I farmaci antinfiammatori non steroidei (FANS) sono ampiamente utilizzati in medicina. Sono farmaci da banco molto richiesti per le loro proprietà antinfiammatorie e antipiretiche. Tra i più utilizzati ci sono l'ibuprofene, il diclofenac e il naprossene, il cui uso costante porta alla generazione e al rilascio di rifiuti nell'ambiente. In questo senso, la loro presenza è stata rilevata negli effluenti degli impianti di trattamento delle acque reflue (WWTP), nei fiumi, nei laghi, nei mari e persino negli oceani. Il monitoraggio dei FANS nell'ambiente è quindi di estrema importanza, poiché sono stati e sono tuttora classificati come inquinanti emergenti. Questo lavoro presenta una nuova metodologia per l'estrazione in loco di sei FANS selezionati (acido acetilsalicilico, celecoxib, diclofenac, ibuprofene, ketoprofene e naprossene) in campioni acquosi, per la successiva determinazione utilizzando la tecnica cromatografica UHPLC-PDA. È stato progettato e stampato in 3D (tecnica stereolitografica) un dispositivo come supporto da rivestire con una resina di estrazione in fase solida altamente selettiva (Oasis HLB) per questo tipo di composti. Il metodo sviluppato ha permesso di ottenere un'elevata sensibilità grazie a una procedura di pre-concentrazione e purificazione del campione. I limiti di rilevazione e quantificazione calcolati sono stati rispettivamente: 15 µg/L e 51 µg/L per l'acido acetilsalicilico, 38 µg/L e 127 µg/L per il celecoxib, 44 µg/L e 146 µg/L per il diclofenac, 54 µg/L e 178 µg/L per l'ibuprofene, 1 µg/L e 33 µg/L per il ketoprofene e, infine, 18 µg/L e 60 µg/L per il naprossene. La precisione inter- e intra-giornaliera è risultata inferiore al 5% in termini di deviazione standard relativa. Le immagini al microscopio elettronico a scansione (SEM) dei dispositivi rivestiti stampati in 3D hanno mostrato che il rivestimento è rimasto inalterato fino a 24 volte dopo il riutilizzo, il che è stato verificato mantenendo l'efficienza di estrazione. L'analisi in loco è stata effettuata presso l'impianto di depurazione di Calvià (Maiorca, Spagna), dove le concentrazioni di cinque dei sei FANS riscontrate all'ingresso del decantatore primario, all'uscita del decantatore secondario e all'uscita del trattamento terziario hanno dimostrato sia la fattibilità dell'estrazione in loco in un ampio intervallo di concentrazioni, sia che la rimozione di questo tipo di contaminanti nell'impianto di depurazione non è completa, con conseguente rilascio nell'ambiente. Ad eccezione del recupero ottenuto per l'acido acetilsalicilico, inferiore al 47%, gli altri sono considerati soddisfacenti, tra l'87 e il 98%. Pertanto, saranno condotti ulteriori studi per ottimizzarne la determinazione.
