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We report a huge organic diversity in the Tissint Mars meteorite and the sampling of several mineralogical lithologies, which revealed that the organic molecules were nonuniformly distributed in functionality and abundance. The range of organics in Tissint meteorite were abundant C 3-7 aliphatic branched carboxylic acids and aldehydes, olefins, and polyaromatics with and without heteroatoms in a homologous oxidation structural continuum. Organomagnesium compounds were extremely abundant in olivine macrocrystals and in the melt veins, reflecting specific organo-synsthesis processes in close interaction with the magnesium silicates and temperature stresses, as previously observed. The diverse chemistry and abundance in complex molecules reveal heterogeneity in organic speciation within the minerals grown in the martian mantle and crust that may have evolved over geological time.

Bio-oils obtained from lignocellulosic biomass pyrolysis are promising energetic resources. However, their high oxygen content is responsible for storage and corrosion issues and does not allow the...

A bronze vessel, containing solid black material, was found in a grave dated to the late eighth century BC and located in the Middle Tyrrhenian region. Two residue samples of this black material were subject to molecular characterization in order to assess first its composition and then the function of this precious object. Two different technique analyses, namely gas chromatography–mass spectrometry (GC–MS) and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry, in negative-ion mode (ESI(−) FTICR MS), were employed in that way. If GC–MS analysis is commonly used for the characterization of archaeological samples by identifying biomarkers related to organic material, FTICR MS was used to achieve a fast global molecular description with up to thousands of assignments. In addition, this technique enabled to hypothesize about the different materials involved in the black material composition. As a result, lipids, beeswax, conifer resin, and pitch from birch bark were supposed, which was thereafter confirmed by GC–MS. Consequently, FTICR MS can be regarded as an efficient tool for the fast profiling of the organic archaeological compounds.

Bio-oils from biomass pyrolysis can be a resource for upgrading to chemicals or fuels. Here, for the first time, we compare the composition of bio-oils produced from two feedstocks (wheat straw, softwood) in pyrolysis units of different mode of operation (continuous—rotary kiln vs. batch) using Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) in different ionization modes (APPI (+), ESI (+/−)). Our results demonstrate that the pyrolysis unit design had only a minor influence on the composition of bio-oils produced from low-mineral containing wood biomass. Yet, the wheat straw-derived bio-oil produced in the continuous unit comprised lower molecular weight compounds with fewer oxygen-containing functional groups and lower O/C and H/C ratios, compared to bio-oils from batch pyrolysis. Longer residence time of vapours in the heated zone in the rotary kiln and a higher mineral content in wheat straw resulted in increased catalytically-mediated secondary reactions that favoured further bio-oil decomposition. This work shows for the first time that it is possible to produce distinct bio-oils without the need for external catalyst addition, by matching reactor type/design and feedstock.

The insoluble organic matter (IOM) contained in carbonaceous chondrites has witnessed a diverse suite of processes possibly starting from the evolution of the parent molecular cloud down to the protosolar nebula and finally to asteroidal processes that occurred on the chondrites’ parent bodies. Laser desorption coupled with ultra-high-resolution mass spectrometry reveals that the IOM of the Paris meteorite releases a large diversity of molecules. Various molecular families ranging from hydrogenated amorphous carbon to CHNOS aromatic molecules were detected with heteroatoms (nitrogen, oxygen, and sulfur) mainly incorporated within aromatic structures. Molecules bearing nitrogen atoms present a significant variation in aromaticity. These unprecedented results allow the proposal that small molecules bearing heteroatoms could be trapped in the large macromolecular network of the IOM by hydrophobic interactions. This molecular diversity could originate from different sources, such as the soluble organic matter, the hydrothermal alteration inside the Paris’s parent body, or even generated during the IOM extraction procedure. It has to be noted that some of the molecular diversity may reflect fragmentation and rearrangement of the IOM constituents during the laser desorption ionization, although care was taken to minimize such damage.

