) was used to assess the presence and morphology of the inorganic and organic soil components in the particle size fractions. Soil lipids were Soxhlet extracted with a dichloromethane-methanol mixture. Fatty acids (FAs) and neutral lipids were separated, derivatized, identified and quantified by gas chromatography/mass spectrometry and gas chromatography/flame ionization detection. The hydrophobicity values of soil samples and fractions were statistically different ( P < 0.05), for both, the unburnt and burnt soils, and particle size fractions. All samples displayed a similar distribution of FAs, straight-chain saturated acids in the C 14 –C 32 range, and neutral lipids ( n -alkan-1-ols, n -alkanes), only differing in their relative abundances. Among possible biogeochemical mechanisms responsible for the changes in soil lipids, the observed depletion of long chain FAs (C ≥24 ) in the coarse fraction is best explained by thermal cracking caused by the heat of the fire. The enrichment of long chain FAs observed in other fractions suggests possible exogenous additions of charred, lipid-rich, material, like cork suberin or other plant-derived macromolecules (cutins). Principal component analysis was used to study the relationships between hydrophobicity with soil organic matter and its different components. Extractable organic matter (EOM) and specifically long chain FAs content were positively correlated to soil hydrophobicity. Therefore, the latter could be used as biomarkers surrogated to hydrophobicity in sandy soils. [ABSTRACT FROM AUTHOR]

This paper describes a novel approach to reassess the water status in vineyards based on compound-specific isotope analysis (CSIA) of wine volatile organic compounds ( δ 13 C VOC/VPDB ) and bulk carbon and nitrogen isotopes, and the C/N molar ratios of the wine solid residues ( δ 13 C SR/VPDB , δ 15 N SR/Air-N2 ). These analyses link gas chromatography/combustion and elemental analysis to isotope ratio mass spectrometry (GC/C/IRMS, EA/IRMS). Field-grown cultivars of Pinot Noir grapevines were exposed during six growing seasons (2009–2014) to controlled soil water availability, while maintaining identical the other environmental variables and agricultural techniques. Wines were produced from the grapes by the same oenological protocol. This permitted for the assessment of the effects in the biochemistry of wines solely induced by the changes in the plant-soil water status. This mimicked the more recurrent and prolonged periods of soil water deficiency due to climate changes. Water stress in grapevine was assessed by the measurement of the predawn leaf water potential ( Ψ pd ) and the stable carbon isotope composition of the berry sugars during harvest (must sugars). For quantitation purposes and the normalization of the measured stable carbon isotope ratios of the VOCs, the wine samples were spiked with three standard compounds with known concentration and δ 13 C VPDB values. VOCs were extracted by liquid–liquid extraction and analyzed by gas chromatography/flame ionization detection (GC/FID), gas chromatography/mass spectrometry (GC/MS), and GC/C/IRMS. δ 13 C values were obtained for eighteen VOCs. The solid residues were obtained by freeze-drying wine aliquots and were analyzed for their C and N content and isotope composition by EA/IRMS. All the isotopic ratios ( δ 13 C SR , δ 15 N SR , δ 13 C VOC ) are highly correlated with the Ψ pd values, indicating that the proposed gas chromatography and isotope ratio mass spectrometry approach is a useful tool to assess the changes in the water status of grapevine cultivars in different terroirs . The combined analytical approach was used for the first time to complement the assessment of soil water availability effects on the grapevine. The δ 13 C values of the volatile compounds helped confirm (or establish) their main source(s) and biosynthetic pathway(s). Importantly, we also show for the first time that the combination of C/N and δ 15 N values of freeze-dried wines have an unexplored potential for the study of nitrogen dynamics in soil/grape/wine systems. [ABSTRACT FROM AUTHOR]

High input of organic carbon and/or slowly renewing bottom waters frequently create periods with low dissolved oxygen concentrations on continental shelves and in coastal areas; such events can have strong impacts on benthic ecosystems. Among the meiofauna living in these environments, benthic foraminifera are often the most tolerant to low oxygen levels. Indeed, some species are able to survive complete anoxia for weeks to months. One known mechanism for this, observed in several species, is denitrification. For other species, a state of highly reduced metabolism, essentially a state of dormancy, has been proposed but never demonstrated. Here, we combined a 4 weeks feeding experiment, using 13C-enriched diatom biofilm, with correlated TEM and NanoSIMS imaging, plus bulk analysis of concentration and stable carbon isotopic composition of total organic matter and individual fatty acids, to study metabolic differences in the intertidal species Ammonia tepida exposed to oxic and anoxic conditions. Strongly contrasting cellular-level dynamics of ingestion and transfer of the ingested biofilm components were observed between the two conditions. Under oxic conditions, within a few days, intact diatoms were ingested, degraded, and their components assimilated, in part for biosynthesis of different cellular components: 13C-labeled lipid droplets formed after a few days and were subsequently lost (partially) through respiration. In contrast, in anoxia, fewer diatoms were initially ingested and these were not assimilated or metabolized further, but remained visible within the foraminiferal cytoplasm even after 4 weeks. Under oxic conditions, compound specific 13C analyses showed substantial de novo synthesis by the foraminifera of specific polyunsaturated fatty acids (PUFAs), such as 20:4(n-6). Very limited PUFA synthesis was observed under anoxia. Together, our results show that anoxia induced a greatly reduced rate of heterotrophic metabolism in Ammonia tepida on a time scale of less than 24 hours, these observations are consistent with a state of dormancy. [ABSTRACT FROM AUTHOR]

Rationale The carbon, hydrogen and oxygen stable isotope composition ( δ13C, δ2H, and δ18O values) of plants and their products is linked to photosynthetic fractionation, environmental factors and agricultural practices. Therefore, they contribute to determining the purity of commercial vegetable oils and may provide information on their geographical origin. Methods Maize, olive, sunflower, groundnut, soybean and rice oils differing in sites of growth in the southern and northern hemispheres were characterized by bulk oil stable isotope ratios ( δ13Cbulk, δ2Hbulk, and δ18Obulk values), fatty acid (FA) concentrations and δ13CFA values using elemental analysis/isotope ratio mass spectrometry, gas chromatography/mass spectrometry, gas chromatography/flame ionization detection and gas chromatography/combustion/isotope ratio mass spectrometry. Principal component analysis was applied to examine the inherent structure of the data. Results The δ13Cbulk values of maize oils (−18.4 to −14.9 ‰) are typical for C4 plants, and those of olive (−30.2 to −28.2 ‰), sunflower (−30.2 to −29.2 ‰), groundnut (−29.3 ‰), soybean (−30.6 ‰), and rice (−34.5 ‰) oils are typical for C3 plants. The δ2Hbulk values vary from −161 to −132 ‰ for maize oils and −171 to −109 ‰ for C3 oils. The δ18Obulk values of all oils vary between 15.2 and 38.9 ‰. The major δ13CFA differences (>5 ‰) within plant species render the inter-C3-species comparison difficult. These differences are explained in terms of variations in the lipid biosynthetic pathways and blend of vegetable oils of different FA composition and δ13CFA values. The samples from the southern hemisphere are generally enriched in 13C compared with those from the northern hemisphere. Differences between the southern and northern hemispheres were observed in δ2H ( p < 0.001) and δ18Obulk ( p = 0.129) values for all C3 oils, and in δ13C18:1 ( p = 0.026) and δ18Obulk ( p = 0.160) values for maize oils. Conclusions The results of this study show that combining bulk and molecular stable isotope ratios, FA compositions and their statistical analysis helps the characterization of the geographic origin of oils. This methodology can be used to detect and source impurities in valuable vegetable oils commercialized worldwide. Copyright © 2016 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

