Clotilde Le Vot

Hélène Mestdagh

Michel Héninger

Pierre Boissel

Gérard Mauclaire

Joël Lemaire

Développement en spectrométrie de masse pour la détection de toxiques dans l'air

La spectrométrie de masse haute résolution permet une identification précise et est en mesure de distinguer des molécules de même masse nominale mais de formules chimiques différentes grâce à la mesure de leurs masses exactes.

La technique que nous avons mise en oeuvre est la spectrométrie de masse à transformée de Fourier, de type FT-ICR (« Fourier Transform Ion Cyclotron Resonance ») et nous utilisons un assemblage d'aimants permanents pour produire le champ magnétique.

Le pouvoir de résolution obtenu est supérieur à 10000 pour une gamme de masse allant de 10 à 300.

Conclusion

L'instrument réalisé dans le cadre du projet DIRECT a permis de montrer l'intérêt de l'association de l'analyse temps réel haute résolution avec une méthode d'ionisation ambiante.

Sur cette base, nous comptons aller vers une plus grande miniaturisation, en mettant en oeuvre le couplage de différents techniques séparatives et en utilisant des sources d'ionisation basées sur un microjet de plasma froid.

PAHs à l'état de traces dans l'air

Les PAHs (hydrocarbures polyaromatiques) sont des composés toxiques, très peu volatils pour ceux de plus grande taille qui nous ont servi de composés tests pour évaluer les performances de l'instrument que nous avons mis au point dans le cadre du projet DIRECT (CSOSG 2009).

Nous avons généré les composés à l'état de traces dans l'air en faisant passer de l'air au dessus d'une petite quantité de composé à l'état solide puis en le faisant passer, à pression atmosphérique entre la source à décharge et le capillaire d'entrée du spectromètre de masse.

La principale difficulté technologique de notre projet était de réussir à faire passer les ions depuis l'atmosphère jusqu'au vide poussé nécessaire à la spectrométrie de masse FTICR (10 -8 mbar), soit 11 ordres de grandeur, ceci en utilisant seulement deux pompes turbomoléculaires.

Les PAHs sont un cas assez particulier : contrairement à beaucoup de composés organiques volatils qui vont être protonés on observe les ions moléculaires ainsi que des produits oxygénés formés dans le plasma. Les spectres obtenus sont cependant assez caractéristiques pour permettre leur identification.

Identifier précisément les composés toxiques

Etant donné l'extrême variété des composés à identifier une technique disposant d'un pouvoir de résolution assez élevé est indispensable. Les instruments de première génération, basés sur la mobilité ionique, qui ont pour atout une mise en oeuvre assez simple et qui se prêtent a une assez grande miniaturisation génèrent facilement des faux positifs en raison d'un trop faible pouvoir de résolution (de l'ordre de 50).

Introduction

La détection des composés toxiques dans le cadre d'applications dans le domaine de la sécurité est particulièrement exigeante:

-il faut être en mesure d'identifier avec précision un très grand nombre de composés (notamment toxiques industriels, narcotiques et explosifs) sans risque de confusion avec des composés inoffensifs -leurs concentrations peuvent aller de la ppb au % Les techniques basées sur la détection d'ions (mobilité ionique et spectrométrie de masse) sont bien placées pour réaliser des détecteurs généralistes disposant d'une grande sensibilité et permettant une réaction rapide à la présence de toxiques.

Techniques d'ionisation ambiante

Les techniques d'ionisation ambiante sont bien adaptées à la recherche de composés peu volatils ou à la recherche de composés déposés sur des surfaces.

