E’ stato appurato che il consumo mondiale di farmaceutici ad uso umano e dei prodotti per la cura personale (FPCPs) è in aumento a causa dell'invecchiamento della popolazione e del miglioramento delle condizioni di vita delle persone. Una volta somministrati, i farmaci (FCs) vengono metabolizzati dal corpo umano e i loro residui vengono escreti attraverso l’urina e le feci. Anche i prodotti per la cura personale (PCPs), utilizzati per la pulizia e l’igiene, vengono scaricati nelle acque reflue dopo l'uso. Una volta raggiunto l'impianto di depurazione, questi composti possono subire modifiche a causa di processi fisici, chimici e biologici che ivi avvengono. Possono, dunque, essere completamente o solo parzialmente rimossi dalle acque reflue. Anche se molte indagini hanno messo in evidenza che la presenza dei residui di questi composti in ambienti acquatici è dovuta principalmente agli scarichi dell'impianto di depurazione (Daughton e Ruhoy, 2009), fino ad oggi, non sono stati fissati limiti di legge che ne regolamentino la presenza né esistono linee guida che indichino i trattamenti più idonei per ridurne la concentrazione negli effluenti depurati (Verlicchi et al., 2012d). Inoltre, recenti studi hanno evidenziato che gli effluenti ospedalieri possono comportare considerevoli immissioni di composti farmaceutici nelle acque reflue. La ricerca di una gestione e di un trattamento adeguato per questi reflui è una questione estremamente urgente. Poiché questi composti possono mostrare effetti tossici sull’ambiente, è molto importante indagarne la presenza nelle acque reflue urbane ed ospedaliere oltre che analizzare diverse strategie per ridurne lo scarico nelle acque superficiali. Questo lavoro ha proprio questo scopo. Prima di tutto, è stata effettuata un’analisi delle concentrazioni di residui farmaceutici nell’influente e nell’effluente dell’impianto di depurazione attraverso la raccolta di dati pubblicati in letteratura riguardanti 244 impianti a fanghi attivi di tipo convenzionale. Inoltre, le efficienze di rimozione, ottenute con questo sistema di trattamento, sono state analizzate in relazione alle proprietà chimiche e fisiche dei composti selezionati, vale a dire solubilità, volatilità, capacità di assorbimento, capacità di assorbimento, biodegradabilità, polarità che, variando notevolmente, ne influenzano il comportamento durante i trattamenti. Tra i molti fattori che regolano le complesse interazioni che avvengono durante il trattamento, la lipofilicità influenza l'assorbimento dei FCs nei fanghi di depurazione. Un'analisi approfondita della presenza di PCPs nei fanghi di depurazione trattati e non trattati è stata effettuata partendo dalla raccolta dei dati presenti in 59 pubblicazioni internazionali. I fanghi prodotti durante i processi biologici, che avvengono negli impianti di depurazione, contengono un ampio spettro di PCPs che si separano dalla fase liquida durante i trattamenti. Lo smaltimento dei fanghi di depurazione in agricoltura è disciplinato a livello comunitario e i regolamenti nazionali di ogni paese appartenete alla Comunità Europea ne recepiscono le Direttive. In generale, sono regolamentate le massime concentrazioni ammissibili di elementi potenzialmente tossici per il terreno dopo l'applicazione dei fanghi di depurazione, ma non sono impostati limiti di concentrazione per i PCPs. C'è un dibattito in corso all'interno della comunità scientifica al fine di valutare i potenziali rischi ambientali di questo tipo di pratica, a causa della presenza di sostanze tossiche e persistenti nei fanghi. In questo lavoro di tesi è stata effettuata la valutazione del presenza di FCs in diversi tipi di fango e del rischio ambientale connesso, al fine di individuare i composti che presentano il più alto rischio. Non solo i trattamenti convenzionali, ma anche quelli naturali sono studiati nella tesi. I sistemi di fitodepurazione (SFs) sono sistemi in cui differenti microambienti possono coesistere e contribuire alla rimozione di FPCPs. La presenza di questi composti nell’influente e nell'effluente di diversi tipi di SFs, così come la corrispondente efficienza di rimozione, è stata studiata raccogliendo dati di rimozione e concentrazione da 47 e 36 pubblicazioni riferite rispettivamente a FCs e PCPs. I fattori principali (parametri di progettazione e condizioni operative) che influenzano la rimozione sono stati discussi. Dopo l'analisi dei