The later stages of Earth's transition to a permanently oxygenated atmosphere during the Great Oxidation Event (GOE; ∼2.43–2.06 Ga) is commonly linked with the suggestion of an "oxygen overshoot" during the ∼2.22–2.06 Ga Lomagundi Event (LE), which represents Earth's most pronounced and longest-lived positive carbon isotope excursion. However, the magnitude and extent of atmosphere-ocean oxygenation and implications for the biosphere during this critical period in Earth's history remain poorly constrained. Here, we present nitrogen (N), selenium (Se), and carbon (C) isotope data, as well as bio-essential element concentrations, for Paleoproterozoic marine shales deposited during the LE. The data provide evidence for a highly productive and well-oxygenated photic zone, with both inner and outer-shelf marine environments characterized by nitrate- and Se oxyanion-replete conditions. However, the redoxcline subsequently encroached back onto the inner shelf during global-scale deoxygenation of the atmosphere-ocean system at the end of the LE, leading to locally enhanced water column denitrification and quantitative reduction of selenium oxyanions. We propose that nitrate-replete conditions associated with fully oxygenated continental shelf settings were a common feature during the LE, but nitrification was not sufficiently widespread for the aerobic nitrogen cycle to impact the isotopic composition of the global ocean N inventory. Placed in the context of Earth's broader oxygenation history, our findings indicate that O 2 levels in the atmosphere-ocean system were likely much lower than modern concentrations. Early Paleoproterozoic biogeochemical cycles were thus far less advanced than after Neoproterozoic oxygenation. • Enhanced oxygenic photosynthesis during the ∼2.22–2.06 Ga Lomagundi carbon isotope excursion. • Fully oxygenated continental shelf seawater column during the Paleoproterozoic Lomagundi Event. • Coevolution of deep redoxcline in the Paleoproterozoic oceans and atmospheric oxygen overshoot during the Lomagundi Event. • Modern biogeochemical cycles were not achieved in the Paleoproterozoic oceans during the Great Oxidation Event. [ABSTRACT FROM AUTHOR]

A continuum of carbon, from atmospheric CO 2 to secondary calcium carbonate, has been studied in a soil associated with scree slope deposits in the Jura Mountains of Switzerland. This approach is based on former studies conducted in other environments. This C continuum includes atmospheric CO 2 , soil organic matter (SOM), soil CO 2 , dissolved inorganic carbon (DIC) in soil solutions, and secondary pedogenic carbonate. Soil parameters (pCO 2 , temperature, pH, C min and C org contents), soil solution chemistry, and isotopic compositions of soil CO 2 , DIC, carbonate and soil organic matter (δ 13 C CO 2 , δ 13 C DIC , δ 13 C car and δ 13 C SOM values) have been monitored at different depths (from 20 to 140 cm) over one year. Results demonstrated that the carbon source in secondary carbonate (mainly needle fiber calcite) is related to the dissolved inorganic carbon, which is strongly dependent on soil respiration. The heterotrophic respiration, rather than the limestone parent material, seems to control the pedogenic carbon cycle. The correlation of δ 13 C org values with Rock-Eval HI and OI indices demonstrates that, in a soil associated to scree slope deposits, the main process responsible for 13 C-enrichment in SOM is related to bacterial oxidative decarboxylation. Finally, precipitation of secondary calcium carbonate is enhanced by changes in soil pCO 2 associated to the convective movement of air masses induced by temperature gradients (heat pump effect) in the highly porous scree slope deposits. The exportation of soil C-leachates from systems such as the one studied in this paper could partially explain the “gap in the European carbon budget” reported by recent studies. [ABSTRACT FROM AUTHOR]

Periodic food shortage is a common ecological stressor for animals, likely to drive physiological and metabolic adaptations to alleviate its consequences, particularly for juveniles that have no option but to continue to grow and develop despite undernutrition. Here we study changes in metabolism associated with adaptation to nutrient shortage, evolved by replicate Drosophila melanogaster populations maintained on a nutrient-poor larval diet for over 240 generations. In a factorial metabolomics experiment we showed that both phenotypic plasticity and genetically-based adaptation to the poor diet involved wide-ranging changes in metabolite abundance; however, the plastic response did not predict the evolutionary change. Compared to nonadapted larvae exposed to the poor diet for the first time, the adapted larvae showed lower levels of multiple free amino acids in their tissues—and yet they grew faster. By quantifying accumulation of the nitrogen stable isotope 15N we show that adaptation to the poor diet led to an increased use of amino acids for energy generation. This apparent "waste" of scarce amino acids likely results from the trade-off between acquisition of dietary amino acids and carbohydrates observed in these populations. The three branched-chain amino acids (leucine, isoleucine, and valine) showed a unique pattern of depletion in adapted larvae raised on the poor diet. A diet supplementation experiment demonstrated that these amino acids are limiting for growth on the poor diet, suggesting that their low levels resulted from their expeditious use for protein synthesis. These results demonstrate that selection driven by nutrient shortage not only promotes improved acquisition of limiting nutrients, but also has wide-ranging effects on how the nutrients are used. They also show that the abundance of free amino acids in the tissues does not, in general, reflect the nutritional condition and growth potential of an animal. [ABSTRACT FROM AUTHOR]

Highlights: [•] Geochemical evidence for use of specific tools in late 4th/early 3rd millennium BC. [•] Tools were maintained with preservative based on oil from plant seeds. [•] Oil mainly from Linum usitatissimum (flax) and Papaver somniferum (poppy). [•] Minor contribution from Corylus avellana (hazelnut) and Brassica rapa (turnip). [ABSTRACT FROM AUTHOR]

The interactions between bacteria and fungi, the main actors of the soil microbiome, remain poorly studied. Here, we show that the saprotrophic and ectomycorrhizal soil fungus Morchella crassipes acts as a bacterial farmer of Pseudomonas putida, which serves as a model soil bacterium. Farming by M. crassipes consists of bacterial dispersal, bacterial rearing with fungal exudates, as well as harvesting and translocation of bacterial carbon. The different phases were confirmed experimentally using cell counting and 13C probing. Common criteria met by other non-human farming systems are also valid for M. crassipes farming, including habitual planting, cultivation and harvesting. Specific traits include delocalization of food production and consumption and separation of roles in the colony (source versus sink areas), which are also found in human agriculture. Our study evidences a hitherto unknown mutualistic association in which bacteria gain through dispersal and rearing, while the fungus gains through the harvesting of an additional carbon source and increased stress resistance of the mycelium. This type of interaction between fungi and bacteria may play a key role in soils. [ABSTRACT FROM AUTHOR]

Abstract: The early Toarcian oceanic anoxic event (Early Jurassic;∼183Myr ago) is associated with one of the largest negative carbon isotope excursion (CIE) in the whole Phanerozoic (3–7‰). Estimates of the magnitude and rate of CO2 injection in the ocean–atmosphere system are compatible with a scenario of ocean acidification. Many carbonate platforms drowned in the Pliensbachian, well before the early Toarcian event. In this paper we test the hypothesis of surface water ocean acidification by presenting data from a resilient carbonate platform: the Apennine Carbonate Platform of southern Italy. The studied sections document a dramatic shift of the carbonate factory from massive biocalcification to chemical precipitation. Lithiotis bivalves and calcareous algae (Palaeodasycladus mediterraneus), which were the most prolific carbonate producers of Pliensbachian carbonate platforms, disappear during the first phase of the early Toarcian CIE, before the most depleted values are reached. We discuss the local versus supraregional significance of this shift and propose a scenario involving abrupt decline of carbonate saturation, forced by CO2 release at the beginning of the early Toarcian CIE, followed by a calcification overshoot, driven by the recovery of ocean alkalinity. Attribution of the demise of carbonate platform hypercalcifiers to ocean acidification is supported by palaeophysiology and reinforced by experimental data on the detrimental effects of ocean acidification on recent shellfishes and calcareous algae. [Copyright &y& Elsevier]

