Identifying transdiagnostic socio-cognitive profiles across 4 clinical populations o Distinct profiles of perspective-takers found in healthy participants 1,2 . o Socio-cognitive impairments and interpersonal difficulties are frequently observed in various mental disorders [4][5] .

o But inconsistent findings: possibly due to overreliance on single-score and self-report measures, and unaccounted heterogeneity within populations sharing the same diagnosis Multidimensional and transdiagnostic assessment of social cognition 1,6 .

We examined socio-cognitive performance across two dimensions 6 posited to underpin mentalizing skills across all populations

• Self-Other Priority: the tendency to focus more (or attentionally prioritize) on one perspective compared to the other.

• Self-Other Distinction: the ability to handle conflicting perspectives and inhibit the interference.

Method

• WHAT (s)he can see

Self-Other priority:

(IES Other-persp. -IES Self-persp.) / (IES Other-persp. + IES Self-persp.)

Self-Other distinction:

(IES Incongruent-persp. -IES Congruent-persp.) / (IES Incongruent-persp. + IES Congruent-persp.)

3 main results:

• High individual differences along both dimensions • 3 similar clusters across VPT1 and VPT2


domain: sde sdv

text:
Note relative à l'utilisation de modèles de dérive inverse pour l'identification de zones à risque d'interaction entre tortues marines et activités humaines

CONTEXTE

Les modèles de dérive inverse permettent de simuler la trajectoire de dérive de carcasses retrouvées échouées, et ainsi d'identifier les zones de mortalité probables. Pour cela, ces modèles dépendent de modèles océanographiques (i.e. courants, marées) et météorologiques (i.e. forçage du vent) ainsi que des données relatives aux échouages (dates, coordonnées spatiales et état de décomposition des carcasses). Les caractéristiques de flottaison (taux d'immersion) des carcasses étant un paramètre clé, les modèles de dérive inverse doivent généralement être adaptés à l'espèce considérée. De plus, une bonne connaissance de la vitesse de décomposition des carcasses en fonction de la température de l'eau dans la zone d'étude est nécessaire pour estimer la date, et donc la zone, de mortalité.

Des modèles de dérive inverse ont déjà été développés pour identifier les zones de mortalité pour plusieurs espèces de tortues marines (Caouanne et tortue de Kemp) dans la baie de Chesapeake aux États-Unis1 . En revanche, aucun modèle n'a à ce jour été développé et testé pour caractériser la dérive de tortues échouées sur les côtes Françaises.

En revanche, un modèle de dérive inverse a été développé et utilisé avec succès par l'UMS PELAGIS (La Rochelle Université-CNRS) pour les petits cétacés (Dauphin commun et marsouin) dans l'Océan Atlantique. Ce modèle, basé sur le modèle MOTHY-Leeway (Modèle Océanique de Transport d'HYdrocarbures), permet l'estimation du nombre total d'échouages et la cartographie des zones de mortalité à partir des données collectées par les réseaux d'échouage (dans ce cas le Réseau National Échouages -RNE) 2,3 . Par conséquent, la dérive inverse a été intégrée au dispositif de suivi « Réseau National Échouages des mammifères marins (RNE) » du Programme de surveillance DCSMM 4 . En particulier, la dérive inverse a contribué à l'évaluation DCSMM cycle 2 en 2018 des mammifères marins, et notamment à celle du critère D1C1 (mortalité par capture accidentelle) dans la région Atlantique nord-est 5 .

En préparation de la prochaine évaluation DCSMM (2024), l'UMS PELAGIS a récemment développé un nouveau modèle de dérive inverse pour la sous-région marine Méditerranée Occidentale. Au vu du nombre relativement élevé d'échouages de tortues marines (principalement tortues caouannes) sur les côtes Méditerranéennes, la question de l'utilisation de la dérive inverse pour l'évaluation DCSMM des tortues marines s'est posé.

Cette note présente les résultats des simulations de dérive inverse réalisées par l'UMS PELAGIS à partir de données d'échouage de tortues caouannes sur les côtes Méditerranéennes collectées par le Réseaux Tortues Marines de Méditerranée Française (RTMMF) entre 2018 et 2020.

DONNÉES UTILISÉES

Les données d'échouage de tortues caouannes (Caretta caretta) collectées par le RTMMF (Réseau Tortues Marine de Méditerranée Française) ont été utilisées pour effectuer les tests de dérive inverse (Tableau 1). Les zones de mortalité potentielles de ces individus sont représentées Figure 1. Chaque dérive correspond à un ensemble de points issus des différentes simulations (8670 simulations pour chaque individu) de dérive. Les zones potentielles de mortalité sont donc représentées par des enveloppes contenant les points les plus proches (50%, 75% et 95% des points les plus proches représentés Figure 1). Malgré les limites présentées ci-dessus, les résultats préliminaires obtenus indiquent que les modèles de dérive inverse, initialement développés pour les mammifères marins, peuvent être adaptés au tortues marines, représentant ainsi un outil pertinent et prometteur pour les futures évaluations du Descripteur 1-tortues marines DCSMM.

Figure 1 .

 1 Figure 1. Zones potentielles de mortalité par capture accidentelle (A, B, C et D) et collision (E) identifiées à partir de tortues caouannes échouées (Tableau 2). Les temps de dérive correspondants ont été estimés à partir de l'état de décomposition des carcasses. Les couleurs (Probabilité) représentent les enveloppes contenant 50%, 75% et 95% des points les plus proches. Les points rouges indiquent la zone d'échouage.

  Tableau 1. Nombre de tortues caouannes échouées et de simulations de dérive inverse ayant abouties par an entre 2018 et 2020.

	Date d'échouage	Cause de mortalité	État de fraicheur Temps de dérive Référence
	20/04/2018	Capture accidentelle	Frais	1	A
	21/04/2018	Capture accidentelle	Frais	1	B
	24/12/2018	Capture accidentelle	Frais	1	C
	Année 28/06/2019 2018 06/07/2020	Nombre d'échouages Capture accidentelle 34 Collision	Putréfié Putréfié	2 Nombre de dérives simulées 27 2	D E
	2019	17		17
	2020	26		26
	 État frais : 1 jour
	 État putréfié : 2 jours
	 État très putréfié : 4 jours
	 Restes : 6 jours
	Le modèle MOTHY-Leeway utilisé est de type « probabiliste ». Par conséquent, 8670 simulations
	ont été lancées pour chaque individu échoué pour prendre en compte l'ensemble des situations
	possibles sur chaque trajectoire (variations de flottabilité, modélisation des courants…). Les
	simulations de dérive intègrent les vents (source Météo-France) et la courantologie (source
	CMEMS -Copernicus) avec une profondeur proche de 30m.

Les vitesses de décomposition, permettant d'estimer le temps de dérive entre la mort et l'échouage des tortues, utilisées correspondent à celles estimées par Santos et al. (2018) pour les tortues Caouannes de la baie de Chesapeake 6 . Les temps moyens de dérive considérés en fonction de l'état de décomposition des carcasses sont les suivants :

Santos B.S., Friedrichs M.A.M., Rose S.A., Barco S.G. et Kaplan D.M.,

Likely locations of sea turtle stranding mortality using experimentally calibrated, time and space-specific drift models. Biological Conservation 226: 127-143. 2 Peltier H., Dabin W., Daniel P., Van Canneyt O., Dorémus G., Huon M. et Ridoux V. 2012. The significance of stranding data as indicators of cetacean populations at sea: Modelling the drift of cetacean carcasses. Ecological Indicators 18: 278-290. 3 Peltier H., Authier M., Dabin W., Dars C., Demaret F., Dorémus G., Van Canneyt O., Laran S., Mendez-Fernandez P., Spitz J., Daniel P. et Ridoux V. 2020. Can modelling the drift of bycaught dolphin stranded carcasses help identify involved fisheries? An exploratory study. Global Ecology and Conservation 21: e00843. 4 Guichard B. 2020. Programme de surveillance 2eme cycle D1 « Mammifères marinstortues marines ». 68p. 5 Spitz J., Peltier H. et Authier M. 2018. Évaluation du descripteur 1 « Mammifères marins » en France Métropolitaine -Rapport scientifique pour l'évaluation 2018 au titre de la DCSMM. 170p.

Santos B.S., Kaplan D.M., Friedrichs M.A.M., Barco S.G., Mansfield K.L. et Manning J.P. 2018. Consequences of drift and carcass decomposition for estimating sea turtle mortality hotspots. Ecological Indicators 84: 319-336.


J Roux

M Seidl

P Branchu

M C Gromaire

P Neveu

L Boudahmane

E Caupos

V Alphonse

N Bousserrhine
email: bousserrhine@u-pec.fr

Accumulation of organic and inorganic micropollutants over time and space in a constructed wetland for urban runoff

Keywords: Organic micropollutant, Metallic micropollutant, Constructed wetland, Vertical reed-bed filter, Urban runoff water, Microbial abundance

published or not. The documents may come

Accumulation of organic and inorganic micro-pollutants over time and space in a constructed wetland for urban run-off

INTRODUCTION

Urban runoff water is known for its contamination with metallic and organic compounds, mainly from road traffic [START_REF] Markiewicz | Emissions of organic pollutants from traffic and roads: Priority pollutants selection and substance flow analysis[END_REF]. This water can contribute to the degradation of the receiving aquatic environments if they are discharged without treatment. To limit these contaminant flows to the Seine River, the European Life Adsorb project has been set up in Paris by the municipality. A vertical flow reed-bed filter, a type of constructed wetland (CW) was built in 2019-2020 to receive and treat road runoff water. This CW is separated in two treatment compartments, with one having a conventional design, and the other having an innovative design for handling dissolved contamination. The innovative system must be able to treat both dissolved and particulate contaminations.

