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Rapport En Français Additifs du 1,1,1-trichloroéthane État de l’art et enjeux en contexte « sites et sols pollués » Rapport final BRGM/RP-70190-FR Décembre 2020 Additifs du 1,1,1-trichloroéthane État de l’art et enjeux en contexte « sites et sols pollués » Rapport final BRGM/RP-70190-FR Décembre 2020 G. Boissard Vérificateur : Approbateur : Nom : Aline Coftier Nom : Sandrine Lemal Fonction : Cheffe de projets Fonction : Responsable Unité Sites Sols Pollués Date : 08/12/2020 Date : 14/12/2020 Signature : Signature : Le système de management de la qualité et de l’environnement est certifié par AFNOR selon les normes ISO 9001 et ISO 14001. Contact : [email protected] Mots-clés : Émergents, Pollution, Solvant, Sites pollués. En bibliographie, ce rapport sera cité de la façon suivante : Boissard G. (2020) - Additifs du 1,1,1-trichloroéthane – État de l’art et enjeux en contexte « sites et sols pollués ». Rapport final. BRGM/RP-70190-FR, 262 p., 4 fig., 23 tab., 12 ann. © BRGM, 2020, ce document ne peut être reproduit en totalité ou en partie sans l’autorisation expresse du BRGM. Additifs du 1,1,1-trichloroéthane - État de l’art et enjeux en contexte « sites et sols pollués » Synthèse Le 1,1,1-trichloroéthane (nommé TCA dans la suite du document) est un composé chloré largement utilisé comme solvant pour le dégraissage des métaux. Comme de nombreux autres solvants chlorés, il est généralement formulé avec des additifs pour augmenter sa stabilité et améliorer ses performances. Le TCA est considéré comme le solvant le moins stable parmi d’autres solvants tels que le trichloroéthylène (TCE), le tétrachloroéthylène (PCE) et le dichlorométhane. Par conséquent, le TCA est le solvant présentant la teneur en additifs la plus élevée. L’objectif de la présente étude est de réaliser une revue des informations françaises disponibles sur les additifs du TCA, dans le contexte des sites et sols pollués, afin de dresser l’état des connaissances sur ces substances sur le territoire national. De plus, un retour d’expérience sur les principales initiatives engagées par d’autres pays est proposé afin de faire un état d’avancement des connaissances majeures acquises sur ces substances en Europe et ailleurs. Une liste de plus de 180 composés (ou familles de composés) ayant été utilisés comme additifs du TCA a été identifiée. Une sélection des composés les plus pertinents pour la suite de l’étude a donc dû être effectuée. Cette sélection a abouti à une liste de 11 composés (n° CAS) : 1,4-dioxane (123-91-1) ; 1,3-dioxolane (646-06-0) ; 1,2-époxybutane (106-88-7) ; nitrométhane (75-52-5) ; nitroéthane (79-24-3) ; acétonitrile (75-05-8) ; tert-butyl alcohol (75- 65-0) ; tert-amyl alcohol (75-85-4) ; 2-methyl-3-butyn-2-ol (115-19-5) ; 3-methyl-1-butyn-1-ol (37365-71-2) et isopropyl nitrate (1712-64-7). Le rapport s’articule en plusieurs parties : Généralités sur le TCA (importance des additifs, utilisation, production, réglementation) ; Généralités sur les additifs du TCA (typologie, sélection des additifs dans la présente étude, composition des mélanges, enrichissement des concentrations, utilisation, production, réglementation) ; Propriétés des additifs (propriétés physico-chimiques, dégradation, toxicité, répartition dans l’environnement, sources) ; Occurrence dans l’environnement (eau, sol, …) ; Outils techniques pour gérer les enjeux liés à ces substances (échantillonnage, analyse, traitement) ; Conclusions. Chaque partie synthétise les données recueillies et davantage d’éléments sont fournis dans chacune des annexes (Annexes 2 à 12) spécifiques à chacun des additifs. Les annexes suivent le même plan que le corps de texte (généralités, propriétés, occurrence dans l’environnement et outils techniques). Les 11 substances sélectionnées dans la présente étude possèdent en commun leur utilisation en tant qu’additifs du TCA. Leur nature est toutefois différente et leurs propriétés (physico- chimiques, toxicologiques, …) le sont donc également. De manière générale, les utilisations de ces substances sont très nombreuses et concernent des domaines d’application très divers. BRGM/RP-70190-FR - Rapport final 3 Additifs du 1,1,1-trichloroéthane - État de l’art et enjeux en contexte « sites et sols pollués » Depuis la diminution très importante d’utilisation du TCA1, l’utilisation des composés sélectionnés en tant qu’additif du TCA est devenue une utilisation parmi de nombreuses autres. Toutefois, cela n’exclut pas l’existence de pollutions anciennes, de pollutions au droit de site produisant ou utilisant toujours du TCA ou de pollutions associées à ces autres utilisations. Les données disponibles pour le 1,4-dioxane sont, de loin, les plus nombreuses. Il s’agit de l’additif qui suscite, depuis plusieurs années, un intérêt et une préoccupation environnementale