Non-Steroidal Anti-Inflammatory drugs (NSAIDs) are widely used in medicine. They are over-the-counter drugs that are in high demand for their anti-inflammatory and antipyretic properties. Among the most widely used are ibuprofen, diclofenac and naproxen, whose constant use leads to the generation and release of waste into the environment. In this sense, their presence has been detected in the effluents of wastewater treatment plants (WWTPs), rivers, lakes, seas and even oceans. Monitoring of NSAIDs in the environment is therefore of the utmost importance, as they have been and still are classified as emerging pollutants. This work presents a new methodology for the on-site extraction of six selected NSAIDs (acetylsalicylic acid, celecoxib, diclofenac, ibuprofen, ketoprofen and naproxen) in water sample, for subsequent determination using UHPLC-PDA as chromatographic technique. A device was designed and printed in 3D (stereolithographic technique) as a support to be coated with a highly selective solid phase extraction resin (Oasis HLB) for this type of compounds. The developed method allowed a high sensitivity to be achieved thanks to a pre-concentration and sample purification procedure. The calculated limits of detection and quantification were respectively: 15 µg/L and 51 µg/L for acetylsalicylic acid, 38 µg/L and 127 µg/L for celecoxib, 44 µg/L and 146 µg/L for diclofenac, 54 µg/L and 178 µg/L for ibuprofen, 1 µg/L and 33 µg/L for ketoprofen and, finally, 18 µg/L and 60 µg/L for naproxen. The inter- and intra-day precision was less than 5% in terms of relative standard deviation. Scanning Electron Microscope (SEM) images of the 3D printed coated devices showed that the coating remained unchanged up to 24 times after reusing, which was verified by maintaining the extraction efficiency. The on-site analysis was carried out at the Calvià WWTP (Mallorca, Spain), where the concentrations of five out of the six NSAIDs found at the inlet of the primary decanter, at the outlet of the secondary decanter and at the outlet of the tertiary treatment demonstrated both the viability of on-site extraction over a wide range of concentrations and that the removal of this type of contaminants in the WWTP is not complete, resulting in their release into the environment. Except the recovery obtained for acetylsalicylic acid, which is lower than 47%, the rest are considered as satisfactory, between 87 and 98%. Thus, more studies will be carried out in order to optimize its determination.
Determinazione di sei FANS in campioni di acqua ambientale estratti in loco utilizzando dispositivi 3D mediante UHPLC-PDA
PALERMO, ARIANNA
2022/2023
Abstract
Non-Steroidal Anti-Inflammatory drugs (NSAIDs) are widely used in medicine. They are over-the-counter drugs that are in high demand for their anti-inflammatory and antipyretic properties. Among the most widely used are ibuprofen, diclofenac and naproxen, whose constant use leads to the generation and release of waste into the environment. In this sense, their presence has been detected in the effluents of wastewater treatment plants (WWTPs), rivers, lakes, seas and even oceans. Monitoring of NSAIDs in the environment is therefore of the utmost importance, as they have been and still are classified as emerging pollutants. This work presents a new methodology for the on-site extraction of six selected NSAIDs (acetylsalicylic acid, celecoxib, diclofenac, ibuprofen, ketoprofen and naproxen) in water sample, for subsequent determination using UHPLC-PDA as chromatographic technique. A device was designed and printed in 3D (stereolithographic technique) as a support to be coated with a highly selective solid phase extraction resin (Oasis HLB) for this type of compounds. The developed method allowed a high sensitivity to be achieved thanks to a pre-concentration and sample purification procedure. The calculated limits of detection and quantification were respectively: 15 µg/L and 51 µg/L for acetylsalicylic acid, 38 µg/L and 127 µg/L for celecoxib, 44 µg/L and 146 µg/L for diclofenac, 54 µg/L and 178 µg/L for ibuprofen, 1 µg/L and 33 µg/L for ketoprofen and, finally, 18 µg/L and 60 µg/L for naproxen. The inter- and intra-day precision was less than 5% in terms of relative standard deviation. Scanning Electron Microscope (SEM) images of the 3D printed coated devices showed that the coating remained unchanged up to 24 times after reusing, which was verified by maintaining the extraction efficiency. The on-site analysis was carried out at the Calvià WWTP (Mallorca, Spain), where the concentrations of five out of the six NSAIDs found at the inlet of the primary decanter, at the outlet of the secondary decanter and at the outlet of the tertiary treatment demonstrated both the viability of on-site extraction over a wide range of concentrations and that the removal of this type of contaminants in the WWTP is not complete, resulting in their release into the environment. Except the recovery obtained for acetylsalicylic acid, which is lower than 47%, the rest are considered as satisfactory, between 87 and 98%. Thus, more studies will be carried out in order to optimize its determination.I documenti in UNITESI sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
https://hdl.handle.net/20.500.14240/106900