The Life Adsorb project aims to reduce the pollutant loads of Parisian urban runoff waters, but also to better understand the processes involved during the vertical filtration of these waters, like adsorption and biodegradation. Metallic (MMPs) and organic (OMPs) micropollutants (MPs) are particularly studied, as well as microbial communities presents, their evolution and their roles in CWs (very limited studies). In this context, the objective of this study is to compare the evolution in time and space of the two CWs through physicochemical and microbiological parameters and to explain the accumulation of MMPs and OMPs.

METHODOLOGY The constructed wetland

The CW, located in the Bois de Boulogne Park in Paris (France, 48°52'28.6"N 2°15'43.6"E) is subdivided into two CWs of approximately 600 m² each and 1 m deep. Their design is similar; from top to bottom there is a filtering layer (40 cm), then a transition layer (10 cm) and finally a drainage layer (50 cm). The difference between these 2 CWs is in the composition of the filtration layer. In the conventional CW (CWS), this layer is composed of 40 cm sand while in the innovative one (CWR), a layer of 20 cm of an industrial adsorbent substrate, the Rainclean® (RC) is inserted between two layers of 10 cm of sand (figure 1). Finally, the CWs are planted with common reeds (Phragmites australis), contributing to the hydrological processes and rhizosphere microorganisms support (Wang and al., 2022). Each CW is fed upstream alternatively (monthly frequency) by pumps from a runoff storage reservoir (one feed zone per CW). The output flow is regulated to a maximum of 20 L/s during rain periods. Finally, the CW also receives parasitic clear water that causes a dry weather flow.

Sampling campaigns and analysis

The CWs began to be fed with contaminated water in February 2021 (almost 2 years of feeding). Three sampling campaigns were carried out, in september 2020 (= T0), september 2021 (= T1) and september 2022 (= T2) to study the space-time evolution of the CWs. During each campaign, core samples were collected from the filtering layer, at the feeding zone (input), the center and the output zone of each CW. The substrates cores were then divided as follows: sediment if present (not at T0), first 10 cm of sand, layer of 10 -30 cm depth, which is whether sand or RC and deep sand layer of 30 -40 cm depth. During this conference, results of the T0 and T1 campaigns will be presented.

To physicochemically characterise the CWs, pH, cation exchange capacity (CEC), particle size distribution but also total organic carbon, nitrogen and carbonates content were analysed.

To assess the accumulation of micropollutants (MPs), analyses of their total contents were carried out. Concerning MMPs, 6 metals are studied: Cd, Cr, Cu, Ni, Pb, Zn (extraction with aqua regia and analysis by ICP-AES). In addition, a fine mapping of the surface metal content undertaken by X-ray fluorescence. Concerning OMPs, groups of compounds widely studied in the literature were measured (15 PAH, C10-C40 hydrocarbons), but also emerging compounds such as alkylphenols, phthalates and bisphenol-A (specific solvent extraction then GS-MS or UPLC-MS-MS analyse).

Finally, as the microbial communities present in the CWs are still too little known, three types of microbiological measurements were carried out: abundance of bacteria and fungi (MPN method), genetic diversity (DNA sequencing) and environmental functions (assays of enzymatic activities).

RESULTS

Results of the physicochemical properties (data not shown) reveal that Rainclean (RC) and sediment are much more organic (around 20 and 150 goc/kg respectively) than sand (less than 10 goc/kg), which implies a higher CEC. On the other hand, the pH of sand and RC are very alkaline (8.6 to 9.2) compared to sediment (7.3 to 7.7). The samples taken in the feeding zone of CWs after one year of operation are richer in organic carbon than the rest of the CWs, due to the water inlet location; runoff organic particulate matter is filtered as soon as it enters the CW. These properties illustrate the physical filtration role of sand (particulate contaminants) and chemical filtration role of RC (dissolved contaminants).

Concerning the horizontal distribution of MMPs in the CWs, results show that the majority is retained in the feeding zone like organic carbon, regardless of the metal (figure 2A, only Zn shown). For example, content of Zn decreases from 65 to 20 mg/kg between input and output zones of the CWR surface sand. Regarding the vertical distribution of MMPs, it should first be noted that RC was initially richer in metals than sand (figure 2) and no sediment was present at T0. After one-year of functioning, accumulated sediments show the highest MMPs contents (574 to 656 mg/kg for Cu, 204 to 215 mg/kg for Pb and 1337 to 1418 mg/kg for Zn) and metals contents of the surface sand got close to that of RC (10 mg/kg for Pb in both, 65 mg/kg for Zn in sand against 79 mg/kg for Zn in RC) which seems to indicate that MMPs are essentially retained in the surface sand. This suggest that MMPs associate preferentially with particulate matter contained in water which are then retained by filtration in the sand. Finally, MMPs contents decrease rapidly with depth, with a slight increase in one year. Comparing the MMPs contents found with those measured in another older CW [START_REF] Walaszek | Micropollutants removal and storage efficiencies in urban stormwater constructed wetland[END_REF], they are higher for Cu, lower for Zn and in the same concentration range for Pb in sediment and they are lower in the surface of sand layer.

Concerning OMPs (BPA and 2 alkylphenols, 4-OP and 4-NP are discussed), very few accumulations were observed between the two campaigns (figure 2B, only 4-NP shown). Again, sediment show the highest contents (0.6 to 0.7 µg/g for BPA, 0.11 to 0.33 µg/g for 4-OP and 2.9 to 3.1 µg/g for 4-NP).

Conventional -CWS Innovative -CWR

Concerning the surface sand, few accumulations are observed for 4-OP and 4-NP in the two CWs; for example, in the feeding zone of CWR, values range from 0.007 to 0.023 µg/g between T0 and T1 for 4-OP and from 0.040 to 0.178 µg/g between T0 and T1 for 4-NP. The RC and the lower sand layers were more contaminated at T0 than at T1 for the 3 compounds suggesting losses (biodegradation and/or release). 4-NP is the most present compound, which is consistent with its dominance measured by other authors in urban runoff [START_REF] Gasperi | Micropollutants in Urban Runoff from Traffic Areas: Target and Non-Target Screening on Four Contrasted Sites[END_REF]. As to our knowledge, no study has measured these compounds in CW for runoff treatment, so the values are compared to those measured by [START_REF] Flanagan | Retention and transport processes of particulate and dissolved micropollutants in stormwater biofilters treating road runoff[END_REF] in the surface substrates of an infiltration swale of approximately one-year-old. Nor sand nor RC reach levels measured in the swale for any of the OMPs; however, the sediment is 20 times richer in BPA, 2 to 6 times richer in 4-OP and 6 times richer in 4-NP than the swale substrate for the same exposure time.

Finally, regarding the bacterial abundance of CWs (figure 2C), they are essentially present in sediment (10 6 UFC/g) and then in the surface sand layer (10 4 UFC/g). Their abundance is still low in the RC (10 3 UFC/g) although it has increased between the two campaigns.

CONCLUSION

The results of this study show that runoff MPs accumulate mainly at the feeding zone and on the surface (sediment and surface sand) of both CWs. At this stage, Rainclean has not yet demonstrated all its retention capacities (metallic and organic). The T2 campaign will make it possible to observe whether RC retention efficacity is improved with time. Regarding MMPs, copper seems to be more retained in sand and RC than other metals, which is consistent with their adsorption coefficient. For OMPs, the low accumulation could be explained by the biodegradation of these compounds by the microorganisms present. A contaminant's mass balance of the CWs and specific laboratory biodegradation tests are being carried out to validate these hypotheses.

Figure 1 .

 1 Figure 1. Vertical profile of the Life Adsorb constructed wetland. The conventional one (CWS, with sand) on the left and the innovative one (CWR, with Rainclean) on the right. Different layers are shown on the left and the nature (substrate with granulometry) of each layer is specified on the right.

Figure 2 .

 2 Figure 2. Vertical profiles of 3 parameters (logarithmic scale) in the input and output zones of CWS (left) and CWR (right) for T0 and T1 sampling campaigns. A: Zn contents (mg/kgds). B: 4-NP contents (µg/gds). C: Bacterial biomass (MPN, CFU/gds).


Jacques Cabau

CRITIQUE, PRÉFACIER Universitaire

André Le Vot

Laurette Véza

Sylvie Mathe

Las Vergnas -« le patron », à qui il dédiera La Prairie perduesur « Thomas Carlyle ou le Prométhée enchaîné, essai sur la genèse de l'oeuvre de 1795 à 1834 », qu'il soutient au plus fort de la révolte de Mai 68. Enseignant très charismatique, il fait partie, avec

Outre sa thèse, publiée aux Presses universitaires de France en 1968, il est l'auteur d'une monographie sur Edgar Poe, Edgar Poe par lui-même, dans la collection « Écrivains de toujours » (Seuil, 1960), ainsi que de nombreuses préfaces essentiellement pour les éditions Rencontre à Lausanne, un des clubs de livres les plus importants de la francophonie dans les années cinquante à soixante-dix, spécialisé dans les grandes collections d'auteurs classiques. La séquence des ouvrages préfacés, rassemblés dans la collection « Sommets du roman américain » en douze volumes, dessine les contours de l'évolution du roman américain, depuis La Prairie de Cooper qui lance la sérieprécédée à ce titre d'une préface générale sur le roman américain signée Cabau également -jusqu'aux grands noms de « l'âge du roman américain » et au roman noir 1977).

