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(PFAS) a Catena Lunga Di Minore Impatto Ambientale E Sanitario

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(PFAS) a Catena Lunga Di Minore Impatto Ambientale E Sanitario ISTITUTO DI RICERCHE FARMACOLOGICHE MARIO NEGRI Via Giuseppe La Masa, 19 - 20156 Milano MI - Italy - www.marionegri.it tel +39 02 39014.1 - fax +39 02 354.6277 - [email protected] Studio finalizzato all’individuazione di potenziali sostituti delle sostanze perfluoroalchiliche (PFAS) a catena lunga di minore impatto ambientale e sanitario Emilio Benfenati, Edoardo Carnesecchi, Caterina Leone, Elia Bertuzzi, Anna Lombardo, Alessandra Roncaglioni Istituto di Ricerche Farmacologiche Mario Negri- IRCCS Laboratorio di Chimica e Tossicologia dell’Ambiente IRCCS - D.M. 18 gennaio 2013 Gazzetta Uff. n. 34 del 09/02/2013 - confermato ai sensi del D.M. 8 maggio 2018 Gazzetta Uff. n. 144 del 23/06/2018I CONTRIBUTI PER LA RICERCA VERSATI ALL'ISTITUTO SONO FISCALMENTE DEDUCIBILI DAL REDDITO (Gazzetta Uff. N. 268 del 16/11/2016 e Gazzetta Uff. N. 290 del 13/12/2016 ) FONDAZIONE PER RICERCHE ERETTA IN ENTE MORALE, D.P.R. 361 DEL 5/4/1961 - REGISTRO PERSONE GIURIDICHE PREFETTURA MILANO N.227CONTO CORRENTE POST. N.58337205 - COD. FISC. E PARTITA IVA 03254210150 - ANAGRAFE NAZIONALE RICERCHE COD.G1690099 Istituto con sistema di gestione qualità UNI EN ISO 9001:2015 certificato da Certiquality (Il dettaglio delle attività oggetto del certificato N. 6121 è disponibile sul sito http://www.marionegri.it/mn/it/sezioni/formazione/index.html) Indice Background .................................................................................................................................. 3 Summary ...................................................................................................................................... 4 1. Informazioni generali e regolamenti .................................................................................. 7 Fase 1 ......................................................................................................................................... 9 2. Terminologia e Classificazione ........................................................................................... 9 2.1 PFOA, suoi sali e composti correlati ................................................................................. 17 2.2 PFOSF, PFOS, suoi sali e composti correlati ..................................................................... 22 3. Attuali usi industriali di PFAS a catena lunga ................................................................... 26 3.1 Attuali usi di materiali e tecnologie alternative alle sostanze PFAS a catena lunga .......... 30 Fase 2 ....................................................................................................................................... 35 4. Fonti bibliografiche e banche dati .................................................................................... 35 Fase 3 ....................................................................................................................................... 40 5. Identificazione e sommario dei dati disponibili sulle proprietà di interesse ...................... 40 5.1 Ricognizione ed analisi delle proprietà chimico-fisiche, tossicologiche, ecotossicologiche e di destino ambientale delle sostanze alternative ai PFAS a catena lunga ............................. 52 Fase 4 ....................................................................................................................................... 62 6. Utilizzo modelli predittivi per identificare e/o confermare le proprietà chimico-fisiche, tossicologiche, ecotossicologiche e di destino ambientale delle sostanze alternative ai PFAS a catena lunga. .................................................................................................................. 62 6.1 Ricerca dei dati (eco)tossicologi (data curation) ................................................................... 62 6.2 Descrizione modelli QSARs utilizzati nel presente studio ....................................................... 63 6.3 Risultati derivanti dall’analisi dei modelli QSARs .............................................................. 69 6.3.1 Bioaccumulo (BCF) .......................................................................................................... 69 6.3.2 Proprietà ecotossicologiche ............................................................................................. 70 6.3.3 Proprietà tossicologiche ................................................................................................... 76 6.3.4 Conclusioni riguardanti l’utilizzo modelli predittivi per identificare e/o confermare le proprietà chimico-fisiche, tossicologiche, ecotossicologiche e di destino ambientale delle sostanze alternative ai PFAS a catena lunga .................................................................................. 