  Les espèces primaires sont produites soit par électrospray (DESI ou EESI) soit par plasma. Nous avons mis en oeuvre une source basée sur une décharge luminescente dans l'hélium et envisageons pour l'avenir l'utilisation de microtorche de plasma froid produite par une décharge à barrière diélectrique Une plus grande miniaturisation et une plus faible consommation d'énergie pourrait être obtenue en utilisant un plasma froid Décharge luminescente Spectre obtenu lors de l'analyse d'air contenant des traces d'acenaphtylene. Le pic observé à la masse 152 correspond à l'ion moléculaire et les pics aux masses 169 et 185 à des dérivés oxygénés protonés. Schéma de la solution mise en oeuvre Caractérisation de la détection en masse en réalisant le spectre du Xénon formé par impact électronique dans la cellule Exemple de séparation de composés de même masse nominale dans le cas de la cyclopentanone protonée C 5 H 9 O + m/z 85.065339 et de l'hexène protoné C 6 H 13 + m/z 85.101725 Spectromètre haute résolution transportable à source atmosphérique


domain: sdv sdv

text:
Lisa M Van Den Berg
email: lisamarijke.vandenberg@wur.nl

Marco Carozzi
email: marco.carozzi@inrae.fr

Francesco Accatino
email: francesco.accatino@inrae.fr

Exploring the determinants of livestock transportation across country borders

Exploring the determinants of livestock transportation across country borders

Summary

Throughout the world, living animals are transported across country borders. Whilst transported for many purposes e.g., slaughtering and fattening abroad, a global view of the drivers of these transports remains missing. We performed a systematic analysis of the available body of scientific literature to get an overview of the existing literature on this topic and the knowledge gaps concerning the transport of living animals across national borders. We found a total of 24 containing statements and examples about factors driving and shaping the international trade of live animals. We found that drivers could be categorized into political, economic, technical, socio-cultural and environmental drivers. In addition, we found that the described main challenges related to livestock transport concern animal welfare and diseases. Our study shows a vast potential for further exploration, specifically regarding the analysis of the grey literature.

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Research questions

The transport of living animals over long distances and across national borders is at the basis of many livestock production chains worldwide (Miranda-de la [START_REF] La Lama | Livestock transport from the perspective of the pre-slaughter logistic chain: A review[END_REF]. These living animals are transported out of their original country most often for further steps in the production cycle. Nevertheless, multiple issues with international transports of living animals are increasingly emergent. One of the issues is related to the public opinion. As animal transport is visible for society, it is subject to the public opinion [START_REF] Buddle | I Feel Sorry for Them": Australian Meat Consumers' Perceptions about Sheep and Beef Cattle Transportation[END_REF]. Another issue along with these specific examples, regards animal welfare and is raised in relation to the condition of international transport of living animals by truck and boat [START_REF] Fleming | Varying opinions about animal welfare in the australian live export industry: A survey[END_REF]. A different issue is the environmental impact of transport of living animals. Recently, research showed that greenhouse gas emissions resulting from transport in the food value chain appeared 3.5 to 7.5 times higher than previously estimated [START_REF] Li | Global food-miles account for nearly 20% of total food-systems emissions[END_REF]. While research focuses mostly on describing the flows between countries within the trade networks of living animals (e.g., [START_REF] Barberis | Economia agro-alimentare / Food Economy Trade Relationships in the European Pork Value Chain : A Network Analysis[END_REF], still a full overview of the determinants of the transports of live animals across country borders is missing. In this paper, we aim to perform an extensive literature review to answer to the following research question: which are the main drivers and shapers of the international transport of living animals and how are they categorized? .

Data and methods

We conducted a systematic literature review following the PRISMA guidelines [START_REF] Page | The PRISMA 2020 statement: an updated guideline for reporting systematic reviews[END_REF]. First, a search question is executed in a chosen data base. Subsequently, the results are screened on predetermined eligibility criteria based on increasing text amounts: in a first step, the article is screened based on the title and abstract; in a second step, the article is screened based on the full article text. Web of Science and Scopus were used as databases with the search question: TITLE-ABS-KEY ( ( "boat" OR "truck" OR "transport" OR "trade" ) AND ( "international" OR "border*" ) AND ( "pig*" OR "pork" OR "cattle" OR "beef" OR "chick*" OR "living animal*" OR "livestock" ) ). Articles were included if peer-reviewed and published in English. Transport of living animals across borders should be the main interest of the article. Furthermore, the articles were included if they describe an original qualitative, quantitative or mixed-method study. On top of that, literature studies were included if describing or giving insight into the transport of living animals across borders. All statements giving insight into the drivers and shapers of international transport of living animals were noted and classified.