Critique littéraire à L'Express, puis au Point, spécialisé dans l'actualité anglo-américaine (Henry Miller, Anaïs Nin, les Beats, Eudora Welty, Alan Sillitoe, Vladimir Nabokov, Saul Bellow, William S. Burroughs, Norman Mailer, Thomas Wolfe, E.L. Doctorow, Jerzy Kosinski, Joyce Carol Oates, John Irving, Jerome Charyn, etc.), Jacques Cabau signe des articles percutants des années soixante aux années quatre-vingt, où sa prose musclée, son sens du raccourci et ses formules choc contribuent à faire rayonner la littérature anglo-saxonne. Ses critiques, qui rencontrent un large public, ont l'art de faire ou défaire les réputations, voire les fortunes éditoriales : en témoigne sa recension du roman érotique de l'auteur à succès Jacqueline Susann, The Love Machine (1969), best seller paru aux États-Unis chez Simon & Schuster à l'apogée de la révolution sexuelle, et traduit aux éditions Belfond par Florent B. Peiré sous le même titre (sans article), que Jacques Cabau descend en flammes dans un article à sensation qui fait l'ouverturetrois pages avec photosde ce numéro de l'Express de mars 1971, avec pour résultat que les ventes du roman rebondissent de plus belle. Pierre Belfond dans ses mémoires, Scènes de la vie d'un éditeur, évoque avec amusement ce revirement miraculeux grâce auquel la critique au vitriol de Cabau a précipité les foules dans les librairies et a ainsi sauvé sa maison d'édition qui était alors au bord du dépôt de bilan : « C'est un massacre ! […] Votre Love Machine est hâché menu, réduit en bouillie. Un carnage. Trois pages au vitriol… Vous ne parviendrez pas à en récupérer une ligne pour un slogan publicitaire. Cabau -c'est un universitaire -s'en est donné à coeur joie », annonce à Belfond le rédacteur en chef des pages « Livres » de L'Express, tout en s'empressant de lui préciser de prévoir sans tarder une réimpression car « Ce sera le best-seller de l'été », et d'envoyer par la même occasion une caisse de champagne à Cabau (17-18).

Pour aussi mineure qu'elle soit dans la carrière d'un intellectuel de l'envergure de Jacques Cabau, cette anecdote en dit néanmoins long sur le style et la personnalité de cet universitaire flamboyant, qui subjuguait dans ses cours à la Sorbonne et captivait dans ses écrits. L'ouvrage phare de Jacques Cabau, celui qui a marqué des générations d'étudiants par son brio, reste La Prairie perdue, publiée au Seuil en 1966 dans la collection « Pierres Vives » (édition révisée et augmentée, coll. « Points », 1981), son histoire du roman américain qui a fait date dans les études américaines. L'étude, dont le titre renvoie l'écho de ces classiques que sont Virgin Land de Henry Nash [START_REF] Smith | Virgin Land: The American West as Symbol and Myth[END_REF] et The Machine in the Garden (1964) de Leo Marx, s'ancre dans la tradition critique fondatrice de l'Ouest américain comme mythe et symbole, qui sert de point de départ à cette anatomie du roman américain. Plus qu'une simple histoire, La Prairie perdue propose une lecture et une mise en perspective à la fois solidement contextualisées et éminemment personnelles de ce qui, entre romance et novel, fait la spécificité du roman américain. Adepte des raccourcis saisissants, aussi éclairant dans ses vues d'ensemble que dans ses plans rapprochés, toujours très stimulant dans ses jugements et incisif dans ses formulations, Jacques Cabau livre un essai singulier qui instruit autant qu'il séduit, et laisse la marque durable d'un tempérament aussi bien que d'une écriture, un « livre profondément original », écrit Monique Nathan dans sa critique pour le journal Le Monde à l'époque de la parution, « réflexion plus qu'histoire, interprétation plus qu'exposé universitaire, sans exclure néanmoins le souci d'une présentation didactique des "quinze romans qui ont fait l'Amérique". Depuis le livre célèbre de C.E. Magny sur l'Âge du roman américain, depuis Michel Mohrt et J.-J. Mayoux, c'est le premier ouvrage qui tente de faire le point en France, tandis qu'outre-Atlantique se multiplient, avec Chase, Kazin, Podhoretz et Fiedler, les critiques et les essais » (Le Monde, 5 octobre 1966). Ouvrage pionnier en son temps, La Prairie perdue ouvre ainsi des pistes et trace la route vers les études à venir que seront La Grand-route de Pierre-Yves Pétillon (Seuil, 1979) et Au-delà du soupçon de Marc Chénetier (Seuil, 1989), ces essais publiés à une décennie d'intervalle, imprégnés chacun de la personnalité de leur auteur, qui à eux trois baliseront la critique de la littérature américaine en France dans la seconde moitié du XX e siècle.

Le volume Écrivains américains (Larousse, coll. « Encyclopoche », 1977) plus sommaire que La Prairie perdue mais incluant poésie et théâtre, brosse un panorama de la littérature étatsunienne de la période coloniale à l'après-guerre. L'illustration de couverture, la photo iconique de Hemingway en col roulé prise par Yousuf Karsh à Cuba en 1957, où se devine dans ses yeux la détresse d'une mort annoncée, est étrangement prémonitoire du sort de l'auteur qui, un 1 er avril, choisira de se donner la même mort tragique qu'Hemingway.

Bibliographie primaire

et Le Faucon de Malte de Dashiell Hammett, douze titres qui préfigurent l'étude fondatrice que sera La Prairie perdue (1966). À ses contributions comme préfacier à l'ensemble de cette collection aux éditions Rencontre viennent s'ajouter la préface de Ivanhoé de Walter Scott et celle de Daphné Adeane de Maurice Baring pour la même maison, puis celles de La Guerre de Mr. Wilson de Dos Passos (Stock, 1970), des Aventures d'Arthur Gordon Pym de Poe (Gallimard

  . S'enchaînent ainsi, après Cooper, La Lettre écarlate de Hawthorne, Moby Dick de Melville, Les Aventures de Huckleberry Finn de Twain, Les Histoires extraordinaires de Poe, Le Tour d'écrou suivi de Les Papiers de Jeffrey Aspern de James, Les Rapaces de Frank Norris, La Jungle d'Upton Sinclair, Tendre est la nuit de Fitzgerald, Lumière d'août de Faulkner, Pour qui sonne le glas de Hemingway, , 1975) et de La Fille de l'optimiste de Welty (Grasset, coll. « Bibliothèque du temps présent »,


Letizia Abis
email: letizia.abis@inra.fr

Benjamin Loubet

Raluca Ciuraru

Florence Lafouge

Samuel Dequiedt

Sabine Houot

Pierre Alain Maron

Sophie Bourgeteau-Sadet

Profiles of volatile organic compound emissions from soils amended with organic waste products

Keywords: VOC, soil, organic waste products, PTR-TOF-MS 1

This study investigates the Volatile Organic Compounds (VOCs) emitted from soil amended with four different organic waste products (OWP) every two years since 1998 and until now at a rate of ~4 tC ha -1 : municipal solid waste compost (MSW), green waste and sludge co-compost (GWS), bio-waste compost (BIOW) and farmyard manure (FYM). Soil samples were collected two years after the last application of OWP. The aim of this study was to detect different VOCs emissions from soils amended with OWP in order to establish a VOCs signature of the OWP and to understand if the total VOCs flux depends on the type of OWP in soil. They were compared to a soil which received no organic inputs (CN). The emissions were detected using a PTR-ToF-MS (Proton Transfer Reaction-Time of Flight-Mass Spectrometry). OWP in soil were detected using a laboratory system made of two pyrex chambers, one with samples and the second one empty. The on-line detection has been made measuring in first place the empty chamber in order to have a blank; secondly, a measure of the emissions in the chamber with the soil has been performed. Our results confirmed that VOCs emissions were affected by the type of organic amendment to soil. Overall, the most emitted compounds were acetone, butanone and acetaldehyde in all treatments. We found some compounds which had statistically different emissions between the treatments. For instance, GWS released more 94.03 m/z, 95.02 m/z, 110.06 m/z (benzamide), 111.07 m/z and 113.01 m/z than the 2 other OWPs. Our results suggest that organic matter and pH jointly influenced total VOC emissions. Other factors explaining the diversity of VOC emitted and the influence of treatments are discussed.

Introduction

The family of volatile organic compounds (VOCs) is composed of a large range of molecules with different functional groups and different chemical and physical properties. The common traits between VOCs are the high vapour pressure under ambient conditions and low boiling points which explain their presence in the atmosphere.

Volatile organic compounds sources have been extensively studied because of their contribution to global warming and pollution [START_REF] Kesselmeier | Biogenic volatile organic compounds (VOC): An overview on emission, physiology and ecology[END_REF]. It has been demonstrated that VOCs are involved in many chemical reactions in the atmosphere among which the production cycle of tropospheric ozone (O3) in combination with the NOx cycle [START_REF] Seinfeld | Atmospheric Chemistry and Physics: From Air Pollution to Climate Change[END_REF]. Another important chemical processes in the atmosphere that involves VOCs are the photolysis of formaldehyde and other carbonyls in presence of NO which are responsible of hydroxyl (OH) formation [START_REF] Atkinson | Atmospheric chemistry of VOCs and NOx[END_REF]. Additionally, VOCs are precursors of secondary organic aerosol (SOA) [START_REF] Singh | High concentrations and photochemical fate of oxygenated hydrocarbons in the global troposphere[END_REF] and are involved in the production of nitrates in the troposphere [START_REF] Monson | Biospheric Trace Gas Fluxes and Their Control Over Tropospheric Chemistry[END_REF]. For these reasons VOCs alter the air quality and thus they have indirectly consequences on human and ecosystems health.

Several studies demonstrate that biogenic VOCs contribute to 90% of the total VOCs emissions [START_REF] Atkinson | Atmospheric chemistry of VOCs and NOx[END_REF], while anthropogenic sources such as industries, solvents, transportations etc. contribute only for the 10% of the total VOCs emissions. Among the most important biogenic sources of VOCs are living plants, with a global emission of 1Pg C y -1 , mainly monoterpenes from broadleaves forests [START_REF] Guenther | A global model of natural volatile organic compound emissions[END_REF]Zemankova and Brechler, 2010;[START_REF] Harrison | Volatile isoprenoid emissions from plastid to planet[END_REF]. Furthermore, it has been shown that the soil and litter can release around 12 to 136 % of monoterpenes compared to canopy emissions in spring and fall [START_REF] Faiola | SOA Formation Potential of Emissions from Soil and Leaf Litter[END_REF].

