Oak Species Quercus robur L. and Quercus petraea Liebl. Identification Based on UHPLC-HRMS/MS Molecular Networks

International audienceTwo species of oak are dominant in French forests: pedunculate oak (Quercus robur L.) and sessile oak (Quercus petraea Liebl.). Their differentiation is not straightforward but is essential to better understand their respective molecular content in order to better valorize them. Thus, to improve oak species identification, an untargeted UHPLC-HRMS/MS method associated with a two-step data treatment was developed to analyze a wide range of specialized metabolites enabling the comparison of both species of oak extracts. Pooled extracts from sessile and pedunculate oaks, composed of extracts from several trees of pure species from various origins, were compared using first the Venn diagram, as a quick way to get an initial idea of how close the extracts are, and then using a molecular network to visualize, on the one hand, the ions shared between the two species and, on the other hand, the compounds specific to one species. The molecular network showed that the two species shared common clusters mainly representative of tannins derivatives and that each species has specific molecules with similar fragmentation patterns, associated in specific clusters. This methodology was then applied to compare these two pooled extracts to unknown individuals in order to determine the species. The Venn diagram allowed for the quick presumption of the species of the individual and then the species could be assigned more precisely with the molecular network, at the level of specific clusters. This method, developed for the first time, has several interests. First, it makes it possible to discriminate the species and to correctly assign the species of unknown samples. Moreover, it gave an overview of the metabolite composition of each sample to better target oak tree utilization and valorization

Characterization of Corn Silk Extract Using HPLC/HRMS/MS Analyses and Bioinformatic Data Processing

In addition to having different biological activities of interest, corn silks play a role in the defense of plants. While benzoxamines and flavonoids have already been identified as molecules of plant defense and growth mechanisms, knowledge on the phytochemical composition of corn silk is lacking. Such knowledge would make it possible to better select the most effective varieties to improve resistance or bioactive properties. In this article, an approach was implemented to map a corn silk extract in two complementary ways. The first one involved working with UHPLC/HRMS data and Kendrick and van Krevelen plots to highlight a homologous series of compounds, such as lipids from 17 to 23 carbons, monoglycosylated flavonoids from 21 to 24 carbons, diglycosylated flavonoids of 26 to 28 carbons and organic acids of 14 to 19 carbons. The second way was to analyze the sample in UHPLC/HRMS2 and to plot mass spectral similarity networks with the GNPS platform and Cytoscape software to refine identification. By combining the information obtained, we were able to propose an identification for 104 detected molecules, including 7 nitrogenous, 28 lipidic and 67 phenolic compounds, leading to the first detailed phytochemical analysis of corn silk extract

TLC-MALDI-TOF-MS-based identification of flavonoid compounds using an inorganic matrix

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Impact of meteorological and social events on human-excreted contaminant loads in raw wastewater: From daily to weekly dynamics

International audienceThe temporal dynamics of the wastewater influent loads of 25 drug target residues (DTR, both pharmaceuticals and illicit drugs) was assessed during 84 consecutive days. This monitoring scale enables longer temporal patterns than weekday/weekend patterns to be explored. In this study, we focus on day to day variations and the potential statistical correlation of each DTR analyzed in order to better understand the potential forcings that lead to the load variation of DTRs (alone or in clusters). The weekly patterns based on the weekly loads of DTRs were also analyzed and the impact of social and meteorological events on their variations was investigated.Two cold events occurred during the monitoring period and were associated with the highest loads of analgesics and non-steroidal anti-inflammatory drugs, as well as the lowest loads of stimulants. During the Easter holidays, a significant decrease in some year-long medication as well as analgesics was found, consistent with the demographic decrease within the catchment during this period. Lastly, a good correlation between the academic calendar and the loads of stimulants was found, emphasizing the overrepresentation of students in the consumption of recreational drugs.This study furnishes new insights in order to better understand the variations in DTR loads in wastewater influents, beyond the weekday/weekend pattern and the seasonal effect. Further investigations remain necessary, especially a real-time monitoring of the population figures within the catchment in order to improve our understanding of these results

Temporal dynamics of human-excreted pollutants in wastewater treatment plant influents: toward a better knowledge of mass load fluctuations

International audienceThe occurrence of 25 drug target residues (illicit drugs or pharmaceutically active compounds) was investigated during 85 consecutive days in the influents of a wastewater treatment plant in the Region Centre-Val de Loire, France. This long tracking period allowed a better understanding of the patterns affecting the occurrence of this type of contaminants. Among them, 2 were never detected (i.e. heroin and amphetamine). Concerning illicit drugs two patterns were found. Cocaine and ecstasy median loads varied considerably between weekdays and weekend days (i.e. 18.3 and 35.9 % respectively) whereas cannabis and heroin (based on 6-mono-acetylmorphine loads) loads were within the same order of magnitude with a significant statistical correlation with pharmaceuticals such as acetaminophen or ketoprofen. 2 The consumption of selected drugs was back-calculated from the loads. Among illicit drugs the highest consumption was found for cannabis with a median consumption of 51 mg.day-1 .inhabitant-1 (inh) whereas the median consumption for cocaine (based on benzoylecgonine loads) and ecstasy was 32 and 6 mg.day-1 .10 3 .inh-1 respectively. The highest consumption values of pharmaceutically active compounds (PACs) were found for acetaminophen and acetylsalicylic acid with 108.8 and 34.1 mg.day-1 .inh-1 respectively, in good agreement with national sales data. A statistically significant weekly pattern was found for several PACs such as metoprolol and trimethoprim, but with the opposite pattern to that of illicit drugs. The variations in daily PAC loads could provide information about the mobility of people in the catchment, especially on the basis of daily taken PACs (i.e. to treat chronicle diseases)

