Among pharmaceutical products (PPs) recalcitrant to water treatments, diclofenac shows a high toxicity and remains at high concentration in natural aquatic environments. The aim of this study concerns the understanding of the adsorption mechanism of this anionic PP onto two organoclays prepared with two long-alkyl chains cationic surfactants showing different chemical nature for various experimental pH and temperature conditions. The experimental data obtained by a set of complementary techniques (X-ray diffraction, elemental analyses, gas chromatography coupled with mass spectrometry, and Fourier transform infrared spectroscopy) and the use of Langmuir, Freundlich and Dubinin-Radushkevish equation models, reveal that organoclays show a good affinity to diclofenac which is enhanced as the temperature is under 35°C and for pH above 4.5 (i.e. >pKa of diclofenac) while the chemical nature of surfactant appears to play a minor role. The thermodynamic parameters derived from the fitting procedure point out the strong electrostatic interaction with organic cations adsorbed within the interlayer space in the organoclays for the adsorption of diclofenac. This study stress out the application of organoclays for the adsorption of a recalcitrant PPs in numerous aquatic compartments that can be used as a complement with activated carbon for waste water treatment.

The Paleocene-Eocene boundary (55.8 Ma) is associated with the Paleocene-Eocene Thermal Maximum (PETM), which is characterized by a negative Carbon Isotope Excursion (CIE), reflecting a major perturbation of the carbon cycle, and by an extreme and rapid global warming. The Cap d'Ailly area (Upper Normandy, France), in which previous studies have revealed the Paleocene-Eocene transition, is a reference locality for organic-rich terrestrial and lagoonal deposits of the-Sparnacian‖ stage, widespread in Northwestern Europe. In this study, we focus on the organic matter content of the Vasterival section. Organic data (Rock-Eval, palynofacies, biomarker analyses and compound specific isotope analyses) were acquired in order to constrain the paleoenvironmental and paleohydrological changes that occurred at the Paleocene-Eocene boundary. Stable carbon isotope compositions of higher plant leaf wax n-alkanes reveal a CIE of-4.5 ‰, extending throughout the second half of the studied section. Palynofacies observations reveal: (i) an abrupt shift from a closed, quiescent marsh pond to an open eutrophic swamp subjected to algal blooms, concomitant with the onset of the CIE; and (ii) the evolution from a swamp to a tidal flat due to the marine transgression that occurred during the PETM. Higher plant biomarkers and their hydrogen isotopic composition compared to nitrogen analyses suggest: (i) dry episodes just before the PETM that may help to understand the triggering of this hyperthermal event; (ii) a moister climate associated with a stronger seasonality during the early PETM.

A total of 207 volatile compounds were identified in extracts of four French labeled brandies: Armagnac, Cognac, Calvados, and Mirabelle. Relative levels of all components were determined using GC-MS after integration of a selected peak of the mass spectrum of each. Each type of brandy could be clearly discriminated using PLS-DA statistical analyses based on these levels. French Mirabelle spirit, which was studied for the first time, was characterized by higher levels of many aldehydes and acetals and by the presence of compounds having an odd number of carbons together with benzaldehyde and some of its derivatives. Many possible derivatives of acrolein and high amounts of butan-2-ol were rather specific for the volatile composition of Calvados. The most important difference between the two wine-based samples seemed to be directly linked to the distillation system used. Many furanic compounds are specific to Cognac, whereas two or three compounds such as 1-(ethoxyethoxy)-2-methylbutane and gamma-eudesmol were specific to Armagnac. These two brandies presented rather high distributions of isobutanol and isopentanols, whereas Mirabelle and Calvados compositions offer more concentrated aliphatic linear alcohols.