Another source of biogenic VOCs is the interaction between soil and microorganisms. Soils VOCs emissions are up to three times lower than the VOCs release from the canopy. Nevertheless, it has been demonstrated that under certain temperatures and soil water contents, and for specific ecosystems, VOCs emissions from soil could reach the same magnitude as canopy emissions [START_REF] Peñuelas | Biogenic volatile emissions from the soil[END_REF]. Additionally, little is known about the emissions from agricultural fields, although they are recognised as large contributors of methanol and acetone to the atmosphere [START_REF] Bachy | Methanol exchange dynamics between a temperate cropland soil and the atmosphere[END_REF][START_REF] Mozaffar | Biogenic volatile organic compound emissions from senescent maize leaves and a comparison with other leaf developmental stages[END_REF][START_REF] Goldan | Hydrocarbon measurements in the southeastern United States: The Rural Oxidants in the Southern Environment (ROSE) Program 1990[END_REF]. It however appears from recent measurements that soils may contribute to a large extent to the overall balance of VOC fluxes in crop rotations [START_REF] Bachy | Are BVOC exchanges in agricultural ecosystems overestimated? Insights from fluxes measured in a maize field over a whole growing season[END_REF] From another perspective, intensive agriculture may lead to the decrease of soil organic matter contents [START_REF] Chan | Soil carbon fractions and relationship to soil quality under different tillage and stubble management[END_REF] and Europe is encouraging the use of organic waste products (OWPs) in crops (European Commision, 2010) to favour carbon storage in soils [START_REF] Peltre | RothC simulation of carbon accumulation in soil after repeated application of widely different organic amendments[END_REF]. The recycling of OWPs in soils also represents an alternative to waste management by landfilling or incineration. The application of OWPs also provides nutrients such as nitrogen (N) and phosphorous (P) which make possible the substitution of mineral fertilizer, improves soil biodiversity and has positive impacts on soil physical properties such as aggregate stability [START_REF] Annabi | Soil Aggregate Stability Improvement with Urban Composts of Different Maturities[END_REF][START_REF] Diacono | Long-term effects of organic amendments on soil fertility[END_REF]. The negative impacts are not negligible though; for instance OWP release contaminants that can be transferred to plants, water or to the atmosphere [START_REF] Belon | An inventory of trace elements inputs to French agricultural soils[END_REF]. Organic wastes also affect soil pH, and pH is one of the chemical properties that impact on VOCs emissions [START_REF] Brinton | Volatile Organic Acids In Compost: Production and Odorant Aspects[END_REF]. Positive and negative impacts in soil vary with the applied organic waste product [START_REF] Obriot | Multi-criteria indices to evaluate the effects of repeated organic amendment applications on soil and crop quality[END_REF]. For example [START_REF] Seewald | Substrate-induced volatile organic compound emissions from compost-amended soils[END_REF] studied VOCs production by adding glucose to soils regularly amended by different composts. There was no impact on the VOCs emissions compared to control sample with one of the composts, while for another one and mineral fertilization they observed different VOCs emissions. Moreover, [START_REF] Potard | Organic amendment practices as possible drivers of biogenic Volatile Organic Compounds emitted by soils in agrosystems[END_REF] showed that different soil organic fertilizers such as pig slurry and methanized pig slurry impact in a different way soil VOCs emissions: pig slurry releases double quantities of VOCs while methanized pig slurry emits even less than the unamended samples. Contrasting type of VOCs emissions from soil have been reported from several studies. For instance, in Mediterranean soils the most emitted compound was methanol (Asensio et al., 2007a) while in soil amended with straw it was acetone [START_REF] Zhao | Volatile organic compound emissions from straw-amended agricultural soils and their relations to bacterial communities: A laboratory study[END_REF]. In fact, emissions of VOCs are strongly related to the substrate quality and it is important to note that even small variations in nutrient composition may change the type and the amount of individual VOCs produced [START_REF] Wheatley | The consequences of volatile organic compound mediated bacterial and fungal interactions[END_REF].

Significant emissions of the VOCs released by soil are produced by microorganisms [START_REF] Isidorov | Volatile organic compounds from leaves litter[END_REF][START_REF] Stahl | Microbial production of volatile organic compounds in soil microcosms[END_REF]. It has been reported that the composition and amount of VOCs emitted are linked to the microbial community living in the soil (Asensio et al., 2007b;[START_REF] Schade | OVOC emissions from agricultural soil in northern Germany during the 2003 European heat wave[END_REF][START_REF] Seewald | Substrate-induced volatile organic compound emissions from compost-amended soils[END_REF].

Microorganisms produce VOCs as a result of the degradation of sugar, alcoholic fermentation, amino acid and fatty acid degradation, terpenoid biosynthesis and sulphur reduction. For instance, acetaldehyde, which is one of the compounds most emitted from soil, is formed during the alcoholic fermentation that produces ethanol [START_REF] Castaldelli | Decomposition dynamics of the bloom forming macroalga Ulva rigida C. Agardh determined using a C-14-carbon radio-tracer technique[END_REF][START_REF] Karl | Seasonal variation of biogenic VOC emissions above a mixed hardwood forest in northern Michigan[END_REF]. Previous studies have reported that microorganisms degrade sugar following three major pathways: (1) Embden-Meyerof pathway, (2) Heterolactic/homolactic pathway and (3) Entner-Douoroff pathway. In these processes, intermediate compounds are produced such as pyruvate, glyceraldehyde-3-phosphate, lactate and acetate which are precursors for the biosynthesis of several VOCs [START_REF] Peñuelas | Biogenic volatile emissions from the soil[END_REF]. VOCs are also released as molecules resulting from the secondary metabolisms of microorganisms [START_REF] Werner | Belowground communication: impacts of volatile organic compounds (VOCs) from soil fungi on other soil-inhabiting organisms[END_REF]. Secondary metabolites might be produced under certain circumstances or development stages; hence they might be used as indicator of the cellular state [START_REF] Patti | Innovation: Metabolomics: the apogee of the omics trilogy[END_REF]. Furthermore, it has been demonstrated that the nature of the substrate can affect microorganisms' community and thus change VOCs emissions [START_REF] Peñuelas | Biogenic volatile emissions from the soil[END_REF]. Moreover, the application of OWP in soil stimulate its diversity, the abundance and the activities of microorganisms in soil compared to soils that only received mineral fertilizers. This is a consequence of the addition of microorganisms previously present in the OWP [START_REF] Ros | Long-term effects of compost amendment of soil on functional and structural diversity and microbial activity[END_REF].

The aim of this study was to determine whether soil regularly amended with different organic waste products for a long period have a differentiated volatile organic compound signature. Four soils amended for 20 years with organic wastes products were considered: bio-waste compost (BIOW), green waste and sludge compost (GWS), municipal solid waste compost (MSW) and farmyard manure (FYM). All these soils were compared with a control sample that had never received any OWP. We measured VOCs fluxes under standardised laboratory conditions with a proton transfer reactiontime of flight-mass spectrometer (PTR-TOF-MS). The VOCs released were identified and quantified and the relationship between VOCs emissions and soil chemical characteristics (pH, organic matter, Iroc…) was studied.

Methods

Site description

Samples were collected in the QuagliAgro site, a field station taking part of the and good drainage. Moreover, the Qualiagro field experiment is in a cropland dominated region, which lead to a low organic carbon and low organic matter concentrations (initial content of 1.1%) [START_REF] Meersmans | A high resolution map of French soil organic carbon[END_REF]. On the other hand, observing QualiAgro site on a smaller scale, differences in the organic carbon content, total nitrogen or pH between samples are due to the different applications of OWP.

The experiment was a randomized block design with 4 replicates comparing 4 organic waste products: BIOW (bio-waste compost derived from the co-composting of green wastes and source-separated organic fractions of municipal solid wastes), GWS (compost derived from the co-composting of green wastes with sewage sludge), FYM (farmyard manure) and MSW (municipal solid waste compost derived from the composting of residual solid wastes after removing dry and clean packaging); plus a control without organic input (CN). Moreover, the 20 field blocks studied were additionally amended with mineral N to reach optimal N application. The field was cropped with a winter wheatmaize rotation. The wheat crop residues were exported, whereas the maize residues were returned to the soil. Since 1998, the organic waste products (OWP) have been applied at a rate of ~4 tC ha -1 every two years on the wheat stubbles in September, after harvesting. In each plot, 5 soil cores were randomly sampled at 0-30 cm depth using a core drill and stored in a cold chamber at 4°C prior to analysis. The sampling was performed in early September 2015, two years after the last amendment of OWP. Each type of amended soil was sampled as described by [START_REF] Noirot-Cosson | Modelling the long-term effect of urban waste compost applications on carbon and nitrogen dynamics in temperate cropland[END_REF].

Experimental setup

Soil analysis

Soil pH was determined following the standard NF ISO 10390 protocol, where a glass electrode was used in a 1:5 (volume ratio) suspension of soil in water. Total carbon in soil was measured by dry combustion and organic carbon calculated after correction of the carbonate content (ISO 10694). Total N was determined also by dry combustion (ISO 13878). Finally, organic matter in soil was calculated by multiplying C organic x 1.72, while organic matter for composts was determined by loss on ignition at 550°C. The soil cation exchange capacity was determined with cobaltihexamine following NF X 31-130 (AFNOR 1999)

Soil sample preparation for PTR-TOF-MS analysis

Samples of the same plot were mixed and homogenized by passing through a 2 mm sieve to remove aboveground plant materials, roots and stones, then dried up at room temperature (~23°C) for 2 weeks.