RATIONALE The choice of containers for storage of aqueous samples between their collection, transport and water hydrogen (2H) and oxygen (18O) stable isotope analysis is a topic of concern for a wide range of fields in environmental, geological, biomedical, food, and forensic sciences. The transport and separation of water molecules during water vapor or liquid uptake by sorption or solution and the diffusive transport of water molecules through organic polymer material by permeation or pervaporation may entail an isotopic fractionation. An experiment was conducted to evaluate the extent of such fractionation. METHODS Sixteen bottle-like containers of eleven different organic polymers, including low and high density polyethylene (LDPE and HDPE), polypropylene (PP), polycarbonate (PC), polyethylene terephthalate (PET), and perfluoroalkoxy-Teflon (PFA), of different wall thickness and size were completely filled with the same mineral water and stored for 659 days under the same conditions of temperature and humidity. Particular care was exercised to keep the bottles tightly closed and prevent loss of water vapor through the seals. RESULTS Changes of up to +5‰ for δ2H values and +2.0‰ for δ18O values were measured for water after more than 1 year of storage within a plastic container, with the magnitude of change depending mainly on the type of organic polymer, wall thickness, and container size. The most important variations were measured for the PET and PC bottles. Waters stored in glass bottles with Polyseal™ cone-lined PP screw caps and thick-walled HDPE or PFA containers with linerless screw caps having an integrally molded inner sealing ring preserved their original δ2H and δ18O values. The carbon, hydrogen, and oxygen stable isotope compositions of the organic polymeric materials were also determined. CONCLUSIONS The results of this study clearly show that for precise and accurate measurements of the water stable isotope composition in aqueous solutions, rigorous sampling and storage procedures are needed both for laboratory standards and for unknown samples. Copyright © 2012 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Stable carbon and oxygen isotope analyses were conducted on pedogenic needle fibre calcite (NFC) from seven sites in areas with roughly similar temperate climates in Western Europe, including the Swiss Jura Mountains, eastern and southern France, northern Wales, and north-eastern Spain. The δ13C values (−12.5 to−6.8 ‰ Vienna Pee Dee Belemnite (VPDB)) record the predominant C3 vegetation cover at the sites. A good correlation was found between mean monthly climatic parameters (air temperature, number of frost days, humidity, and precipitation) and δ18O values (−7.8 to−3.4‰ VPDB) of all the NFC. Similar seasonal variations of δ18O values for monthly NFC samples from the Swiss sites and those of mean monthly δ18O values of local precipitation and meteorological data point out precipitation and preferential growth/or recrystallisation of the pedogenic needle calcite during dry seasons. These covariations indicate the potential of stable isotope compositions of preserved NFC in fossil soil horizons as a promising tool for palaeoenvironmental reconstructions. [ABSTRACT FROM AUTHOR]

Abstract: Stable isotopes of carbonates (δ13Ccarb, δ18Ocarb), organic matter (δ13Corg, δ15Norg) and major, trace and rare earth element (REE) compositions of marine carbonate rocks of Late Permian to Early Triassic age were used to establish the position of the Permian–Triassic boundary (PTB) at two continuous sections in the Velebit Mountain, Croatia. The chosen sections — Rizvanuša and Brezimenjača — are composed of two lithostratigraphic units, the Upper Permian Transitional Dolomite and the overlying Sandy Dolomite. The contact between these units, characterized by the erosional features and sudden occurrence of ooids and siliciclastic grains, was previously considered as the chronostratigraphic PTB. The Sandy Dolomite is characterized by high content of non-carbonate material (up to ~30wt.% insoluble residue), originated from erosion of the uplifted hinterland. A relatively rich assemblage of Permian fossils (including Geinitzina, Globivalvulina, Hemigordius, bioclasts of gastropods, ostracods and brachiopods) was found for the first time in Sandy Dolomite, 5m above the lithologic boundary in the Rizvanuša section. A rather abrupt negative δ13Ccarb excursion in both sections appears in rocks showing no recognizable facies change within the Sandy Dolomite, −2‰ at Rizvanuša and −1.2‰ at Brezimenjača, 11m and 0.2m above the lithologic contact, respectively. This level within the lower part of the Sandy Dolomite is proposed as the chemostratigraphic PTB. In the Rizvanuša section, the δ13Corg values decline gradually from ~−25‰ in the Upper Permian to ~−29‰ in the Lower Triassic. The first negative δ13Corg excursion occurs above the lithologic contact, within the uppermost Permian deposits, and appears to be related to the input of terrigenous material. The release of isotopically light microbial soil-biomass into the shallow-marine water may explain this sudden decrease of δ13Corg values below the PTB. This would support the hypothesis that in the western Tethyan realm the land extinction, triggering a sudden drop of woody vegetation and related land erosion, preceded the marine extinction. The relatively low δ15Norg values at the Permian–Triassic (P–Tr) transition level, close to ≈0‰, and a secondary negative δ13Corg excursion of −0.5‰ point to significant terrestrial input and primary contribution of cyanobacteria. The profiles of the concentrations of redox-sensitive elements (Ce, Mn, Fe, V), biogenic or biogenic-scavenged elements (P, Ba, Zn, V), Ce/Ce* values, and normalized trace elements, including Ba/Al, Ba/Fe, Ti/Al, Al/(Al+Fe+Mn) and Mn/Ti show clear excursions at the Transitional Dolomite–Sandy Dolomite lithologic boundary and the chemostratigraphic P–Tr boundary. The stratigraphic variations indicate a major regression phase marking the lithologic boundary, transgressive phases in the latest Permian and a gradual change into shallow/stagnant anoxic marine environment towards the P–Tr boundary level and during the earliest Triassic. [Copyright &y& Elsevier]

Abstract: Archaeological leather samples recovered from the ice field at the Schnidejoch Pass (altitude 2756 m amsl) in the western Swiss Alps were studied using optical, chemical molecular and isotopic (δ13C and δ15N of the bulk leather, and compound-specific δ13C analyses of the organic-solvent extracted fatty acids) methods to obtain insight into the origin of the leather and ancient tanning procedures. For comparison, leathers from modern native animals in alpine environment (red deer, goat, sheep, chamois, and calf/cow) were analyzed using the same approach. Optical and electron microscopically comparisons of Schnidejoch and modern leathers showed that the gross structure (pattern of collagen fibrils and intra-fibrils material) of archaeological leather had survived essentially intact for five millennia. The SEM studies of the hairs from the most important archaeological find, a Neolithic leather legging, show a wave structure of the hair cuticle, which is a diagnostic feature for goatskins. The variations of the bulk δ 13C and δ 15N values, and δ 13C values of the main fatty acids are within the range expected for pre-industrial temperate C3 environment. The archaeological leather samples contain a mixture of indigenous (from the animal) and exogenous plant/animal lipids. An important amount of waxy n-alkanes, n-alkan-1-ols and phytosterols (β-sitosterol, sitostanol) in all samples, and abundant biomarker of conifers (nonacosan-10-ol) in the legging leathers clearly indicate that the Neolithic people were active in a subalpine coniferous forest, and that they used an aqueous extract of diverse plant material for tanning leather. [Copyright &y& Elsevier]

The molecular and isotopic chemistry of organic residues from archaeological potsherds was used to obtain further insight into the dietary trends and economies at the Constance lake-shore Neolithic settlements. The archaeological organic residues from the Early Late Neolithic (3922-3902 BC) site Hornstaad-Hornle IA/Germany are, at present, the oldest archaeological samples analysed at the Institute of Mineralogy and Geochemistry of the University of Lausanne. The approach includes 13C/12C and 15N/14N ratios of the bulk organic residues, fatty acids distribution and 13C/12C ratios of individual fatty acids. The results are compared with those obtained from the over 500 years younger Neolithic (3384-3370 BC) settlement of Arbon Bleiche 3/Switzerland and with samples of modern vegetable oils and fat of animals that have been fed exclusively on C3 forage grasses. The overall fatty acid composition (C9 to C24 range, maximizing at C14 and C16), the bulk 13C/12C and 15N/14N ratios (δ13C, δ15N) and the 13C/12C ratios of palmitic (C16:0), stearic (C18:0) and oleic acids (C18:1) of the organic residues indicate that most of the studied samples (25 from 47 samples and 5 from 41 in the δ13C18:0 vs. δ13C16:0 and δ13C18:0 vs. δ13C18:1 diagrams, respectively) from Hornstaad-Hornle IA and Arbon Bleiche 3 sherds contain fat residues of pre-industrial ruminant milk, and young suckling calf/lamb adipose. These data provide direct proof of milk and meat (mainly from young suckling calves) consumption and farming practices for a sustainable dairying in Neolithic villages in central Europe around 4000 BC.† [ABSTRACT FROM AUTHOR]