Untargeted UHPLC‐Q‐TOF‐HRMS based determination of discrimating compounds for oak species Quercus robur L. and Quercus petraea Liebl. identification

International audienceIntroduction Two species of oak are dominant in French forests: pedunculate oak (Quercus robur L.) and sessile oak (Quercus petraea Liebl.). Differentiating oak species is difficult, since features such as morphological characters, geographical origin and grain are not always relevant. Even if the former is generally richer in tannin compounds while the latter is often richer in aromatic compounds, the intra-species variability is high. The characterisation of the oak species remains a suitable indicator of the molecular composition and quality of the wood. Objectives The aim of this study was to determine differentiating molecules allowing oak species identification in order to assist in a suitable wood selection for a better oak tree valorisation since the selection of the oak wood to be used in the production of barrels plays an essential role in wine ageing. Materials and Methods Oak wood samples were collected both in forests and in cooperage timber yards. An untargeted metabolomic approach using ultra-high-pressure liquid chromatography qualitative time-of-flight high-resolution mass spectrometry (UHPLC-Q-TOF-HRMS) associated to multivariate statistical analyses (hierarchical ascendant clustering and partial least squares discriminant analysis) was implemented to determine molecular markers of oak species. Results Heartwood was identified as the suitable wood part to distinguish oak species. Discriminating molecules did not depend on the sample set. The pedunculate species showed overexpression of bartogenic derivatives while sessile oak presented a higher content in oak lactone precursors and in quercotriterpenosids. Conclusion The developed method allowed the identification of relevant compounds for oak species identification to a better wood valorisation and selection

Clay minerals for the removal of pharmaceuticals: Initial investigations of their adsorption properties in real wastewater effluents

International audienceThe adsorption of pharmaceutical products (PPs) onto kaolinite and raw and sodium-exchanged montmorillonite was investigated in real wastewater effluents (WWE). The important role of the charge state of the PPs in controlling the adsorption extent was highlighted. Whereas cationic PPs were mostly adsorbed through cation exchange, the adsorption of neutral and anionic PPs appeared to be controlled by the nature of compensating inorganic cations and/or the simultaneous adsorption of organic moieties onto clay minerals. In raw WWE, the concentration of PPs is indeed far lower than the concentration of other organic molecules. Among the adsorbents tested, kaolinite displayed the lowest adsorption capacity of both PPs and other organic molecules, compared to raw montmorillonite which presented the highest adsorption capacity. The sodium-exchanged montmorillonite displayed intermediate adsorption properties, highlighting the key role of divalent inorganic cations in the adsorption of non-cationic PPs and other organic molecules. Hence, raw montmorillonite appears to be the most promising adsorbent for further investigations aiming to test the practicability of a clay-based adsorbent for the removal of organic contaminants, such as PPs, in WWE

Use of a clay mineral and its nonionic and cationic organoclay derivatives for the removal of pharmaceuticals from rural wastewater effluents

International audienceA Na+ exchanged montmorillonite clay (Na-Mt) and its organoclay derivatives prepared with benzyldimethyltetradecylammonium (BDTA) cationic and polyoxyethylene(20)oleyl-ether (Brij-O20) non-ionic surfactants were used for first time at our knowledge as adsorbents the removal diverse pharmaceuticals (PPs) from samples collected in a rural wastewater facility (town of Josnes in France). The selected facility showed a poor efficiency for the elimination of PPs that were permanently release to the environment. Although involving different interactional mechanisms, the whole adsorbents Na-Mt, nonionic Brij-Mt and cationic BDTA-Mt organoclays, could remove the entire PPs of various chemical nature in a low concentration regime (ng L-1), where electrostatic interactions mainly controlled the adsorption. Thus, the organic PPs cations were preferentially adsorbed onto Na-Mt and Brij0.4-Mt (with its dual hydrophilic-hydrophobic nature) while anionic PPs showed a bold affinity to BDTA-Mt. The hydrophobic environment generated by the intercalation of surfactants within the interlayer space of organoclays conferred a versatility for the adsorption of numerous PPs through weak molecular forces (Van der Waals and/or pi-pi interactions). The study confirmed the proper efficiency of the studied layered materials including organoclays and emphasized about their promising interests in water remediation strategy

Occurrence of drug target residues within decantation tank sediments: a good clue to assess their historical excretion?

International audienceAbstract This study investigated the potential of sediments accumulated in sewer systems to record human activities through the occurrence of drug target residues (DTR). The installation studied is 17 m deep underground decantation tank that traps the coarse fractions of a unitary sewer system (northern part of Orléans, France), collecting both stormwater and wastewater. The sediments deposited in this tank could constitute a nonesuch opportunity to study the historical evolution of illicit and licit drug consumption in the catchment, however, the deposition processes and the record of DTRs remain largely unknown at present. Five cores were acquired from 2015 to 2017. One hundred fifty-two sediment samples were extracted using a mixture of ultra-pure water:methanol (1:1) prior to analysis of the extracts by high-pressure liquid chromatography coupled to tandem mass spectrometry. Several classical sedimentological analyses such as total organic carbon, facies description and granulometry were also performed on these samples, in order to understand the most important factors (e.g., physico-chemical properties of the DTRs, solid type, assumed load in wastewater) impacting their deposition. The key role of the speciation of DTRs was highlighted by the higher contents in neutral and anionic DTRs in organic layers, whereas only cationic DTRs were found in mineral layers. The considerable modifications in the sediments’ properties, generated by distinct origins (i.e., stormwater or wastewater), are therefore the most important drivers that must be taken into account when back-calculating the historical patterns of drug consumption from their DTR concentrations in decantation tank sediments. Further research remains necessary to fully understand the deposition process, but this study provides new clues explaining these temporal evolutions