Laboratory flux chambers

In order to measure VOC emissions, soil samples were first moisturised to the field capacity by adding ultrapure water (resistivity 18.2 MΩ). The amount of water necessary was determined on a sub-sample and used for all samples (15 mL of water for each sample). Soil samples were then inserted, one at a time, in a pyrex chamber having a volume of 106 cm 3 . The quantity of soil inserted in the chamber (𝑚 𝑑𝑟𝑦 𝑠𝑜𝑖𝑙 ) was 60 g (dry mass) for each measurement. Soil was homogeneously spread on the chamber surface (132 cm 2 ). An empty chamber was used as a reference for zero emissions. Figure 1 represents the design of the measurement scheme. An air flow (𝑄 𝑎𝑖𝑟 ) of 0.2 L min -1 (equivalent volumetric flow at 0°C and 1 atm) of dry synthetic air (Alphagaz 1 Air: 80% nitrogen, 20% oxygen, 99.9999%, Air Liquide®) was passed through a hydrocarbons and humidity filter (Filter for fuel gas, final purity=99.999%, Restek®) and a Hydrocarbon Trap (Supelco, Supelpure® HC) prior to injection in the chambers.

A mass flowmeter (Bronkhorst® model F-201CV, accuracy: standard 0.5% Rd plus 0.1% FS, range: 0.2 L min -1 to 5 L min -1 air) was used to control the synthetic air flow rate. Air was sampled at the chamber outlet into a PTR-ToF-MS with a 0.05 L min -1 flow rate with a 2 m long, 1 mm internal diameter PEEK tube, heated at 80 °C. A measurement cycle consisted in measuring the VOC mixing ratio at the outlet of the chamber containing the soil (𝑥 𝑉𝑂𝐶 𝑠𝑜𝑖𝑙 in ppb) for 180 s. Then air was sampled for 120 s on the empty chamber to determine 𝑥 𝑉𝑂𝐶 𝑒𝑚𝑝𝑡𝑦 (ppb).

We sampled the empty chamber less than the chamber with soil because the signal was stable after only ~10 s.

Only the last 60 s of each measurement were kept to calculate averaged mixing ratios in order to ensure a stable VOCs mixing ratio. The VOC emission (𝐸 𝑉𝑂𝐶 in nmol g -1 s -1 dry soil) was calculated as:

𝑬 𝑽𝑶𝑪 = 𝑸 𝒂𝒊𝒓 × (𝛘 𝑽𝑶𝑪 𝒔𝒐𝒊𝒍 -𝛘 𝑽𝑶𝑪 𝒆𝒎𝒑𝒕𝒚 ) 𝑽 𝒎𝒐𝒍 𝒂𝒊𝒓 × 𝒎 𝒅𝒓𝒚 𝒔𝒐𝒊𝒍 (1)
Where 𝑉 𝑚𝑜𝑙 𝑎𝑖𝑟 is the air molar volume at standard temperature and pressure (22.4 L mol -1 at 0°C and 1 atm). In total 15 samples were measured: 3 replicates for each of the 5 treatments. Each measurement was further repeated 3 times to compute the mean and standard deviation of the measurement. This led to 45 measurements in total. After each measurement, the chamber was cleaned with diluted sodium hydroxide in order to destroy any organic compound that could affect the next measurements, and then rinsed with ultrapure water (resistivity 18.2 MΩ).

VOC analysis with the proton transfer reaction time of flight mass spectrometer (PTR-TOF-MS)

The VOCs were analysed with a PTR-TOF-MS (PTR-Quadrupole Ion guide-TOF, Ionicon, Analytik GmbH, AU).

The analyser is described in details by [START_REF] Sulzer | A Proton Transfer Reaction-Quadrupole interface Time-Of-Flight Mass Spectrometer (PTR-QiTOF): High speed due to extreme sensitivity[END_REF] It consists in a drift tube where VOCs are ionised and accelerated prior to be injected into a quadrupole ion guide and electromagnetic lenses. The electromagnetic lenses focus the ions in a time of flight mass spectrometer detector (TOF, TofWerk, Switzerland) which separates the ions by inertia prior to detection. The detection is made with a multi-channel-plate (MCP) detector and a time-to-digital converter (Burle Industries Inc., Lancaster, PA, USA). In this study, ionisation was carried out with H3O + as proton donor. The transfer reaction was effective for VOCs with a proton affinity higher than 691.7kJ mol -1 , which is the proton affinity of the water. In the drift tube, the pressure was tuned to 4 mbar, the temperature to 80°C, and the drift voltage to 1000 V, while the extraction voltage at the end of the tube (UDx) was 44 V. The E/N ratio (Electric field/density of natural particles) was 132 Td where 1 Td is 10 V m 2 . These parameters were controlled in order to maintain constant ionization conditions within the drift tube. The setup of the time of flight timing was: TOF extraction period 40000 ns, pulse width 2000 ns, trigger delay 100 ns. The number of channels was 240.000. This gave a mass spectrum measurement up to 510 m/z. The measurement period was set to 1 s, which means that each sample corresponded to 60 acquisitions of 25000 individual spectra. Raw PTR-ToF-MS data were recorded by TofDaq software (Tofwerk AG, Switzerland).

Peak detection of the mass spectra and mass calibration

We used the PTR viewer 3.1.0.29 software (Ionicon, Analytik GmbH) to detect mass peaks in each spectrum. The mass calibration was performed using the oxygen isotope of the ion source H3 18 O + (21.022 m/z) and acetone, C3H7O + , (59.0449 m/z). These two were chosen as they were present in all samples. Mass calibration was made over the entire dataset allowing for a change of 0.1 m/z around the peak maximum between consecutive samples and using a moving average of 50 successive samples for better stability. Overall the instrument resolution was around 4000. In order to create a peak table including the largest number of peaks, we used the automatic research feature of the software selecting as search mode "multiple peaks" with a threshold of 5 counts per second.

Following this step, a manual check of each peak was performed in order to correct for any software miss-fits.

Each peak was manually readjusted. The modes used to auto-select and manually adjust the peak areas that are used for mixing ratio calculation were the Gaussian or the multi-peak modes. The Gaussian peak mode was used for the analysis of isolated peaks; while for a better fit of multiple peaks we used the multi-peak mode. The range of the mass detection was limited between 31 and 400 m/z. Finally, masses deriving from the water cluster such as 37.03 m/z, 38.03 m/z, 39.03 m/z, and 55.03 m/z were not taken into account during the analysis of the dataset.

Isotopes and fragments identification

In order to make sure that a compound was not twice counted, we identified likely isotopes and fragments by performing a correlation analysis on the mass spectra. The Pearson's correlation coefficient was computed between each m/z based on all measured mixing ratios during the experiment (N=45). The m/z having a correlation coefficient larger than 0.99 were considered either fragments or isotopes depending on the m/z difference. In total 16 isotopes and 2 likely fragments were identified (Table S1).

PTR-TOF-MS mixing ratio calibration

The MCP provides the counts per seconds of detected ions after the TOF. In order to calculate the mixing ratio of gases in ppb that enter the PTR, a series of calculations was performed. The mixing ratio was calculated using the PTR-viewer software, which uses the following equation:

χ i standard transmission =1.657e -11 U drift T act 2 [K] k p act 2 [mbar] R + H 3 O + TR H 3 O + TR R + (2)
Where χ 𝑖 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑡𝑟𝑎𝑛𝑠𝑚𝑖𝑠𝑠𝑖𝑜𝑛 is the mixing ratio of the compound in ppb, U drift is the voltage of the drift (V), T act is the drift-tube temperature in Kelvin, R + is the signal of the product ion in count per second (cps), k is the protonation reaction rate constant (2 10 -9 cm 3 s -1 ) assumed equal for all compounds, TR H 3 O + is the transmission factor for mass of primary ion, TR R + is the transmission factor for mass of product, p act is the pressure of the drift, ion H 3 O + is the primary ions signal in cps. The standard transmission curve from supplier was used to compute In order to account for the normal loss of sensitivity of the PTR-TOF-MS, due to the MCP degradation over time, the change of H3 18 O + produced in the source, or other factors, we used a calibration procedure to account for the actual sensitivity of the analyser. We used benzene, toluene and ethylbenzene as reference compounds for this calibration. The mixing ratio of these compounds was modulated using a dilution system with a standard cylinder containing 102 ppb of benzene, 104 ppb of toluene, 130 ppb of ethylbenzene and 336 ppb of xylene (Btex, Messer®). We used the same synthetic air for the dilution system as the one described for the chamber set up. The sensitivity 𝑆 𝑛𝑜𝑟𝑚 was calculated as the slope of the regression between measured mixing ratio with the standard transmission provided by Ionicon and mixing ratio calculated with equation (2), and forcing a zero intercept. The calibrated mixing ratio of all compounds was then calculated as:

TR H 3 O + TR R + ⁄ (see
χ 𝑖 = [χ 𝑖 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑡𝑟𝑎𝑛𝑠𝑚𝑖𝑠𝑠𝑖𝑜𝑛 -χ 𝑖 (0) ] × 𝑆 𝑛𝑜𝑟𝑚 (3)
Where χ 𝑖 is the mixing ratio of the compound in ppb, χ 𝑖 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑡𝑟𝑎𝑛𝑠𝑚𝑖𝑠𝑠𝑖𝑜𝑛 is the mixing ratio calculated using the standard transmission as in equation ( 2), χ 𝑖 (0) is the mixing ratio of the compound measured for dry synthetic air.

The procedure was applied for the three compounds cited above for the calibration. We found that the sensitivity was 3.11±0.15. A single sensitivity value of 3 was applied for all masses, since the protonation reaction constant was assumed equal for all masses. In total we selected 754 peaks in the mass spectra used for these analyses.

VOC identification

We first identified the molecular formula with the Spectra Analyser within the PTR viewer 3.1.0.29 software (Ionicon, Analytik GmbH). The spectra analyser is a tool that allows the manual selection of the peaks chosen for the identification. The identification of the compounds corresponding to each mass peak was performed by searching the possible combinations of elements that led to the closest molecular weight. The following elements were selected for all peaks: C, N, O and H. Other compounds were selected on purpose for masses higher than 70 m/z like S, Si, Cl, Ca and K, when C, N, O and H did not lead to a good agreement with the peak mass. The maximum number of atoms per molecule was set to 50, while the error on the molecular weight was fixed to ± 0.01 m/z. Subsequently, a list of possible compounds was produced. The compounds listed represent the best matches for the selected exact m/z. Finally, a match of the isotopes of each compound was evaluated. Once the molecular formula was determined, we tried to identify the potential compounds with the use of the literature reviews. We have to stress that this method does not provide an undoubtable identification of the compounds as several compounds could have the same molecular mass but not the same chemical structure. Moreover, even with this procedure, some compounds could not be identified at all.