The stable isotope composition of waters (δ²H, δ18O) can be used as a natural tracer of hydrologic processes in systems affected by acid mine drainage. We investigated the δ²H and δ18O values of pore waters from four oxidizing sulfidic mine tailings impoundments in different climatic regions of Chile (Piuquenes at La Andina with Alpine climate, Cauquenes and Carén at El Teniente with Mediterranean climate, and Talabre at the Chuquicamata deposit with hyperarid climate). No clear relationship was found between altitude and isotopic composition. The observed displacement of the tailings pore waters from the local meteoric water line toward higher δ18O values (by ∼ +2‰ δ18O relative to δ²H) is partly due to water-rock interaction processes, including hydration and O-isotope exchange with sulfates and Fe(III) oxyhydroxides produced by pyrite oxidation. In most tailings, from the saturated zone toward the surface, isotopically different zones can be distinguished. Zone I is characterized by an upward depletion of ²H and 180 in the pore waters from the saturated zone and the lowermost vadose zone, due to ascending diffused isotopically light water triggered by the constant loss of water vapor by evaporation at the surface. In zone II, the capillary flow of a mix of vapor and liquid water causes an evaporative isotopic enrichment in ²H and 18O. At the top of the tailings in dry climate a zone III between the capillary zone and the surface contains isotopically light diffused and atmospheric water vapor. Intemperate climates, the upper part of the profile is affected by recent rainfall and zone III may not differ isotopically from zone II. [ABSTRACT FROM AUTHOR]

Abstract: Molecular and stable carbon isotope compositions of source-specific hydrocarbons have been used to reconstruct palaeoenvironmental conditions during deposition of the Middle Hettangian to Upper Sinemurian sediments on the northern epicontinental Tethys margin, Frick Swiss Jura. Increasing algal, cyanobacterial and phytoplanktonic (i.e., dinoflagellate) contributions associated with the 13C-enrichment of cyanobacteria derivatives (i.e., hopanes and monomethylalkanes) suggest enhanced primary productivity upsection. This is related to the 13C-enrichment of dissolved CO2 in the upper layers and the progressive increase of depth and oxygenation of the water column. In the Middle Hettangian shallow-water environments (lagoon), the occurrence of green sulfur bacteria (Chlorobiaceae) derivatives indicates that the lower part of the water column was strictly anoxic and rich in H2S. Since these bacteria require very low light intensity to grow, these euxinic conditions may be extended up to the photic zone, allowing for anaerobic photosynthesis. Light penetration depth is most likely reduced by high productivity and/or turbidity in the photic zone. In these sediments, 13C-depleted hopanoids (−39.5‰) are most likely associated with phototrophic purple sulfur bacteria utilizing isotopically light organic carbon at the base of the aerobic zone. These purple sulfur bacteria may have consumed the H2S used by Chlorobiaceae in the deeper layers and thus, sustained the algae and cyanobacteria productivity in the upper layers. The 13C-depleted carbonate (−13.3‰) may be partially related to the anaerobic oxidation of the organic matter during bacterial sulfate-reduction. [Copyright &y& Elsevier]

A preparation of organic working standards for the online measurement of 13 C/ 12 C and 18 O/ 16 O ratios in biological material is presented. The organic working standards are simple and inexpensive C 3 and C 4 carbohydrates (sugars or cellulose) from distinct geographic origin, including white sugar, toilet and XEROX papers from Switzerland, maize from Ivory Coast, cane sugar from Brazil, papyrus from Egypt, and the core of the stem of a Cyperus papyrus plant from Kenya. These photosynthetic products were compared with International Atomic Energy standards CH-3 and CH-6 and other calibration materials. The presented working standards cover a 15 ‰ range of 13 C/ 12 C ratios and 9 ‰ for 18 O/ 16 O, with a precision 10. [ABSTRACT FROM AUTHOR]

Abstract: Fatty acids distribution and stable isotope ratios (bulk δ 13C, δ 15N and δ 13C of individual fatty acids) of organic residues from 30 potsherds have been used to get further insights into the diet at the Late Neolithic (3384–3370 BC) site of Arbon Bleiche 3, Switzerland. The results are compared with modern equivalents of animal and vegetable fats, which may have been consumed in a mixed ecology community having agrarian, breeding, shepherd, gathering, hunting, and fishing activities. The used combined chemical and isotopic approach provides valuable information to complement archaeological indirect evidence about the dietary trends obtained from the analysis of faunal and plant remains. The small variations of the δ 13C and δ 15N values within the range expected for degraded animal and plant tissues, is consistent with the archaeological evidence of animals, whose subsistence was mainly based on C3 plants. The overall fatty acid composition and the stable carbon isotopic compositions of palmitic, stearic and oleic acids of the organic residues indicate that the studied Arbon Bleiche 3 sherds contain fat residues of plant and animal origin, most likely ruminant (bovine and ovine). In several vessels the presence of milk residues provides direct evidence for dairying during the late Neolithic in central Europe. [Copyright &y& Elsevier]

Sulfur speciation and the sources of water-soluble sulfate in three oxidizing sulfidic mine tailings impoundments were investigated by selective dissolution and stable isotopes. The studied tailings impoundments–Piuquenes, Cauquenes, and Salvador No. 1–formed from the exploitation of the Rio Blanco/La Andina, EI Teniente, and EI Salvador Chilean porphyry copper deposits, which are located in Alpine, Mediterranean, and hyperarid climates, respectively. The water-soluble sulfate may originate from dissolution of primary ore sulfates (e.g., gypsum, anhydrite, jarosite) or from oxidation of sulfide minerals exposed to aerobic conditions during mining activity. With increasing aridity and decreasing pyrite content of the tailings, the sulfur speciation in the unsaturated oxidation zones showed a trend from dominantly Fe(III) oxyhydroxide fixed sulfate (e.g., jarosite and schwertmannite) in Piuquenes toward increasing presence of water-soluble sulfate at Cauquenes and Salvador No. 1. In the saturated primary zones, sulfate is predominantly present in water-soluble form (mainly as anhydrite and/or gypsum). In the unsaturated zone at Piuquenes and Cauquenes,the δ34SSO4 values ranged from + 0.5‰ to +2.0‰ and from -0.4‰ to +1.4‰ Vienna Canyon Diablo Troilite (V-CDT), respectively, indicating a major sulfate source from pyrite oxidation (δ34Spyrite = -1.1‰ and -0.9‰). In the saturated zone at Piuquenes and Cauquenes, the values ranged from -0.8‰ to +0.3‰ and from +2.2‰ to +3.9‰, respectively. At Cauquenes the 34S enrichment in the saturated zone toward depth indicates the increasing contribution of isotopically heavy dissolved sulfate from primary anhydrite (∼+10.9‰). At EI Salvador No. 1, the δ34SSO4 average value is -0.9‰, suggesting dissolution of supergene sulfate minerals (jarosite, alunite, gypsum) with a δ34S ∼ -0.7‰ as the most probable sulfate source. The gradual decrease of δ18OSO4 values from the surface to the oxidation front in the tailings impoundments at Piuquenes (from -4.5‰ to -8.6‰ Vienna Standard Mean Ocean Water, V-SMOW) and at Cauquenes (from -1.3‰ to -3.5‰) indicates the increasing importance of ferric iron as the main electron acceptor in the oxidation of pyrite. The different δ18OSO4 values between the tailings impoundments studied here reflect the local climates. [ABSTRACT FROM AUTHOR]