The water-based extraction of bioactive components from flavonoid-rich medicinal plants is a key step that should be better investigated. This is especially true when dealing with easy-to-use home-made conditions of extractions, which are known to be a bottleneck in the course for a better control and optimization of the daily uptake of active components from medicinal plants. In this work, the water-based extraction of Blackcurrant (Ribes nigrum) leaves (BC) and Chrysanthellum americanum (CA), known to have complementary pharmacological properties, was studied and compared with a previous work performed on the extraction of Hawthorn (Crataegus, HAW). Various extraction modes in water (infusion, percolation, maceration, ultrasounds, microwaves) were compared for the extraction of bioactive principles contained in BC and CA in terms of extraction yield, of amount of flavonoids, phenolic compounds, and proanthocyanidin oligomers, and of UHPLC profiles of the extracted compounds. The qualitative and quantitative aspects of the extraction, in addition to the kinetic of extraction, were studied. The optimized easy-to-use-at-home extraction protocol developed for HAW was found very efficient to easily extract bioactive components from BC and CA plants. UHPLC-ESI-MS and high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) were also implemented to get more qualitative information on the specific and common chemical compositions of the three plants (including HAW). Their antihyaluronidase, antioxidant, and antihypertensive activities were also determined and compared, demonstrating similar activities as the reference compound for some of these plants.

An integrated approach using contextual, use-wear, scientific and experimental methods was used to analyze the role of stone troughs of up to 165 l capacity at the Early Neolithic site Gobekli Tepe in the context of other stone containers found there. Around 600 (mostly fragmentary) vessels from the site constitute the largest known assemblage from the Pre-Pottery Neolithic of the Near East. Besides the large limestone troughs, it encompasses middle-sized, coarsely made limestone vessels, finely executed platters and ‘greenstone’ vessels. All lines of evidence taken together indicate the use of limestone troughs for the cooking of cereals.

Hawthorn (Crataegus) is used for its cardiotonic, hypotensive, vasodilative, sedative, antiatherosclerotic, and antihyperlipidemic properties. One of the main goals of this work was to find a well-defined optimized extraction protocol usable by each of us that would lead to repeatable, controlled, and quantified daily uptake of active components from hawthorn at a drinkable temperature (below 60 &deg, C). A thorough investigation of the extraction mode in water (infusion, maceration, percolation, ultrasounds, microwaves) on the yield of extraction and the amount of phenolic compounds, flavonoids, and proanthocyanidin oligomers as well as on the Ultra High Performance Liquid Chromatography (UHPLC) profiles of the extracted compounds was carried out. High-resolution Fourier transform ion cyclotron resonance mass spectrometry was also implemented to discriminate the different samples and conditions of extraction. The quantitative and qualitative aspects of the extraction as well as the kinetics of extraction were studied, not only according to the part (flowers or leaves), the state (fresh or dried), and the granulometry of the dry plant, but also the stirring speed, the temperature, the extraction time, the volume of the container (cup, mug or bowl) and the use of infusion bags.

As part of a multidisciplinary project concerning the practices of mummification in ancient Egypt, we studied a series of 33 human remains, collected during the late 19th century. These heads of human mummies belong to the Osteology collection from the Musée des Confluences of Lyon. One of the important issues of this research project was to establish a chronology of the mummification processes. However, the lack of archaeological data and excavation reports does not allow the dating of the specimens. Thus, during this project, these heads have been radiocarbon dated in order to place the individuals in a reliable chronological and cultural framework. As a result, 20 samples of hair and 13 samples of linen textiles of the wrappings have been taken. The results raised a lot of uncertainties about the chronology of these mummies and the need to validate or correct the original date attributions were given by the discoverers. As an example, among the 13 mummies thought to be dated between the 11th and 20th Dynasties, none appears from this period. In the same way, six mummies were originally dated from the Ptolemaic period. However, only one belongs to this period, four are Roman, and the last one is from the New Kingdom.

The investigation of the abundant organic matter in primitive meteorite such as carbonaceous chondrites is of major interest in the field of origin of life. In this study, the soluble organic fraction of the Murchison meteorite was analyzed by atmospheric pressure photoionization (APPI) and electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), in both detection modes. Such an approach ensured that we obtained an extensive description of the organic matter of the CM2 meteorite. Indeed, while in total close to 16,000 unique features were assigned, only 4% are common to all analyses, illustrating the complementarity of both the detection modes and the ionization sources. ESI FT-ICR MS analysis, in negative-ion mode, ensured to observe specifically CHOS and CHNOS species, whereas the positive-ion mode is more dedicated to the detection of CHNO and CHN species. Moreover, new organomagnesium components were observed in (+) ESI. Eventually, (+) APPI FT-ICR MS analysis was a preferred method for the detection of less polar or nonpolar species such as polycyclic aromatic hydrocarbons but also heteroatom aromatic species composing the organic matter of Murchison.