les plus importants. Plusieurs états américains ont notamment été concernés par des cas de pollution des eaux souterraines et des sources d'eau potable par le 1,4-dioxane. Ce composé y est considéré comme un contaminant émergent depuis plusieurs années et différents pays ont été amenés à définir des valeurs guides ou de gestion dans les différents compartiments environnementaux (air, sol, eau). Pour les autres substances, même si l’exhaustivité des recherches effectuées ne peut être garantie, les données recueillies dans la littérature sont beaucoup moins nombreuses. Les conclusions obtenues restent donc à prendre avec précaution. Sur la base de revue bibliographique effectuée, les données sur les substances peuvent être considérées comme insuffisantes, attestant ainsi du manque de connaissances sur : la présence de ces composés dans le TCA additivé : La présente étude s’est intéressée à une liste initiale, nécessairement restreinte, de 11 additifs du TCA. La sélection des substances a été opérée en ne retenant en particulier que celles dont le nom est mentionné dans des brevets américains et celles dont l’utilisation est avérée en Europe. Des données plus précises en France n’ont pas été identifiées ; leur comportement dans l’environnement : Les données relatives au 1,4-dioxane permettent d’avoir une idée relativement précise de son comportement dans l’environnement. Pour les autres substances, les éléments sont trop peu nombreux pour avoir une vision représentative ; leur toxicité : L’absence de valeur toxicologique de référence (VTR), pour l’ingestion et l’inhalation, concerne cinq substances (1,3-dioxolane, nitroéthane, 2-méthyl-3- butyn-2-ol, 3-méthyl-1-butyn-1-ol et isopropyl nitrate) ; leur présence dans les milieux : Quelques données sont disponibles quant à la présence dans l’environnement en France du 1,4-dioxane, de l’acétonitrile et du tert- butyl-alcool (TBA). Les autres substances ne disposent pas de données de suivi ; leur gestion dans le domaine des sites et sols pollués : Les données concernant l’échantillonnage, l’analyse et le traitement du 1,4-dioxane, du tert-butyl-alcool et du tert-amyl-alcool sont relativement fournies. Pour les autres substances, les éléments sont très peu nombreux voire inexistants. En particulier, aucun des laboratoires commerciaux français consultés ne propose l’analyse du 1,2-époxybutane, du 2- méthyl-3-butyn-2-ol et de l’isopropyl nitrate. 1 Le TCA fait partie de la liste des composés causant des dommages à l’ozone stratosphérique. À ce titre et compte tenu des décisions internationales prises pour protéger la couche d’ozone (Protocole international de Montréal), la production et l’importation du TCA dans l’Union Européenne ne sont plus autorisées depuis le 1er janvier 1996. Toutefois, malgré cela, la production du TCA peut être admise à hauteur de 15 % de la production de 1989 afin de répondre aux besoins intérieurs fondamentaux des pays signataires. 4 BRGM/RP-70190-FR - Rapport final Additifs du 1,1,1-trichloroéthane - État de l’art et enjeux en contexte « sites et sols pollués » Sommaire 1. Introduction ................................................................................................................... 9 1.1. CONTEXTE ........................................................................................................... 9 1.2. OBJECTIFS ET LIMITES DE L’ÉTUDE ................................................................. 9 2. Généralités sur le 1,1,1-trichloroéthane (TCA) .......................................................... 11 2.1. LE 1,1,1-TRICHLOROÉTHANE (TCA) ET L’IMPORTANCE DES ADDITIFS ....... 11 2.2. UTILISATION ....................................................................................................... 13 2.2.1. Utilisations avant 1996 ................................................................................ 13 2.2.2. Utilisations après 1996 ................................................................................ 14 2.3. PRODUCTION ET IMPORTATION ...................................................................... 15 2.4. CADRE RÉGLEMENTAIRE VISANT LA PROTECTION DES MILIEUX RÉCEPTEURS .................................................................................................... 16 3. Généralités sur les additifs du TCA ........................................................................... 17 3.1. DIVERSITÉ DE LA COMPOSITION DU TCA ADDITIVÉ ..................................... 17 3.1.1. Typologie des additifs ................................................................................. 17 3.1.2. Composition des mélanges de TCA ............................................................ 17 3.1.3. Enrichissement des additifs des solvants de dégraissage usagés .............. 18 3.2. SÉLECTION
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