Abstract: Hydrocarbon distributions and stable isotope ratios of carbonates (δ13Ccar, δ18Ocar), kerogen (δ13Cker), extractable organic matter (δ13CEOM) and individual hydrocarbons of Liassic black shale samples from a prograde metamorphic sequence in the Swiss Alps were used to identify the major organic reactions with increasing metamorphic grade. The studied samples range from the diagenetic zone (<100°C) to amphibolite facies (∼550°C). The samples within the diagenetic zones (<100 and 150°C) are characterized by the dominance of C<20 n-alkanes, suggesting an origin related with marine and/or bacterial inputs. The metamorphic samples (200 to 550°C) have distributions significantly dominated by C12 and C13 n-alkanes, C14, C16 and C18 n-alkylcyclopentanes and to a lesser extend C15, C17 and C21 n-alkylcyclohexanes. The progressive 13C-enrichment (up to 3.9‰) with metamorphism of the C>17 n-alkanes suggests the occurrence of cracking reactions of high molecular weight compounds. The isotopically heavier (up to 5.6‰) C<17 n-alkanes in metamorphic samples are likely originated by thermal degradation of long-chain homologous with preferential release of isotopically light C1 and C2 radicals. The dominance of specific even C-number n-alkylcyclopentanes suggests an origin related to direct cyclization mechanism (without decarboxylation step) of algal or bacterial fatty acids occurring in reducing aqueous metamorphic fluid conditions. The regular increase of the concentrations of n-alkylcycloalkanes vs. C>13 n-alkanes with metamorphism suggests progressive thermal release of kerogen-linked fatty acid precursors and degradation of n-alkanes. Changes of the steroid and terpenoid distributions are clearly related to increasing metamorphic temperatures. The absence of 18α(H)-22,29,30-trisnorneohopane (Ts), the occurrence of 17β(H)-trisnorhopane, 17β(H), 21α(H)-hopanes in the C29 to C31 range and 5α(H),14α(H),17α(H)-20R C27, C29 steranes in the low diagenetic samples (<100°C) are characteristic of immature bitumens. The higher thermal stress within the upper diagenetic zone (150°C) is marked by the presence of Ts, the disappearance of 17β(H)-trisnorhopane and thermodynamic equilibrium of the 22S/(22S + 22R) homohopane ratios. The increase of the ααα-sterane 20S/(20S + 20R) and 20R ββ/(ββ + αα) ratios (from 0.0 to 0.55 and from 0.0 to 0.40, respectively) in the upper diagenetic zone indicates the occurrence of isomerization reactions already at <150°C. However, the isomerization at C-20 (R → S) reaches thermodynamic equilibrium values already at the upper diagenesis (∼150°C) whereas the epimerisation at C-14 and C-17 (αα → ββ) arrives to constant values in the lower anchizone (∼200°C). The ratios Ts vs. 17α(H)-22,29,30-trisnorneohopane [(Ts/(Ts + Tm)] and 18α(H)-30-norneohopane (C29Ts) vs. 17α(H),21β(H)-30-norhopane [C29Ts/(C29Ts + C29)] increase until the medium anchizone (200 to 250°C) from 0.0 to 0.96 and from 0.0 to 0.44, respectively. An opposite trend towards lower values is observed in the higher metamorphic samples. The occurrence of specific hydrocarbons (e.g., n-alkylcyclopentanes, cadalene, hydrogenated aromatic compounds) in metamorphic samples points to kerogen degradation reactions most probably occurring in the presence of water and under reducing conditions. The changes of hydrocarbon distributions and carbon isotopic compositions of n-alkanes related to metamorphism suggest that the organic geochemistry may help to evaluate the lowest grades of prograde metamorphism. [Copyright &y& Elsevier]

Bulk and molecular stable C isotopic compositions and biomarker distributions provide evidence for a diverse community of algal and bacterial organisms in the sedimentary organic matter of a carbonate section throughout the Permian–Triassic (P/Tr) transition at the Idrijca Valley, Western Slovenia. The input of algae and bacteria in all the Upper Permian and Lower Scythian samples is represented by the predominance of C15–C22 n-alkanes, odd C-number alkylcyclohexanes, C27 steranes and substantial contents of C21–C30 acyclic isoprenoids. The occurrence of odd long-chain n-alkanes (C22–C30) and C29 steranes in all the samples indicate a contribution of continental material. The decrease of Corg and Ccarb contents, increase of Rock-Eval oxygen indices, and 13C-enrichment of the kerogen suggest a decrease in anoxia of the uppermost Permian bottom water. The predominance of odd C-number alkylcycloalkanes, C27 steranes, and C17 n-alkanes with δ13C values ∼−30‰, and 13C-enrichment of the kerogens in the lowermost Scythian samples are evidence of greater algal productivity. This increased productivity was probably sustained by a high nutrient availability and changes of dissolved CO2 speciation associated to the earliest Triassic transgression. A decrease of Corg content in the uppermost Scythian samples, associated to a 13C-depletetion in the carbonates (up to 4‰) and individual n-alkanes (up to 3.4‰) compared to the Upper Permian samples, indicate lowering of the primary productivity (algae, cyanobacteria) and/or higher degradation of the organic matter. [Copyright &y& Elsevier]

Changes in leaf carbon and nitrogen isotope composition (δ 13C and δ 15N values) and the accumulation of epicuticular lipids have been associated with plant responses to water stress. We investigated their potential use as indicators of early plant water deficit in two grapevine (Vitis vinifera L.) cultivars, Chasselas and Pinot noir, that were field-grown under well-watered and water-deficient conditions. We tested the hypothesis that the bulk δ 13C and δ 15N values and the concentrations of epicuticular fatty acids may change in leaves of similar age with the soil water availability. For this purpose, leaves were sampled at the same position in the canopy at different times (phenological stages) during the 2014 growing season. Bulk dry matter of young leaves from flowering to veraison had higher δ 13C values, higher total nitrogen content, and lower δ 15N values than old leaves. In both cultivars, δ 15N values were strongly correlated with plant water deficiency, demonstrating their integration of the plant water stress response. δ 13C values recorded the water deficiency only in those plants that had not received foliar organic fertilization. The soil water deficiency triggered the accumulation of C >26 fatty acids in the cuticular waxes. The compound-specific isotope analysis (CSIA) of fatty acids from old leaves showed an increase in δ 13C among the C 16 -C 22 chains, including stress signaling linoleic and linolenic acids. Our results provide evidence for leaf 13C-enrichment, 15N-depletion, and enhanced FA-chain elongation and epicuticular accumulation in the grapevine response to water stress. The leaf δ 13C and δ 15N values, and the concentration of epicuticular fatty acids can be used as reliable and sensitive indicators of plant water deficit even when the level of water stress is low to moderate. They could also be used, particularly the more cost-efficient δ 13C and δ 15N measurements, for periodic biogeochemical mapping of the plant water availability at the vineyard and regional scale. Unlabelled Image • The potential of leaf composition as early plant water stress marker is explored. • δ 13C increases with water deficit only in non-organic-fertilized vines. • δ 15N and N content decrease with water deficit during the growing season. • Total vine epicuticular fatty acids content increases in response to water deficit. [ABSTRACT FROM AUTHOR]