Main results

The search string identified 6,635 articles in total, with 5,719 unique entries. A number of 5,435 articles were excluded based on the abstract and title. Based on the full-text assessment, 240 of the 284 remaining articles were excluded, resulting in a total of 44 included studies in the systematic literature review. Of these articles, 24 statements were noted and five main categories emerged. The category 'political' (number of articles containing relevant statements N=12), consists of all drivers and shapers of international livestock transport that are related to policies and laws, either on global or regional scale. A specific example consists of the legislative requirements for identification of farm animals in the EU (e.g. 92/102/EEC) [START_REF] Ammendrup | Legislative requirements for the identification and traceability of farm animals within the European Union European Community legislation on identification of livestock , except Equidae[END_REF]. The category 'economical' (N=7) consists of monetary drivers and shapers of international trade of living animals. As examples, in case of slaughtering the monetary value of the meat is the main driver of the transport (Seng and Laport, 2005), whilst for fatting purposes the economies of scale and cost efficiency are main driving factors (Haxsen, 2010;[START_REF] Hop | Cross-border collaboration in the Field of Highly Contagious Livestock Diseases : A General Framework for Policy Support[END_REF]. The category 'socio-cultural' (N=7) consists of socio-cultural factors regarding transport of animals driving or shaping the international transport of living animals. Research conducted by [START_REF] Sinclair | Welfare Issues[END_REF] showed that perceptions on the livestock transport industry is mainly depending on the culture and country. The category 'technical' (N=6) consists of infrastructural and technical factors driving or shaping the international transport of living animals. Infrastructure is a prerequisite for transport, wherefore infrastructure can be a barrier as well as an enabler for cross-border transport of living animals [START_REF] Valerio | Network analysis of regional livestock trade in West Africa[END_REF]. The category 'environmental' consists of ecological and natural factors driving and shaping transport of living animals. As an example, the transport of living animals over the border between Somali and Kenya, increases as a result of droughts [START_REF] Ng'asike | Livestock trade and devolution in the Somali-Kenya transboundary corridor[END_REF]. In addition to the drivers and shapers of living animal transports, insights from the literature review showed that the main challenges related to livestock trade regard animal welfare and diseases.

Our study shows a vast potential for further exploration, specifically regarding the analysis of the grey literature.


Francesco Accatino

Yang Li

The trade-off between satisfying meat demand and avoiding excess manure nitrogen at the regional scale in China