To investigate how slight differences in the total particulate organic matter (OM) assemblage and maceral types of marine mudstones influence the development and the evolution of OM porosity throughout the same formation, laboratory gold-tube anhydrous confined thermal maturation was applied on low-mature organic-rich marine Kimmeridge clay mudstones (Yorkshire, UK). Organic petrography (palynofacies and maceral analysis), SEM observations, global and molecular geochemical characterization and low-pressure nitrogen adsorption measurements were performed to examine, to our knowledge for the first time, the role of the OM composition and properties on the evolution of porosity during thermal maturation. Evidence from organic petrography and geochemical analyses showed that organic-rich Kimmeridge clay samples containing a higher relative proportion of brown amorphous organic matter (AOM), known to be derived essentially from the cell walls of microalgae, exhibit a different pore evolution compared to samples containing a higher proportion of oil-prone orange AOM derived primarily from preservation by natural sulfurization of phytoplanktonic organic components naturally rich in lipidic compounds. OM conversion of orange AOM-rich samples has led to the production of higher amounts of low viscous oil and abundant gaseous hydrocarbon that are more 2 favorable to the formation of abundant but small OM micropores and mesopores in the condensate/wet gas zone and less abundant large modified mineral pores in the dry gas zone. The secondary cracking of the heavier oil produced by brown-AOM-rich OM has led to the formation of a greater quantity of CO2 and an abundant organic-rich residue more favorable to the formation of larger mesopores. Moreover, the more abundant thick laminar bituminite macerals forming a continuous ductile network particularly prone to compaction and the higher amounts of oil/bitumen generated during their conversion may have led to a higher pore collapse after oil/gas generation and migration, responsible for the destruction of part of the secondary pore network observed on some samples. Despite their slightly lower oil-prone potential, brown AOM-rich samples have thus developed larger mesopores during thermal maturation, resulting in higher pore volumes in the dry gas zone. Thus, the ability of marine mudstones to develop pores during maturation do not increase proportionally with the OM oil prone quality. These results show that variations in the individual particulate OM assemblage of a similar type II kerogen can significantly influence the amount of oil and gas generated during thermal maturation throughout the same formation, resulting in different pore evolution models. This reveals the importance of clearly identifying the composition of the original particulate OM assemblage to better predict the amount of bitumen, oil and gas generated during thermal maturation and the associated pore development.

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As a part of a wider study aimed at determining new molecular biomarkers in soils and sediments that could be specific of distinct vegetation types with respect to unravelling past changes in land use, we analysed the neutral lipid content of soil developed in the catchment of a small lake in central France. The ketone/acetate lipid fraction of soil under pasture or meadow contains a series of pentacyclic triterpenyl acetates of wide structural diversity, most being reported in soil for the first time. The restricted number of potential plant sources of triterpenyl acetates (some produced by a single species) underlines the potential of triterpenyl acetates as new biomarkers to track past vegetation change in palaeoenvironmental studies, when found in natural archives such as soil, sediments or peat.

bution of miliacin (olean-18-en-3β-ol methyl ether) and related compounds in broomcorn millet (Panicum miliaceum) and other reputed sources: Implications for the use of sedimentary miliacin as a tracer of millet. Organic Geochemistry, Elsevier, 2013Elsevier, , 63, pp.48-55. <10.1016Elsevier, /j.orggeochem.2013 Miliacin biosynthesis has been proposed for other Panicum species, Setaria italica (Italian or foxtail millet), Pennisetum sp., and Chaetomium olivaceum (an olive green mold). We found miliacin concentrations in seeds of different varieties of P. miliaceum to be similarly high (with trace amounts of β-and α-amyrin methyl ethers). It was absent from hulls and roots, and nominally present in leaves and stems. The transfer of miliacin from plant to sediments is therefore mostly from seeds. Miliacin was abundant (often with larger amounts of β-and α-amyrin methyl ethers) in all other Panicum species studied but only in some species of the genus Pennisetum and absent in * Corresponding author e-mail address: jeremy.jacob@univ-orleans.fr 2 Setaria italica. Neither C. olivaceum nor its growth medium (rice) showed any trace of miliacin.Our results of no miliacin from S. italica and C. olivaceum , high miliacin concentrations in seed of P. miliaceum relative to other PTMEs and to other grasses, and considering the high biomass that cultivated broomcorn millet has relative to other potential plant sources, support the use of sedimentary records of miliacin in some contexts, to track past millet agricultural dynamics.

The objective of the study was to evaluate the sorption of a pool of pharmaceutically active compounds (PhACs) onto a clay–sand filter in a dynamic sorption experiment.