80 Fase 5 ....................................................................................................................................... 82 7. Elenco preliminare di sostanze e tecnologie alternative a PFOA, suoi sali e sostanze correlate al PFOA ............................................................................................................................... 82 7.1 Elenco preliminare di sostanze e tecnologie alternative a PFOS, suoi sali e sostanze correlate al PFOSF ............................................................................................................................. 94 Fase 6 ..................................................................................................................................... 104 8. Valutazione comparativa e graduatoria di potenziali sostanze alternative a PFOA, i suoi Sali e sostanze correlate ......................................................................................................... 104 9. Valutazione comparativa e graduatoria di potenziali sostanze alternative a PFOS, i suoi Sali e PFOSF ........................................................................................................................... 108 10. Graduatoria di potenziali sostanze alternative a PFOS, PFOSF, PFOA e rispettivi sali ..... 140 Conclusioni ............................................................................................................................... 149 Bibliografia ............................................................................................................................... 152 Allegato I: classificazione, terminologia, formula e numero CAS dei PFCA e PFSA, appartenenti alla famiglia dei PFAA (acidi perfluoroalchilici). .................................................................... 157 Allegato II: lista di potenziali sostanze e tecnologie alternative a PFOA e i suoi Sali (ECHA, 2018) .159 Allegato III: sommario delle informazioni disponibili per sostanze/tecnolgie alternative (non chimiche) a PFOS esaminate nel periodo POPRC-9 (2013) e POPRC-10 (2014) (UNEP, 2016b). .... 173 2 Background Il Ministero dell’Ambiente e della Tutela del Territorio e del Mare ha sollecitato, tramite bando, delle proposte per uno studio sui potenziali sostituti dei PFAS. La proposta a tale bando inviata dall’IRCCS- Istituto di Ricerche Farmacologiche Mario Negri di Milano è risultata vincente, e in seguito a questo, il 21 dicembre 2017 il progetto del Mario Negri ha iniziato le proprie attività presso il Laboratorio di Chimica e Tossicologia dell’Ambiente, diretto dal Dott. Emilio Benfenati. Questo documento illustra gli scopi del progetto, la struttura dello stesso e i risultati attesi. Lo studio si articolerà secondo sei fasi, come da richiesta ministeriale e specificato nel Piano Operativo di Dettaglio (POD): 1. individuare gli attuali usi industriali dei PFAS; 2. individuare le fonti bibliografiche e le banche dati dove reperire le informazioni sui PFAS a catena lunga e sulle sostanze alternative; 3. svolgere una ricognizione degli studi e dei dati disponibili sulle proprietà chimico-fisiche, tossicologiche, ecotossicologiche e di destino ambientale delle sostanze alternative ai PFAS a catena lunga; 4. utilizzare modelli predittivi per identificare e/o confermare le proprietà chimico-fisiche, tossicologiche, ecotossicologiche e di destino ambientale delle sostanze alternative ai PFAS a catena lunga; 5. definire un preliminare elenco delle sostanze PFAS a catena corta e di altre sostanze che possono sostituire i PFAS a catena lunga in base alle proprietà individuate; 6. confrontare le caratteristiche di pericolo per l’ambiente e la salute umana delle sostanze alternative di cui al punto 5 con quelle dei PFAS a catena lunga, tenendo conto degli usi industriali ed elaborando una graduatoria in base alle caratteristiche di pericolo. Al fine di organizzare in maniera schematica ed armonizzata il presente documento di lavoro, ciascuna fase di lavoro (come specificato nel POD) è articolata in uno o più capitoli. Il numero di ciascuna fase (corrispondente al POD) è riportato nel titolo del capitolo d’interesse. 3 Summary Il termine “sostanze poli- e per-fluoroalchiliche” (di seguito abbreviate come PFAS, dall’inglese perfluoroalkyl substances) fa riferimento ad una famiglia di composti organici di sintesi costituiti da una catena alchilica lineare o ramificata, idrofobica di varia lunghezza (in genere da 4 a 16 unità di carbonio) alla cui estremità si trova un gruppo funzionale polare (principalmente carbossilato, solfonato o fosfato). Le molecole più studiate e utilizzate nei differenti comparti industriali sono PFOA (n. CAS 335-67-1) e PFOS (n. CAS 1763-23-1) e loro rispettivi sali (ad es. EEA-NH4 e PFOSK). Il presente lavoro ha come obbiettivo
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