The trade-off between satisfying meat demand and avoiding excess manure nitrogen at the regional scale in China Francesco Accatino 1* , Yang Li 2 , Zhigang Sun 2 1 UMR SADAPT. INRAE, AgroParisTech, Université Paris-Saclay, 75000, Paris, France 2 Institute of Geographic Sciences and Natural Research Research, Chinese Academy of Sciences, Beijing 100101 , China * francesco.accatino@inrae.fr Achieving self-sufficiency in meat at the regional scale might increase resilience (e.g., to price fluctuations), however such objective might be in contrast with the objective of avoiding locally the excess of manure nitrogen. In China, both the achievement of meat self-sufficiency and the avoidance of manure nitrogen excess are key objectives and studying their trade-off is of primary importance. The aims of this study are 1) to classify the regions of 261 regions of Eastern China (the most intensive from the point of view of crops and livestock) according their ability/inability to satisfy local meat demand and their deficiency/excess of manure; 2) to analyse scenarios of decrease in livestock number in the regions. For aim 1) we compared meat demand (based on healthy diet recommendations) and meat production (based on data of livestock abundance and productivity) as well as manure production (based on data of livestock abundance and productivity) and manure demand (based on crop data and nitrogen crop demand), considering also the fraction (30%) of synthetic fertilizer that is substituted with organic manure. For objective 2) we set livestock in each region to some key quantities: the quantity that meets local meat self-sufficiency (scenario A), the quantity that meets local manure demand (scenario B), the quantity that meets local meat self-sufficiency in case manure nitrogen is not in excess, otherwise manure nitrogen excess avoidance is given priority (scenario C). Concerning 1), our results showed that 15% of the regions analysed could meet meat self-sufficiency without any manure nitrogen excess, however in 76% of the regions meat self-sufficiency was met but while causing manure excess. Concerning 2) scenario C was the best performing, with 50% of the regions that could meet meat self-sufficiency (according to healthy diet recommendations) while avoiding manure balance. In addition, this scenario made it possible to achieve, at the level of the whole Eastern China (all the 261 studied regions pulled together), a global meat selfsufficiency and avoidance of nitrogen excess. Our study suggests that, while a trade-off exists between achieving meet self-sufficiency and avoiding excess of manure nitrogen, livestock is in excess in many regions and it is important to give priority to the avoidance of manure nitrogen excess for allocating livestock quantities in the region. Solutions must be adopted to increase the use of manure nitrogen as substitute of synthetic fertilizer in order to soften the trade-off. Further perspectives should also take into account the self-sufficiency of feed (Li et al., 2021).


M Heninger

Joël Lemaire

E Louarn

H Mestdagh

R Herren

F Da Costa

S Pasquiers

J Santos Sousa

N Blin-Simiand

V Puech

B Bournonville

G Bauville

M Fleury

J Leprovost

D Robin

P Gremillet

Cold Plasmas for Analytical Applications

la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d'enseignement et de recherche français ou étrangers, des laboratoires publics ou privés.

Introduction

Through the PLASPAMS project we will develop an instrument dedicated to the real time detection and identification of species present in air at trace concentration or deposited on surfaces. We will combine plasma techniques and mass spectrometry in order to build a compact detector suitable for field operation.

Analytic applications in the field of security are particularly demanding:

-dangerous or prohibited molecules must be identified with precision among the many species potentially present ; -concentrations can go from the ppb range (1 molecule per billion) to % ;

-the more volatile molecules can be detected directly in air but species of low volatility will stay on surfaces and we need to desorb them efficiently in order to detect them. This will be the case for many explosives or narcotics ;

-the detector must be broadband, very sensitive and must have a fast response time. The most used ion molecule reaction for trace detection in air is the proton transfer from H 3 O + ions (protonated water)

H 3 O + + M  H 2 O + MH +
The reaction will be fast and efficient for molecules having a proton affinity higher than water (such as aromatic compounds, alcohols, aldehydes, nitrated explosives, narcotics,…) but will not occur with compounds having a proton affinity lower than water (which is the case for the main constituent of air N 2 , O 2 , Ar and also for alkanes, CFCs,…)

The precursor ions formed in the source will react with the sample air in a reaction zone where radiofrequency electric fields will help in guiding and transmitting the ions to the mass analyzer.

The intermediate zone can be used to break apart the cluster ions eventually formed in the source or to switch to another ionic precursor.

In a first time the analyzer will be a quadrupole. Then an ion trap will be developed in which collision induced fragmentation will help for precise identification.

Conclusion

The PLASPAMS project combines plasma techniques and mass spectrometry. The project team associates cold plasma specialists, physico-chemist experienced in real time trace analysis and the AlyXan company (commercializing high-resolution mass spectrometers). The compact instrument developed will allow real-time analysis of traces present in air and of low volatility species deposited on surfaces . They will be transferred in the gas phase using cold plasma jets (without heating the surface) and detected with the very high sensitivity of mass spectrometry associated to chemical ionization.

  photo LPGP