Bio-oils obtained from the thermochemical conversion of the lignocellulosic biomass are potential sources of renewable materials (bio-fuels, chemicals, …). However, their high chemical complexity and the high amount of oxygenated compounds limit their ready-to-use capacity. Upgrading treatments, such as deoxygenation and/or cracking, have to be applied. In order to assess the most suited and the most efficient upgrading process, it is necessary to obtain an extensive composition description of the bio-oils at all processing stages. In this respect, the non-targeted approach, using Fourier transform high-resolution mass spectrometry combined with different ionization sources, has demonstrated its great abilities to characterize thousands of bio-oil components over a large range of mass and polarity. In this chapter, an exhaustive review of the studies performed in this field will be presented. To define the main challenges related to the bio-oil characterization, some relevant information will be briefly given in regards to the biomass composition and the used processes that ensure its conversion into bio-oils. Additionally, information achieved by “classical” analytical methods will be presented. This will allow demonstrating the contribution of high-resolution Fourier transform mass spectrometry (FTMS) analyses to characterization of bio-oils.

On July 10, 2018 at 21:29 UT extended areas of South-Western Germany were illuminated by a very bright bolide. This fireball was recorded by instruments of the European Fireball Network (EN). The records enabled complex and precise description of this event including the prediction of the impact area. So far six meteorites totaling about 1.23 kg have been found in the predicted location for a given mass during dedicated searches. The first piece of about 12 g was recovered on July 24 close to the village of Renchen (Baden-Wurttemberg) followed by the largest fragment of 955 g on July 31 about five km north-west of Renchen. Renchen is a moderately-shocked (S4) breccia consisting of abundant highly recrystallized rock fragments as well as impact melt rock clasts. The texture, the large grain size of plagioclase, and the homogeneous compositions of olivine (similar to Fa(26)) and pyroxene (similar to Fs(22)) clearly indicate that Renchen is composed of metamorphosed rock fragments (L5-6). An L-group (and ordinary chondrite) heritage is consistent with the data on the model abundance of metal, the density, the magnetic susceptibility as well as on O-, Ti-, and Cr-isotope characteristics. Renchen does not contain solar wind implanted noble gases and is a fragmental breccia. An unusually large mm-sized merrillite-apatite aggregate shows trace element characteristics like other phosphates from ordinary chondrites. Data on the bulk chemistry, IR-spectroscopy, cosmogenic nuclides, and organic components also indicate similarities to other metamorphosed L chondrites. Noble gas studies reveal that the meteorite has a cosmic ray exposure (CRE) age of 42 Ma and that most of the cosmogenic gases were produced in a meteoroid with a radius of at max. 20 cm based on the radionuclide Al-26 and 10-150 cm based on cosmogenic Ne-22/Ne-21. K-Ar and U/Th-He gas retention ages are both in the range similar to 3.0-3.2 Ga. Both systems do not show evidence for a complete reset 470 Ma ago, and may instead have recorded the same resetting event 3.0 Ga ago.

The conversion of lignocellulosic biomass by catalytic fast pyrolysis (CFP) is a promising route to producing green aromatics and sustainable biofuels. The zeolite catalysts present a strong ability to produce light aromatics but also heavy products. In this work, these heavy products are monitored by a well-established petroleomic approach. The selectivity toward the heavy bio-oil components of both a common HZSM-5 zeolite and a hierarchical zeolite was investigated. Part of the molecular species from lignin derivatives is still present in the upgraded bio-oils. Deoxygenation and aromatization are the main modifications of the heavy compounds caused by zeolites, especially for the sugar derivatives. These effects are stronger for the hierarchical zeolite for which numerous heavy hydrocarbons (not oxygenated) are generated due to enhanced mass transfers within the crystallites. Moreover, this catalyst demonstrates a better stability upon an increase in the biomass-to-catalyst ratio.