Nitrogen deficit affects both crop production and composition, particularly in crops requiring an optimal fruit N content for aroma development. The adaptation of cultural practices to improve N use efficiency (NUE) (i.e. N uptake, assimilation and partitioning) is a priority for the sustainable production of high-quality crops. A trial was set on potted grapevines (Vitis vinifera L. cv. Chasselas) to investigate the potential of crop limitation (via bunch thinning) to control plant NUE and ultimately fruit N composition at harvest. A large crop load gradient was imposed by bunch thinning (0.5–2.5 kg m–2) and N traceability in the plant was realised with an isotope-labelling method (10 atom % 15N foliar urea). The results indicate that the mobilisation of root reserves plays a major role in the balance of fruit N content. Fertiliser N uptake and assimilation appeared to be strongly stimulated by high-yielding conditions. Fertilisation largely contributed to fulfilling the high fruit N demand while limiting the mobilisation of root reserves under high yield conditions. Plants were able to modulate root N reserve mobilisation and fertiliser N uptake in function of the crop load, thus maintaining a uniform N concentration in fruits. However, the fruit free amino N profile was modified, which potentially altered the fruit aromas. These findings highlight the great capacity of plants to adapt their N metabolism to constraints, crop thinning in this case. This confirms the possibility of monitoring NUE by adapting cultural practices. [ABSTRACT FROM AUTHOR]

Sediment-hosted ore deposits contribute a significant amount (up to 65%) of the global resources of lead and zinc. Among them, the Mississippi-Valley type deposits and related oil fields often comprise large-scale hydrothermal systems where regional host rocks are stained with disseminated liquid petroleum (crude oil) and other organic compounds. Current models for the formation of those epigenetic Pb-Zn sulphide deposits consider that metals are mostly leached from basement rocks and their detrital erosional products, and transported by oxidized basinal hydrothermal fluids as chloride complexes. Sulphide precipitation mainly occurs when these basinal brines interact with fluids rich in reduced sulphur species produced mostly by thermochemical sulphate reduction (TSR) mediated by hydrocarbons. Here, using organic geochemistry and Pb isotopes, we provide evidence that petroleum and associated water were key for the formation of sulphide mineralization in the world-class sandstone-hosted ore deposit at Laisvall, not only by supplying reduced sulphur but also by contributing metals in significant amounts. The lead originally found in bitumen of the Alum Shale Formation was transported —during an arc-continent collisional event— by liquid petroleum and associated water to the site of sulphide mineralization. The alteration of petroleum by TSR made lead available for precipitation as sulphide. The petroleum-associated lead represents 40 to 60% of the metal budget in the deposit, the remainder being sourced by leaching of basement rocks. [ABSTRACT FROM AUTHOR]

The 50 m-thick Berriasian organic-rich interval (BORI) of the Vaca Muerta Formation (Neuquén Basin, Argentina) represents one of the most attractive stratigraphic intervals for unconventional hydrocarbon exploration in the unit. Nevertheless, little is known about the environmental conditions prevailing during the accumulation of the sediments. To unravel the causes that favored the preservation of the organic matter (OM) in the BORI, a detailed multiproxy sedimentological approach was conducted. The study included the analyses of microfacies, palynological content, calpionellid-calcisphere dinocysts, mineralogy, spectral gamma-ray, inorganic geochemistry, Rock-Eval pyrolysis and stable carbon isotopes of whole rock carbonate (δ13C carb), and associated OM (δ13C org). The BORI presents a late Early to early Late Berriasian age and is subdivided into a lower and upper interval. The lower interval (25.6 m-thick) is primarily formed by radiolaritic wackestones and presents higher total organic carbon (TOC) content (4.2 wt% on average), mainly in the form of amorphous OM (AOM), with variable contribution of phytoclasts. The geochemical analyses (Si, Ni, Cu, Mo, U, V) indicate high productivity of the water column and overall sea bottom anoxia. Oppositely, the upper interval (24.4 m-thick) is mostly constituted by peloidal packstones/grainstones and presents a lower TOC content (1.5 wt% on average) mainly constituted by phytoclasts, with variable contribution of AOM. A decrease of the productivity and an increase of sea bottom oxygenation is recorded based on the geochemical analyses. The high OM content of the BORI responds to the combination of high productivity of the water column and sea bottom anoxia in response to the Berriasian transgression and a worldwide paleoclimatic change towards more humid conditions. The results of our study position the BORI as an attractive interval for unconventional hydrocarbon production due to its high TOC, low bulk clay mineral and high biogenic quartz content, granting an adequate geomechanical behavior. • The mineralogy and geochemistry of the Berriasian organic interval of the Vaca Muerta Fm was studied for the first time. • The interval presents a late Early to early Late Berriasian age (upper Calpionella -lower Calpionellopsis zones). • The high TOC content is in response to the high productivity of the water column and overall anoxia at the sea bottom. • The interval presents appropriate mineralogical and geochemical features for unconventional hydrocarbon production. [ABSTRACT FROM AUTHOR]

The Sunnhordland area in SW Norway hosts more than 100 known mineral occurrences, mostly of volcanogenic massive sulfide (VMS) and orogeny Au types. The VMS mineralization is hosted by plutonic, volcanic and sedimentary lithologies of the Lower Ordovician ophiolitic complexes. This study presents new trace element and δ34S data from VMS deposits hosted by gabbro and basalt of the Lykling Ophiolite Complex and organic-rich sediments of the Langevåg Group. The Alsvågen gabbro-hosted VMS mineralization exhibits a significant Cu content (1.2 to >10 wt.%), with chalcopyrite and cubanite being the main Cu-bearing minerals. The enrichment of pyrite in Co, Se, and Te and the high Se/As and Se/Tl ratios indicate elevated formation temperatures, while the high Se/S ratio indicates a contribution of magmatic volatiles. The δ34S values of the sulfide phases also support a substantial influx of magmatic sulfur. Chalcopyrite from the Alsvågen VMS mineralization shows significant enrichment in Se, Ag, Zn, Cd and In, while pyrrhotite concentrates Ni and Co. The Lindøya basalt-hosted VMS mineralization consists mainly of pyrite and pyrrhotite. Pyrite is enriched in As, Mn, Pb, Sb, V, and Tl. The δ34S values of sulfides and the Se/S ratio in pyrite suggest that sulfur was predominantly sourced from the host basalt. The Litlabø sediment-hosted VMS mineralization is also dominated by pyrite and pyrrhotite. Pyrite is enriched in As, Mn, Pb, Sb, V and Tl. The δ34S values, which range from −19.7 to −15.7 ‰ VCDT, point to the bacterial reduction of marine sulfate as the main source of sulfur. Trace element characteristics of pyrite, especially the Tl, Sb, Se, As, Co and Ni concentrations, together with their mutual ratios, provide a solid basis for distinguishing gabbro-hosted VMS mineralization from basalt- and sediment-hosted types of VMS mineralization in the study area. The distinctive trace element features of pyrite, in conjunction with its sulfur isotope signature, have been identified as a robust tool for the discrimination of gabbro-, basalt- and sediment-hosted VMS mineralization. [ABSTRACT FROM AUTHOR]

Geochemical indicators are emerging as important predictors of soil organic carbon (SOC) dynamics, but evidence concerning the role of calcium (Ca) is scarce. This study investigates the role of Ca prevalence in SOC accumulation by comparing otherwise similar sites with (CaCO3-bearing) or without carbonates (CaCO3-free). We measured the SOC content and indicators of organic matter quality (C stable isotope composition, expressed as δ13C values, and thermal stability) in bulk soil samples. We then used sequential sonication and density fractionation (DF) to separate two occluded pools from free and mineral-associated SOC. The SOC content, mass, and δ13C values were determined in all the fractions. X-ray photoelectron spectroscopy was used to investigate the surface chemistry of selected fractions. Our hypothesis was that occlusion would be more prevalent at the CaCO3-bearing site due to the influence of Ca on aggregation, inhibiting oxidative transformation, and preserving lower δ13C values. Bulk SOC content was twice as high in the CaCO3-bearing profiles, which also had lower bulk δ13C values, and more occluded SOC. Yet, contrary to our hypothesis, occlusion only accounted for a small proportion of total SOC (< 10%). Instead, it was the heavy fraction (HF), containing mineral-associated organic C, which accounted for the majority of total SOC and for the lower bulk δ13C values. Overall, an increased Ca prevalence was associated with a near-doubling of mineral-associated SOC content. Future investigations should now aim to isolate Ca-mediated complexation processes that increase organo-mineral association and preserve organic matter with lower δ13C values. [ABSTRACT FROM AUTHOR]