Statistical analysis

Several statistics test were performed on the VOCs emissions calculated for each treatment in order to identify the VOCs that mark the differences between the OWP treatments. All statistical analysis were performed using R software (Version 1.0.153 -© 2009-2017 RStudio). First, a normality test (Shapiro-Wilk test, W> 0.9) has been applied to verify that the mean mixing ratios were normally distributed for each VOC. Secondly, the homogeneity of the variances was verified for each treatment using the Levene test. Once the normality and the homogeneity of de variances were validated, the ANOVA test followed by Tukey post hoc test were performed. Finally, the Between Class Analysis (BCA, Package Ade4 Version 1.0.153 -© 2009-2017 R Studio) was performed. The ANOVA and BCA were specifically used to identify the VOCs that differentiate between each OWP treatment.

The Between-Class analysis is a particular case of a Principal Component analysis, it calculates the axes maximizing the covariance between the different treatments analysed.

RESULTS

Soil characteristics of each treatment

The Figure 2 summarizes soils characteristics as a function of OWP. The carbon content is in the range 10-18 g kg - 1 DM which spans from typical to high carbon content for a silt-loam. Organic matter was mainly found in the clay fraction of the soil (60%) and in the smaller fraction of the particulate organic matter, mainly in the form of Oalkyls, Alkyls and Aryls [START_REF] Paetsch | Urban waste composts enhance OC and N stocks after long-term amendment but do not alter organic matter composition[END_REF].

The CN samples showed the lowest cation exchange capacity, organic matter content, total nitrogen content, pH and organic carbon while its C/N ratio was not different from BIOW and GWS treatments (Figure 2). The treatment with the highest cation exchange capacity was BIOW while we found the highest C/N ratio in the FYM.

Furthermore, the total N, organic carbon and organic matter were higher for the BIOW and the GWS treatments.

Concerning the pH, BIOW and MSW had the highest values, while CN and GWS had the lowest values.

These results show that the repeated application of OWP has significantly increased soil organic carbon content (OC in Figure 2) in all organic treatments compared to the CN, but not in the same amount. Although all OWP are applied based on the same input of organic C, their different characteristics can explain their varying efficiencies at increasing soil organic carbon [START_REF] Peltre | RothC simulation of carbon accumulation in soil after repeated application of widely different organic amendments[END_REF]. Indeed, the index of residual organic carbon (Iroc) that represents the portion of organic carbon potentially incorporated into soil organic carbon after the organic waste application [START_REF] Lashermes | Indicator of potential residual carbon in soils after exogenous organic matter application[END_REF] was similar to OC: Iroc was the lowest for the MSW samples (Iroc=49% Org C), and was the highest for BIOW and GWS (Iroc=77% and 75 % Org C, respectively) [START_REF] Obriot | Multi-criteria indices to evaluate the effects of repeated organic amendment applications on soil and crop quality[END_REF].

Total organic nitrogen (Ntot) was also greater in the organic treatments compared to CN and was ordered similarly as soil organic carbon. The C/N ratio is in the same order of magnitude for all the samples. The soil CEC was increased in treatments receiving OWP, which in line with previous finding, that CEC increased with organic matter in soils [START_REF] Kaiser | Cation Exchange Capacity and Composition of Soluble Soil Organic Matter Fractions[END_REF]. Finally, the BIOW and MSW treatments increased soil pH mainly because of their contents in carbonates. FYM only slightly increased pH compared to control while GWS had no effect on soil pH. [START_REF] Paetsch | Urban waste composts enhance OC and N stocks after long-term amendment but do not alter organic matter composition[END_REF] further showed that the C/N ratio of the fine fraction of particulate organic matter rather represented the crops residues than organic waste inputs. They deduced lower degradability of organic matter in BIOW and GWS although they show the highest OM content.

VOCs Emissions

In order to verify whether the treatments affected the bulk production of VOCs, the fluxes of all compounds detected with the PTR-TOF-MS were summed up. They ranged between 36 ± 8 10 -4 nmol s -1 g -1 and 52 ± 12 10 -4 nmol s -1 g -1 (Figure 3a and Supplementary material Table S2). The treatment with the highest total flux rate is the BIOW and the treatment with the lowest total flux rate is the MSW while the other three treatments have nonsignificantly different total VOC emissions (ANOVA and a post hoc Tukey test with p value < 0.05). Moreover, the Shannon diversity indexes are similar in all treatments, though slightly smaller in BIOW indicating that BIOW less compounds contribute to the overall VOC flux.

Differentiating VOCs for each treatment

In order to determine if OWP amended soils affect the profile of VOCs emissions, we performed a Between Component Analysis (BCA). The first two components of the BCA explained 40.2% and 33.8% of the total dataset variability. In Figure 4 we observe that GWS and BIOW treatments are isolated from the other OWP (FYM, MSW and CN), which means that they have a VOC profile which is different from the other OWP. The VOCs that most explained the variance in the two first components of the BCA were selected as those having a coordinate larger than 0.9 on the first component and 0.5 on the second one (in absolute value). The m/z of these VOCs is shown in S4.

Furthermore, an ANOVA analysis was performed in order to determine the VOCs that significantly differentiated the treatments. A Tukey test was performed on those compounds to detect significance in means differences. The emission rates of the 21 compounds statistically different are plotted in Figure 5. Table S4 summarises the most emitted VOCs and those highlighted by the BCA and the ANOVA analysis. These 49 compounds listed in Table S4 contribute between 70% and 91% of the total emission rate. For all treatments includes the control we found that acetone, butanone and acetaldehyde were the most emitted compounds always as first, second and third. In Table S4 we added a tentative identification of the compounds and the corresponding chemical class. BIOW generally showed larger emissions than other treatments for small weighed compounds while GWS showed clearly higher emissions than other treatments for compounds in the mass range 80-130.

DISCUSSION

Identification and quantification of VOCs emitted

Most emitted VOCs: acetone, butanone, acetaldehyde, methanol, isoprene and ethanol

This study was focused on VOCs emissions from soils regularly amended with 4 different organic waste products compared to unamended soil. However, the soils were sampled two years after the last OWP application. Thus the differences in VOCs emitted could be associated to long-lasting effects of the OWP applications and to changes in soil organic matter characteristics due to these repeated OWP applications. We first notice that in all treatments including the control, the 3 most emitted compounds were acetone, 2-butanone and acetaldehyde regardless of amendments.

This study showed acetone emissions of 1000 ± 240 µg m -2 h -1 . Smaller acetone emissions are usually reported from laboratory experiments such as those by Asensio et al. (2007a) for a Mediterranean soil who found 10 times smaller fluxes than what we measured here. On the contrary, [START_REF] Schade | Fluxes of oxygenated volatile organic compounds from a ponderosa pine plantation[END_REF] reported acetone emissions in the same range as our study using a field chamber and a dual GC-FID system on a ponderosa pine plantation; they indeed found peak emissions of 800 µg m -2 h -1 following rain but smaller emissions 260 µg m -2 h -1 on average. [START_REF] Peñuelas | Biogenic volatile emissions from the soil[END_REF], in their review, reported emissions ranging from 4 to 800 µg m -2 h -1 . Acetone is often observed in rural areas [START_REF] Goldan | Hydrocarbon measurements in the southeastern United States: The Rural Oxidants in the Southern Environment (ROSE) Program 1990[END_REF][START_REF] Lamanna | In situ measurements of C2-C10 volatile organic compounds above a Sierra Nevada ponderosa pine plantation[END_REF][START_REF] Riemer | Observations of nonmethane hydrocarbons and oxygenated volatile organic compounds at a rural site in the southeastern United States[END_REF]. Acetone emissions seem to be mainly driven by biogenic sources such as litter decomposition [START_REF] Gray | Emissions of volatile organic compounds during the decomposition of plant litter[END_REF], microorganisms in soils [START_REF] Bunge | On-Line Monitoring of Microbial Volatile Metabolites by Proton Transfer Reaction-Mass Spectrometry[END_REF][START_REF] Schöller | Volatile metabolites from actinomycetes[END_REF]Schöller et al., 2006;Penuelas et al., 2014) but also functioning leaves [START_REF] Karl | A new European plant-specific emission inventory of biogenic volatile organic compounds for use in atmospheric transport models[END_REF][START_REF] Mozaffar | Biogenic volatile organic compound emissions from senescent maize leaves and a comparison with other leaf developmental stages[END_REF]. However, acetone was also found to be produced from abiotic degradation of plant material in the soil at a rate of 100 µg g -1 DM by [START_REF] Warneke | Acetone, methanol, and other partially oxidized volatile organic emissions from dead plant matter by abiological processes: Significance for atmospheric HOx chemistry[END_REF]. Emissions of acetone from soils depend on moisture, temperature and on the technique used to detect the fluxes which could explain the differences between the fluxes reported in the studies cited previously [START_REF] Peñuelas | Biogenic volatile emissions from the soil[END_REF]. Organic matter seem to enhance acetone emissions as reported by [START_REF] Zhao | Volatile organic compound emissions from straw-amended agricultural soils and their relations to bacterial communities: A laboratory study[END_REF] who found that acetone was the most emitted compound from soil amended with straw contributing to 50 ± 9% of the total VOCs emissions. For comparison, in our study acetone contributed to around 30% of the total mass of VOC emissions (Table S4).