Ammonia is well suited to favor deprotonation process in electrospray ionization mass spectrometry (ESI-MS) to increase the formation of [M - H]-. Nevertheless, NH3 may react with carbonyl compounds (aldehyde, ketone) and bias the composition description of the investigated sample. This is of significant importance in the study of complex mixture such as oil or bio-oil. To assess the ability of primary amines to form imines with carbonyl compounds during the ESI-MS process, two aldehydes (vanillin and cinnamaldehyde) and two ketones (butyrophenone and trihydroxyacetophenone) have been infused in an ESI source with ammonia and two different amines (aniline and 3-chloronaniline). The (+) ESI-MS analyses have demonstrated the formation of imine whatever the considered carbonyl compound and the used primary amine, the structure of which was extensively studied by tandem mass spectrometry. Thus, it has been established that the addition of ammonia, in the solution infused in an ESI source, may alter the composition description of a complex mixture and leads to misinterpretations due to the formation of imines. Nevertheless, this experimental bias can be used to identify the carbonyl compounds in a pyrolysis bio-oil. As we demonstrated, infusion of the bio-oil with 3-chloroaniline in ESI source leads to specifically derivatized carbonyl compounds. Thanks to their chlorine isotopic pattern and the high mass measurement accuracy, (+) ESI Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) unambiguously highlighted them from the numerous CxHyOz bio-oil components. These results offer a new perspective into the detailed molecular structure of complex mixtures such as bio-oils. Graphical Abstract ᅟ.

The comprehensive description of complex mixtures such as bio-oils is required to understand and improve the different processes involved during biological, environmental or industrial operation. In this context, we have to consider how different ionization sources can improve a non-targeted approach. Thus, the Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) has been coupled to electrospray ionization (ESI), laser desorption ionization (LDI) and atmospheric pressure photoionization (APPI) to characterize an oak pyrolysis bio-oil. Close to 90% of the all 4500 compound formulae has been attributed to CxHyOz with similar oxygen class compound distribution. Nevertheless, their relative abundance in respect with their double bound equivalent (DBE) value has evidenced significant differences depending on the ion source used. ESI has allowed compounds with low DBE but more oxygen atoms to be ionized. APPI has demonstrated the efficient ionization of less polar compounds (high DBE values and less oxygen atoms). The LDI behavior of bio-oils has been considered intermediate in terms of DBE and oxygen amounts but it has also been demonstrated that a significant part of the features are specifically detected by this ionization method. Thus, the complementarity of three different ionization sources has been successfully demonstrated for the exhaustive characterization by petroleomic approach of a complex mixture.

International audience; The pyrolysis of the lignocellulosic biomass is a promising process to produce biofuels or green chemicals. Specific analytical methods have to be developed in order to better understand the composition of biomass and of its pyrolysis products and therefore to optimize the design of pyrolysis processes. For this purpose, different biomasses (Douglas and Miscanthus) and one biochar were analyzed by laser desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry (LDI FT-ICR MS). This method allowed the biomass and biochar to be analyzed without any sample preparation and with a spatial resolution of about 100 μm. The influence of LDI conditions (laser wavelength and laser irradiance) and the nature of the biomass and biochar on the obtained mass spectrum were investigated. The nature and origin of the observed ions highly depended on LDI conditions. In the softest laser–biomass interaction conditions (low laser irradiance), the detected ions were related to the nature of the investigated biomass. Indeed, the main part of the detected species came from the different biomass subunits and was produced by photolysis of covalent bonds. When more severe laser irradiation conditions were used, the obtained mass spectra gathered the ions relative to (i) the chemical components of the investigated samples, (ii) the recombination products of these species in the gas phase after their ejection from the sample surface, and (iii) the compounds produced by laser pyrolysis of the sample. This was expected to be useful to mimic thermal pyrolysis.

Pyrolysis or liquefaction processes can be applied to lignocellulosic biomass to produce a bio-oil which allows the access of green chemicals or sustainable energy. Among the different existing resources, this raw material has the advantage to come from nonfood feedstocks such as agricultural wastes (wood, grass, ...) or dedicated plantations. Whatever the considered bio-oil, the development of high performance analytical techniques is needed to achieve an exhaustive characterization. The use of Fourier transform ion cyclotron resonance mass spectrometry coupled to electrospray ionization (ESI-FT-ICR-MS) has the potential to chemically identify the components of bio-oil at the level of the molecular formula. In this work, we investigated the influence of the sample preparation (use and nature of dopant and ion detection mode) on the development of a robust methodology for lignocellulosic based bio-oil characterization. Commonly used ESI dopants have been studied to increase the ionization yield and the me...