The topographic history of an orogen, a key element to study the interactions of the climate and tectonic conditions that drove it, can be reconstructed by inverting the sedimentary record of its adjacent basins. Previous tectono-stratigraphic studies, including flexural models, and sparse stable oxygen and carbon isotope data from the South-Pyrenean foreland basin suggest a major topographic rise occurred in the late Paleocene-early Eocene. To further test this hypothesis, we present a stack of 658 stable isotope measurements on whole-rock marine carbonate mudstone from a 4800-m-thick composite sedimentary succession which provides a 12 Ma continuous record of environmental conditions during the early to middle Eocene (54 to 42 Ma). From the base of this record (at 54 Ma), oxygen isotopes (δ18O values) show a faster decrease rate than the coeval global negative excursion associated with the Early Eocene Climatic Optimum (EECO). This local alteration of the global δ18O signal indicates that topographic growth during this period, associated with significant tectonic activity, perturbed the oxygen isotopic composition of foreland waters. Thus, our data suggest that significant topographic uplift of the Pyrenean orogen started from at least 54 Ma and continued until ca. 49 Ma, reaching the maximum elevations of 2000 ± 500 m in this phase from previous isotope and flexural studies. In addition, our record shows that the long-term carbon stable isotope composition during this period remained relatively stable with no similarity to the global bell-shaped long-term trend of the EECO. This is consistent with the restricted physiography of the South-Pyrenean foreland basin, mainly influenced by local sedimentary and water inputs. Overall, the Pyrenean topographic growth from the late Cretaceous to the Miocene displays several growth stages that seem to be primarily determined by episodes of increased rate of tectonic plate convergence. The duration of these growth stages (several millions of years) is a possible documentation of the response time of mountain ranges to tectonic perturbations. The results of this work, therefore, demonstrate that stable isotope measurements on whole-rock sediments in foreland basins can provide key information for tectono-climatic and topographic reconstructions of mountain ranges. [ABSTRACT FROM AUTHOR]

Zooplankton can spend winter actively under the ice cover of lakes. However, dietary resources under lake ice are both quantitatively and qualitatively limited, and feeding might not be energetically rewarding for most zooplankton species. Many zooplankters are expected to fast throughout the winter, exhausting their previously accumulated fat storage. We hypothesised that only a fraction of the actively overwintering zooplankton contributes to an active food web under lake ice, leading to few trophic linkages within the planktonic community.Zooplankton habitats and feeding were investigated under the ice of Lake Onego. Zooplankton habitats and migrations were studied by coupling zooplankton sampling around the clock to measurements of particle movement using an acoustic Doppler current profiler. Secondly, fatty acid‐specific stable isotope compositions were used to determine whether and which zooplankton fatty acids ultimately came from the assimilation of under‐ice seston.The algal biomass was low under ice and mostly dominated by large diatoms. Copepods dominated the zooplankton community. Species present as late copepodite and adult instars were confined to the deeper layers, while nauplii occupied the surface layer. Diel vertical migration by Cyclops was the most tangible observation of persistent feeding under the ice. Previously accumulated fat storage represented most of zooplankton fatty acids, with few, yet detectable, fatty acids recently acquired by feeding under the ice.Although some zooplankton taxa maintained feeding activity under the ice of Lake Onego, the food source available beneath the ice was not sufficiently rewarding to leave an isotopic imprint upon the dominant fatty acids of bulk zooplankton. The seston fatty acids that were passed on to zooplankton from feeding under ice were not provided by diatoms, although they made up most of the phytoplankton biovolume. Instead, the zooplankton food web was supported by mixotrophic phytoplankton (i.e. cryptophytes and chrysophytes) that represented <5% of the under‐ice biovolume. Consequently, the planktonic food web under the ice of Lake Onego had few trophic linkages, and thereby low connectance.Environmental conditions under the ice of Lake Onego do not depart significantly from those observed in lakes of similar latitudes. Therefore, low connectance food webs could be relatively common under ice for lakes above 60° latitude. Our methodological approach is applicable to other lakes and could thus disclose the variability of under‐ice food webs. This would provide a much more complete picture of annual dynamics of food webs in lakes that ice over. [ABSTRACT FROM AUTHOR]

The Archean Eon was a time of predominantly anoxic Earth surface conditions, where anaerobic processes controlled bioessential element cycles. In contrast to “oxygen oases” well documented for the Neoarchean [2.8 to 2.5 billion years ago (Ga)], the magnitude, spatial extent, and underlying causes of possible Mesoarchean (3.2 to 2.8 Ga) surface-ocean oxygenation remain controversial. Here, we report δ15N and δ13C values coupled with local seawater redox data for Mesoarchean shales of the Mozaan Group (Pongola Supergroup, South Africa) that were deposited during an episode of enhanced Mn (oxyhydr)oxide precipitation between ∼2.95 and 2.85 Ga. Iron and Mn redox systematics are consistent with an oxygen oasis in the Mesoarchean anoxic ocean, but δ15N data indicate a Mo-based diazotrophic biosphere with no compelling evidence for a significant aerobic nitrogen cycle. We propose that in contrast to the Neoarchean, dissolved O2 levels were either too low or too limited in extent to develop a large and stable nitrate reservoir in the Mesoarchean ocean. Since biological N2 fixation was evidently active in this environment, the growth and proliferation of O2-producing organisms were likely suppressed by nutrients other than nitrogen (e.g., phosphorus), which would have limited the expansion of oxygenated conditions during the Mesoarchean. [ABSTRACT FROM AUTHOR]

The article presents a research which utilizes the chemistry of organic residues from archaeological potsherds in getting data into the dietary trends and economies during the Neolithic period in Central Europe. The approach includes δ13C and δ15N of the bulk organic residues and fatty acids distribution. The researchers claim that the data offer direct proof of milk and meat consumption and farming practices for a sustainable dairying.

The article discusses the research which evaluates the molecular and isotopic records of the PermianTriassic transition at the Mount Velebit, Croatia. As part of the procedure, several detailed paleontological, isotopic, organic, and inorganic geochemical studies were examined in order to investigate the environmental changes during the said period. Information about the results of the studies is discussed.

Abstract Soft-sediment deformation structures (SSDSs) with bedding-parallel lenticular morphology have been occasionally reported and called different names, such as loop bedding or pillow bed. However, there is no understanding of the formative conditions that give rise to them versus other SSDSs. Similar bedding-parallel, lenticular, dolomite bodies, tens of centimeters thick with quite variable lengths (30 cm–30 m), occur across a large area (>3000 km2), exclusively in the St. Louis Member (Late Vasean, Mississippian) of the Slade Formation in east-central Kentucky, USA. Field investigations indicate that the lenticular structures, along with other associated SSDSs, represent a persistent deformed horizon that is correlative with and occurs symmetrically around the more intensely deformed Big Sinking Bed, which was previously interpreted as earthquake-induced SSDSs. Based on multiple lines of evidence, the lenticular structures are interpreted to represent distal expressions of the same seismic event that generated the proximal Big Sinking Bed. The lenticular structures were subsequently dolomitized and their selective dolomitization is attributable to their brittle deformation during the earthquake, which resulted in preferentially developed fracture porosity that allowed more efficient circulation of Mg2+ fluids throughout the lenticular structures. Petrographic and stable-isotopic evidence also suggests that the selective dolomitization postdates the deformation, probably related to a brine-reflux system developed during the first marine transgression following subaerial exposure of the St. Louis carbonates. Based on comparative analysis with other global cases, the bedding-parallel, lenticular structures are interpreted to represent a distinct type of SSDS, comparable to boudinage in tectonic deformation. Their formation reflects a situation in which seismically-elevated pore-fluid pressure is lower than vertical confining stress but higher than horizontal confining stress. A prominent occurrence of lenticular-type SSDS is a potential indicator of syndepositional extensional stress regime, which is testified by tectonic settings of all known cases, including the Kentucky dolomite bodies. Highlights • Bedding-parallel Lenticular structures from St. Louis Member, Slade Formation (Eatern Kentucky) are seismites. • Later selective dolomitization of lenticular structures due to earthquake-induced fracture porosity • Bedding-parallel Lenticular soft-sediment deformation structures indicate syndepositional extensional settings. • Useful indicators for rheological behaviors and fluid-pressure evolution during soft-sediment deformation. [ABSTRACT FROM AUTHOR]