Butanone was the second most emitted compound from our samples contributing up to 20% of the total VOCs emissions. [START_REF] Zhao | Volatile organic compound emissions from straw-amended agricultural soils and their relations to bacterial communities: A laboratory study[END_REF] also reported butanone emissions with a contribution of 9 ± 2% to the total VOCs emissions. [START_REF] Mcneal | Volatile Organic Metabolites as Indicators of Soil Microbial Activity and Community Composition Shifts[END_REF] also detected butanone production by soil microcosm, while Larsen and Frisvad (1995a;1995b) showed that butanone was one of the VOCs emitted from fungi. Apart from these references butanone was not detected in other studies, at least not as one of the major compound emitted such as we found here.

The third most emitted compound from soil was acetaldehyde which was detected by Asensio et al. (2007a) as the second most emitted compound from their Mediterranean soil samples. [START_REF] Schade | Fluxes of oxygenated volatile organic compounds from a ponderosa pine plantation[END_REF] detected a flux of acetaldehyde of 100 µg m -2 h -1 at 24°C quite similar to what we found ~280 µg m -2 h -1 . Similar to this study, though smaller, [START_REF] Peñuelas | Biogenic volatile emissions from the soil[END_REF] reported between 2 and 100 µg m -2 h -1 emissions of acetaldehyde for different type of soil, such as: forest soil, ponderosa pine plantation and shrubland soil. [START_REF] Gray | Biotic and abiotic controls on biogenic volatile organic compound fluxes from a subalpine forest floor[END_REF] reported much smaller emissions (0.2 µg m -2 h -1 ), but demonstrated that acetaldehyde emissions were largely coming from the roots system which was partly removed from our measurements by sieving at 2 mm. [START_REF] Mancuso | Soil volatile analysis by proton transfer reaction-time of flight mass spectrometry (PTR-TOF-MS)[END_REF] also detected acetaldehyde as the most emitted compound. It is noticeable that acetaldehyde is an oxidation product of ethanol. We should also stress that measurements of acetaldehyde with PTR-MS (not TOF ones) may catch some CO2.H + and hence include some soil respiration. Indeed, although CO2 has a proton-affinity lower than the one of water, we found that CO2 was protonated in our TOF at m/z = 44.997 (Loubet, personal communication).

Methanol, isoprene and ethanol were also detected with a significant emission rate in this study (Table S4).

Methanol has already been reported by [START_REF] Mancuso | Soil volatile analysis by proton transfer reaction-time of flight mass spectrometry (PTR-TOF-MS)[END_REF], [START_REF] Seewald | Substrate-induced volatile organic compound emissions from compost-amended soils[END_REF] and was the compound most emitted as reported by Asensio et al. (2007) and [START_REF] Ramirez | Microbial consumption and production of volatile organic compounds at the soil-litter interface[END_REF]. [START_REF] Peñuelas | Biogenic volatile emissions from the soil[END_REF] reported emissions in field conditions ranging from 4 to 530 µg m -2 h -1 , while [START_REF] Bachy | Methanol exchange dynamics between a temperate cropland soil and the atmosphere[END_REF] found a range from -50 to 200 µg m - 2 h -1 , which agreed with [START_REF] Schade | OVOC emissions from agricultural soil in northern Germany during the 2003 European heat wave[END_REF] measuring the emissions from a bare soil. Our results (~66 µg m -2 h -1 ) are in good agreement with the cited studies. [START_REF] Ramirez | Microbial consumption and production of volatile organic compounds at the soil-litter interface[END_REF] showed that methanol contributed to 89% of the total VOCs emissions by a forest soil while in our study methanol emissions contributed around 2% of the total mass VOCs emissions only. Methanol was also reported by [START_REF] Potard | Organic amendment practices as possible drivers of biogenic Volatile Organic Compounds emitted by soils in agrosystems[END_REF] as one of the most emitted compounds by soil. In fact it contributed between 20% to 40% of the total VOCs emissions in the control treatment and between 20% and 90% in soil amended with methanized pig slurry [START_REF] Potard | Organic amendment practices as possible drivers of biogenic Volatile Organic Compounds emitted by soils in agrosystems[END_REF].

Several studies showed different methanol sources from soil, i.e. abiotic production through SOM degradation [START_REF] Schade | OVOC emissions from agricultural soil in northern Germany during the 2003 European heat wave[END_REF], (a)biotic production from the litter [START_REF] Gray | Emissions of volatile organic compounds during the decomposition of plant litter[END_REF][START_REF] Ramirez | Microbial consumption and production of volatile organic compounds at the soil-litter interface[END_REF]Bachy et al., 2018). Methanol might be produced via the microbial breakdown of plant pectin [START_REF] Jayani | Microbial pectinolytic enzymes: A review[END_REF][START_REF] Schink | Microbial methanol formation-a major end product of pectin metabolism[END_REF]. The small amount of plant residues in our samples may explain the lower contribution of methanol to VOCs emissions compared to [START_REF] Potard | Organic amendment practices as possible drivers of biogenic Volatile Organic Compounds emitted by soils in agrosystems[END_REF] and [START_REF] Ramirez | Microbial consumption and production of volatile organic compounds at the soil-litter interface[END_REF]. It is also important to stress that methanol, as a soluble compound is adsorbed and desorbed from water films [START_REF] Laffineur | Abiotic and biotic control of methanol exchanges in a temperate mixed forest[END_REF].

This mechanism may have boosted emissions due to water evaporation in the chamber exposed to dry air.

Isoprene was reported as a compound emitted by agricultural soils amended with straw at only 0.1% of the total emissions by [START_REF] Zhao | Volatile organic compound emissions from straw-amended agricultural soils and their relations to bacterial communities: A laboratory study[END_REF]. Our results showed that around 6% of the total VOCs emissions were represented by isoprene emissions. [START_REF] Mancuso | Soil volatile analysis by proton transfer reaction-time of flight mass spectrometry (PTR-TOF-MS)[END_REF] measured isoprene emissions from agricultural and forest soil samples. Isoprene is a metabolite directly related to the presence of microorganisms in soil even if the role of this compound in microorganisms cell has not been clarified yet [START_REF] Hess | Coregulation of Terpenoid Pathway Genes and Prediction of Isoprene Production in Bacillus subtilis Using Transcriptomics[END_REF].

Ethanol is one of the compounds emitted during the sugar degradation as showed by [START_REF] Seewald | Substrate-induced volatile organic compound emissions from compost-amended soils[END_REF]. [START_REF] Schade | Fluxes of oxygenated volatile organic compounds from a ponderosa pine plantation[END_REF] reported emission of ethanol from bare soil between 300 and 500 µg m -2 h -1 while we found lower emissions around 100 µg m -2 h -1 ).

Other compounds detected

Several aromatic compounds have been observed as emitted from our soil samples. Microorganisms and plants release aromatic compounds through the shikimate pathway or by the degradation of phenylalanine or tyrosine.

Aromatic compounds are known to be emitted by plants under stress conditions [START_REF] Misztal | Atmospheric benzenoid emissions from plants rival those from fossil fuels[END_REF] and absorbed by humic substances in soil [START_REF] Lu | Sorption of Apolar Aromatic Compounds to Soil Humic Acid Particles Affected by Aluminum(III) Ion Cross-Linking[END_REF]. Toluene is one of the aromatic compounds most emitted by our samples, but in a similar amount between treatments which was also reported by Asensio et al. (2007b).

Toluene is rather a compound linked to oil, either natural (crude oil) or from derivatives, such as solvents, gasoline or other fuels as well as in the production process of coke from coal. The flux of this compound from soil is always very low but due to the several impacts that this compound might have on the health is important to quantify and characterize the emissions. It is interesting to notice that we also detected monoterpenes and p-cymene, which is an aromatic compound formed by the oxidation of monoterpenes [START_REF] Gratien | Surprising Formation of p-Cymene in the Oxidation of α-Pinene in Air by the Atmospheric Oxidants OH, O3, and NO3[END_REF]. We found around 0.018 nmol m -2 s -1 which is higher than the range of monoterpenes emissions detected by Asensio et al. (2007a) (between -0.004 nmol m -2 s -1 and 0.004 nmol m -2 s -1 ). [START_REF] Hayward | Monoterpene emissions from soil in a Sitka spruce forest[END_REF] reported that emissions of monoterpenes from soil of Sitka spruce forest were 0.026 nmol m -2 s -1 , and were strongly related to soil temperature [START_REF] Raza | Profiling of soil volatile organic compounds after long-term application of inorganic, organic and organic-inorganic mixed fertilizers and their effect on plant growth[END_REF].

It is also known that monoterpene emissions from forests exceed those from agriculture [START_REF] Guenther | Seasonal and Spatial Variations in Natural Volatile Organic Compound Emissions[END_REF][START_REF] Kesselmeier | Biogenic volatile organic compounds (VOC): An overview on emission, physiology and ecology[END_REF]. Assuming soil emissions are linked to plant residues degradation in the soil this might explain the higher emissions from forest's soils compared to what we find here.

Other noticeable compounds detected are the organosulfur compounds such as dimethylsulfide, dimethethydisulfide and diethylsulfide. Other studies have reported emissions of these compounds from soils. For instance, [START_REF] Potard | Organic amendment practices as possible drivers of biogenic Volatile Organic Compounds emitted by soils in agrosystems[END_REF], [START_REF] Veres | Volatile Organic Compound emissions from soil: using Proton-Transfer-Reaction Time-of-Flight Mass Spectrometry (PTR-TOF-MS) for the real time observation of microbial processes[END_REF], [START_REF] Zhao | Volatile organic compound emissions from straw-amended agricultural soils and their relations to bacterial communities: A laboratory study[END_REF], [START_REF] Mayrhofer | Microbial community related to volatile organic compound (VOC) emission in household biowaste[END_REF][START_REF] Raza | Profiling of soil volatile organic compounds after long-term application of inorganic, organic and organic-inorganic mixed fertilizers and their effect on plant growth[END_REF] reported emissions of dimethylsulfide from soils. Dimethethydisulfide is a fungistatic produced by Bacillus, Pseudomonas and Actinomicetes [START_REF] Schöller | Volatile metabolites from some gram-negative bacteria[END_REF][START_REF] Wilkins | Volatile metabolites from actinomycetes[END_REF]. It represents also a precursor of atmospheric aerosols which hence has impacts on climate and health [START_REF] Ayers | The CLAW hypothesis: a review of the major developments[END_REF].

Propene is also in our list of characteristic compound, and was reported by [START_REF] Zhao | Volatile organic compound emissions from straw-amended agricultural soils and their relations to bacterial communities: A laboratory study[END_REF] from amended agricultural soil as one of the most emitted compound with a significantly positive correlation between this compound and bacterial communities in soil. In [START_REF] Zhao | Volatile organic compound emissions from straw-amended agricultural soils and their relations to bacterial communities: A laboratory study[END_REF], propene contributed to 1.1% of the total emissions similar to what we found in this study (1.4%).

The VOCs emitted from the soil samples may derivate from the microbial activity in soil. In fact, different VOCs derive from several metabolic pathways. Fermentative pathways such as ethanol fermentation, with acetaldehyde as an intermediate product, and butyric acid, acetone and methanol fermentation take part of the microorganisms' primary metabolism [START_REF] Castaldelli | Decomposition dynamics of the bloom forming macroalga Ulva rigida C. Agardh determined using a C-14-carbon radio-tracer technique[END_REF][START_REF] Karl | Seasonal variation of biogenic VOC emissions above a mixed hardwood forest in northern Michigan[END_REF][START_REF] Raza | Profiling of soil volatile organic compounds after long-term application of inorganic, organic and organic-inorganic mixed fertilizers and their effect on plant growth[END_REF]. On the other hand, more complex molecule with a higher molecular weight may derive from secondary metabolism pathways, such as production of signalling compounds or antibiotics [START_REF] Mathivanan | The Effect of Fungal Secondary Metabolites on Bacterial and Fungal Pathogens[END_REF][START_REF] Splivallo | Biological Significance of Truffle Secondary Metabolites[END_REF][START_REF] Wheatley | The consequences of volatile organic compound mediated bacterial and fungal interactions[END_REF].

It is important to bear in mind in the previous discussion that our measurement set up was giving potential emissions since zero air was supplied at the chamber inlets. This may have led to marked differences when compared to other in-situ measurements that captured the bi-directionality of some fluxes (e.i. [START_REF] Mozaffar | Biogenic volatile organic compound emissions from senescent maize leaves and a comparison with other leaf developmental stages[END_REF]. Moreover, we should also stress that evaluations of percentage of total VOC emissions are sensitive to the number of peaks identified. We could hence expect larger percentages by studies using PTR-MS with small number of peaks or GC-MS focussed on certain masses compared to PTR-TOF that screens all peaks.

Effects of organic waste product applications on VOCs emission rates by soils

Total VOCs emissions were statistically higher in BIOW than in MSW (Figure 3). Despite the fact that the amount of carbon imported in these two treatments was the same over 17 years, The Iroc indicator which is the fraction of carbon stored in the soil to that applied was found to be lower in MSW (49% Org C) than in BIOW (77% Org C) [START_REF] Lashermes | Indicator of potential residual carbon in soils after exogenous organic matter application[END_REF]. As a consequence, the organic matter (OM) content is higher in BIOW compared to MSW (Figure 2). This suggests that total VOC production is linked to OM content in the soil. However, the OM content is not the only driver of the total VOCs emissions, because otherwise GWS, which shows the largest OM content, would have had the highest VOCs emission which was not the case.

The BCA and ANOVA analysis show that the emitted compounds from BIOW and GWS were the most differentiated and were also differentiated from emissions by CN, MSW and FYM, which were grouped. It is noticeable that the same classification was also found in the C/N ratio of the small particle organic matter (POM) fraction reported by [START_REF] Paetsch | Urban waste composts enhance OC and N stocks after long-term amendment but do not alter organic matter composition[END_REF] on the same site. Indeed, they found higher C/N ratios of these fractions in CN, MSW, FYM. Higher C/N ratios indicate higher organic matter degradability. This would mean that the VOC compounds that are mostly associated with CN, MSW and FYM treatments may be more representative of the degradation of the small fraction of POM.

Overall, BIOW emitted more alcohols and alkenes, N compounds and terpenes than the other treatments, while GWS mainly emitted more aromatic compound (Figure S1). [START_REF] Peñuelas | Biogenic volatile emissions from the soil[END_REF] reported that bacterial VOCs emissions contain mostly alkenes, ketones, terpenes and pyrazines while fungi emit more aldehydes, benzenoids, nitriles and alkynes. We could hence argue that BIOW promote bacterial-mediated VOCs emissions as shown by the dominance of alkenes and terpenes, and also by the larger total VOC emissions (Figure 3a). Since, BIOW has also the lowest VOC diversity index; this suggests that BIOW may promote more specific VOC emission processes than other treatments.

A notable difference in the measured soil characteristics between BIOW and GWS treatments is the soil pH.

Since soil pH affects nutrient availability and the physiological state of microorganisms, we could also expect that pH may affect VOCs emission profiles. [START_REF] Insam | Volatile organic compounds (VOCs) in soils[END_REF] reported that VOC are largely adsorbed by the mineral and organic fraction of soil. This adsorption depends on soil pH, with higher adsorption in alkaline soils and lowers in acid soils. We tend to observe a complex dependency to pH which also interacts with organic matter.

The total emission of VOC tends indeed to increase with the product of pH with organic matter (Figure S2).

Furthermore, it has been shown by [START_REF] Seewald | Substrate-induced volatile organic compound emissions from compost-amended soils[END_REF] that anaerobic conditions lead to increased amount and diversity of VOCs emitted as opposed to aerobic conditions that leads to CO2 as the end product of microbial decomposition. The increase of soil organic matter in treatments receiving OWP is known to improve soil structure and aggregate stability [START_REF] Annabi | Soil Aggregate Stability Improvement with Urban Composts of Different Maturities[END_REF][START_REF] Diacono | Long-term effects of organic amendments on soil fertility[END_REF]. [START_REF] Gupta | Estimating soil water retention characteristics from particle size distribution, organic matter percent, and bulk density[END_REF] have shown that OM content increases water soil retention which may promote anaerobic conditions in microsites and hence modify VOC emission diversity and amounts. OM content may also modify the porosity and hence gas diffusivity which can affect the emission and storage processes of VOCs in soil system (Penuelas et al., 2014). One should however keep in mind that the soils used in our study were sieved before VOCs analysis, which would suppress any effects of OM on soil porosity above 2 mm.

According to the BCA and ANOVA analysis, GWS and BIOW have different VOC emission spectra: 21 compounds were found to have statistically different emissions between the treatments. BIOW released more acetone, more 74.06 m/z (unidentified compound), and C3H8O2 (77.05 m/z). At this stage we are not able to say why the BIOW samples released these three compounds in higher quantities than the other samples. What we can conclude is that the compounds cited above can be used as marker compounds for the bio-waste treatment. The GWS treatment has other marker compounds such as: 94.03 m/z, 95.02 m/z, 110.06 m/z (benzamide), 111.07 m/z and 113.01 m/z. Benzamide is an intermediate compound produced by microorganisms during the degradation of 2,6-dichlorobenzonitrile which is a persistent herbicide in soil [START_REF] Holtze | Transformation of the herbicide 2,6dichlorobenzonitrile to the persistent metabolite 2,6-dichlorobenzamide (BAM) by soil bacteria known to harbour nitrile hydratase or nitrilase[END_REF]. The last herbicide application was two years before the sampling period. The content of Benzamide could be related also to the herbicide present in the green wastes used for the GWS compost. Similarly, CN can be differentiated from the other treatments with high emissions of 136.02 m/z and 221.15 m/z. For the FYM and MSW no distinctive compound was found.

Conclusions

Our results confirmed that VOCs emissions were affected by the type of organic waste product in soil. Overall, the most emitted compounds were acetone, butanone and acetaldehyde in all treatments. We further found that 21 compounds had statistically different emissions between the treatments. We hence suggest that a certain number of VOCs could be used as marker of soils. For instance, GWS released more 94.03 m/z, 95.02 m/z, 110.06 m/z (benzamide), 111.07 m/z and 113.01 m/z than the other OWPs. These differences can be explained by abiotic factors among which pH and temperature, and biotic factors, such as the presence of certain microorganisms in soil. We also observed that organic matter content and pH jointly influenced total VOC emissions, with larger emissions for higher pH and OM content. Our results also suggest that the VOC emissions profiles are linked to C/N ratio of the small fraction of particulate organic matter which is an indicator of OM degradability. It is difficult to draw conclusions concerning the biological pathway (i.e. degradation of sugar, mineralisation of the organic matter ;..) leading to VOCs emissions observed. Other analysis of microorganisms' activity and diversity are necessary to unveil these aspects.

Figure 4 .

 4 Figure 4. The tentative identification of the compound listed above is shown in TableS4.

Table S2 in supplementary material).

	We used the following primary ions mass: 21.02 m/z (H3 18 O + , multiplier factor 487.56), 38.03 m/z (water cluster
	H2 18 O•H3 18 O + with two 18 O isotopes, multiplier factor 819.51) and mass 55.03 m/z (H2O•H3O + •H3O + multiplier
	factor 1.0008).

Acknowledgement

We gratefully acknowledge ANAEE-France that provided the PTR-TOF-MS, ADEME for funding partially funding this study through the projects COV3ER (n°1562C0032) and DICOV (n°1662C0020). The Qualiagro site conducted in partnership with Veolia, forms part of the SOERE-PRO integrated as a service of the infrastructure AnaEE-France, overseen by the French National Research Agency (ANR-11-INBS-0001). The QUALIAGRO field experiment forms part of the SOERE-PRO (network of long-term experiments dedicated to the study of impacts of organic waste product recycling) certified by ALLENVI (Alliance Nationale de Recherche pour l'Environnement) and integrated as a service of the ''Investment d'Avenir'' infrastructure AnaEE-France, overseen by the French National Research Agency (ANR-11-INBS-0001)'.