Abstract The Briançonnais domain is an important paleogeographic unit in the Alps, which represents a structural high within the former Alpine Tethys Ocean. Expressions of the most important Cretaceous oceanic anoxic events (OAE1a-d and OAE2) are exceptionally well preserved in the Subbriançonnais unit at Roter Sattel in the Fribourg Prealps, Switzerland. The main objective of this study was to reconstruct oxygen contents and trophic levels in the water column for each OAE. To accomplish this we used an integrated multi-proxy approach, including total organic carbon (TOC), phosphorus (P), and redox and productivity-sensitive trace-element contents (RSTE, PSTE). RSTE enrichments associated with the highest TOC values (up to 5.4 and 4.8 wt%) and with the lowest Mn contents in sediments equivalent to the Selli and Paquier OAEs (1a and 1b) indicate the presence of intermittent anoxic to euxinic conditions during these events. Sediments equivalent to Bonarelli OAE2 near the Cenomanian-Turonian (CT) boundary are also characterized by significant trace-element enrichments in comparison to average shale values. Mo and U enrichment factors (EFs) in the lower Aptian and lower Albian intervals are characteristic of an unrestricted marine environment, and in the Cenomanian-Turonian boundary interval they indicate a relationship with a particulate Fe-Mn-oxyhydroxide shuttle within the water column. In the OAE1a interval the elevated total P content associated with higher C org /P tot ratios and maxima in TOC values suggests that a part of the remobilized P remained trapped in the sediments. By contrast, the lower P tot values associated with RSTE and C org /P tot enrichments in the OAE1b and OAE2 intervals indicate that a significant part of P was remobilized and escaped to the bottom water. Our results highlight the combined roles of regional and global parameters in the development of oxygen-deficient conditions that may lead to anoxia and increase in organic matter preservation during the OAEs. The differentiated topography of the Briançonnais domain associated with global climate and sea-level change and its influence on weathering in general, and more specifically on the mobilization of sediments on the adjacent ridge, modulated nutrient availability in different proportions during the different "mid"-Cretaceous OAEs. Highlights • RSTE indicate dysoxic to anoxic conditions in the Briançonnais during OAEs. • Mo and U EFs in the OAE1a and b suggest an unrestricted marine environment. • In the OAE2, they point to a particulate Fe-Mn-oxyhydroxide shuttle. • Productivity played a key role in the development of anoxic conditions. • Our data suggest dynamic and complex interplay between regional and global changes. [ABSTRACT FROM AUTHOR]

The Oceanic Anoxic Event 2 (OAE2, ca. ∼93.5 Ma) represents a major phase of environmental change during the Mesozoic, and is associated with a pronounced positive excursion in the carbon-isotope record. Short-term climate oscillations within the OAE2 are recorded as Milankovitch cycles, which have been used to establish a precise temporal framework for the OAE2. However, few studies discuss the sedimentary expression of Milankovitch cycles during the OAE2, and its paleoenvironmental implications. Here we present carbonate and organic-carbon isotope data from a biostratigraphically well-dated, organic-rich OAE2 interval in a sedimentary succession outcropping in the Briançonnais Domain at Roter Sattel (Fribourg Prealps, Switzerland). We sampled the OAE2 interval (4.28 m) for proxies of detrital sediment quantification (Al, Ti, magnetic susceptibility) at ultra-high resolution (1 cm). Time-series analysis of multiple detrital proxies permits the construction of an orbital timescale for the OAE2 based, for the first time, on the stable 173 kyr (s3–s6) obliquity modulation cycle. The resulting OAE2 orbital timescale at Roter Sattel is consistent with previous timescales obtained in the Western Interior Basin, and in southern Tibet (China). Our cyclostratigraphic results show an unusually strong obliquity signal during the initiation of OAE2. Previous studies have demonstrated that the onset of OAE2 was associated with magmatic pulses coupled with increases in atmospheric p CO 2 , followed by an overall, gradual drawdown of CO 2 . Accordingly, we suggest that detrital input during the OAE2 was the result of intensified continental weathering related to magmatic activity, the substantially release of greenhouse gases, and an accelerated hydrological cycle modulated by obliquity cycles. [ABSTRACT FROM AUTHOR]

Our contribution presents an integrated litho-, bio- and chemostratigraphic study of the best-preserved outcrops of the post-Urgonian marly cover (A 1 unit) of the North Provence carbonate platform. The study of the rich ammonite fauna from the Apt–Gargas area (SE Vaucluse) confirms that the A 1 unit is older than previously assumed and dated to the upper (but non-uppermost) part of the lower Aptian Deshayesites forbesi Zone of the Mediterranean standard zonation. This interval is assigned to the lower part of the Roloboceras hambrovi Subzone as defined in the present contribution which is time equivalent to the spreading of the OAE 1a. Microfossil occurrences previously documented in the A 1 unit are consistent with our ammonite-age calibration. Unfortunately, the curves of the carbon and oxygen stable isotopes exhibit a correlative signal probably caused by an early diagenetic overprint which questions the previous use of the C-isotope signal for precise chronostratigraphic correlation with respect to the OAE 1a excursion. The top of the A 1 unit is marked by a burrowed firmground locally infilled and capped by glauconite-rich sandy marls which grade into the blue–grey muddy marls of the overlying A 2 unit. The hiatus associated to this discontinuity is equivalent to the culmination of the OAE 1a, including the uppermost D. forbesi Zone (= upper R. hambrovi Subzone as herein defined) and the lower D. deshayesi Zone. The revised calibration of the post-Urgonian marl implies that the ammonite-age calibration of the North Provence carbonate platform should be revised and questions the timing and driving mechanisms of its stepwise demise. [ABSTRACT FROM AUTHOR]

The Aptian stage, between ∼113 and ∼121 million years ago (Ma), was punctuated by a succession of Oceanic Anoxic Events (OAEs), recording extreme global warmings, dramatic expansions of the ocean's oxygen minimum zones, along with perturbations to the biotic and carbon cycles. However, the chronology of the Aptian stage is poorly constrained, impacting the duration and timing of OAEs. Using a greatly expanded sedimentary composite record (380 m) of key outcropping sections in the Vocontian Basin (SE France) combined with available radiometric dates and correlations to a set of astronomical solutions, we provide a constrained absolute astrochronology of the Aptian stage. The 405 kyr (g Venus –g Jupiter) eccentricity astronomical timescale indicates a minimal duration of ∼9.4 Myr for the Aptian stage and an age of 122.6 ± 0.3 Ma for the base of the Aptian, consistent with radioisotope dating. We find a deviation in the periodicity of g Mercury –g Jupiter eccentricity term in the mid-Aptian stage, at ca. 117.19 ± 0.3 Ma, that we ascribe as an expression of the resonance transition σ = (g Mercury – g Jupiter) – (s Mercury – s Venus), in relation with a strong chaotic orbital motion of Mercury. Such a geological observation is supported by a concomitant resonant transition in the La2004 astronomical model. • The tuned MS data indicates a minimal duration of ∼9.4 Myr for the Aptian stage. • Our revised Aptian duration appears concordant with numerical calibration. • A shift in the g Mercury –g Jupiter eccentricity term is observed at 117.19 ± 0.3 Ma. • Geological observation is supported by a resonant transition in astronomical model. [ABSTRACT FROM AUTHOR]