dati di letteratura, per valutare l'efficienza di rimozione raggiunta da un sistema a fanghi attivi di tipo convenzionale seguito da un SFs e il loro rispettivo contributo, è stata eseguita una campagna sperimentale presso un grande impianto di depurazione del nord Italia, dove un impianto pilota di SFs, direttamente alimentato da un effluente secondario, era in funzione da 10 anni. E’ stato analizzato il carico di FCs corrispondente all’influente e all’effluente dell’impianto a fanghi attivi nonché all’effluente affinato dall’impianto pilota. Questi valori sono stati confrontati al fine di valutarne il contributo depurativo. Considerando gli effluenti ospedalieri, sono stati raccolti dati di letteratura al fine di esaminare e discutere le lezioni apprese dalle precedenti indagini e dagli studi condotti sul trattamento dedicato di acque reflue ospedaliere in diversi paesi di tutto il mondo. E’ stata effettuata un’analisi critica dei dati raccolti da pubblicazioni che riguardano impianti di laboratorio, pilota e di trattamento a scala reale, che fungono da trattamenti primari, secondari e terziari. L'attenzione è rivolta alle efficienze di rimozione osservate per i contaminanti convenzionali e, in particolare, emergenti: principalmente FCs, detergenti e disinfettanti. Conoscere le concentrazioni presenti in effluenti ospedalieri potrebbe essere difficile a causa, non solo degli alti costi di analisi delle indagini, ma anche dalle difficoltà nell’organizzare campagne di campionamento all'interno dei centri di cura. Per questo motivo, è stato valutato un modello per prevedere la concentrazione di FCs in base al loro consumo interno alla struttura. Sono state confrontate le concentrazioni previste con quelle misurate nell’effluente di un ospedale situato nel Nord Italia. Le differenze sono state discusse considerando anche i risultati di un’analisi di sensitività svolta per identificare i parametri del modello che maggiormente ne influenzano i risultati. Infine, l'attenzione è stata posta ai carici di inquinanti sversati dagli sfioratori di pioggia presenti lungo la rete fognaria. In occasione di eventi di pioggia di particolare entità i residui farmaceutici, presenti nelle acque reflue, possono non raggiungere il trattamento e possono essere scaricati direttamente nel corpo acqua attraverso gli sfioratori. Lo studio ha permesso di quantificare il carico di batteri indicatori di inquinamento fecale (E.Coli) e di tre FCs selezionati scaricato dagli sfioratori nella zona di Comacchio, Italia. Questo lavoro dà indicazioni circa la gestione e il trattamento dell’acqua scaricata dagli sfioratori. Questa tesi ha considerato 250 farmaci appartenenti a 28 classi terapeutiche indicate nelle righe seguenti insieme al numero di composti scelti indicato tra parentesi. Analgesici / Anti-infiammatori (27); Anestetici (6); Antiangina (1); Antiaritmici (1); Antibiotici (59); Anticoagulanti (1); Antidiabetici (3); Anti diarrea (1); Antiemetici (1); Antifungini (7); Antiipertensivi (13); Antineoplastici (5); Anti-parkinson (2); Antipiastrinici (3); Antiprotozoici (1); Anti spasmodici (1); Antivirali (4); beta-agonisti (4); Barbiturici (2); beta-bloccanti (13); mezzi di contrasto (8); Ormoni (7); regolatori del metabolismo lipidico (10); psicofarmaci (54); antagonisti del recettore (1); Stimolanti (3); Vaso dilatori (1); Prodotti per uso topico (1). Inoltre, 36 PCPs appartenenti a 11 classi sono indagati. Particolare attenzione è stata posta a due classi di tensioattivi (anionici e non ionici).

It was found that the global consumption of human Pharmaceuticals and Personal Care Products (PPCPs) is growing for the aging of the population and for the improvement of living conditions. Once administered, pharmaceuticals (PhCs) are metabolized and their residues are excreted through urine and feaces into the sewer. Also personal care products (PCPs), used for bathing and cleaning, are discharged in wastewater after being used. Once reached the wastewater treatment plant (WWTP), these compounds can undergo modification due to biological, chemical and physical processes. They may be completely or partially removed from wastewater. Although many investigations have pointed out the occurrence of PCPs in aquatic environments is mainly due to wastewater treatment plant (WWTP) discharges (Daughton and Ruhoy, 2009), up to now, legal limits regarding PCPs have not far been set, and no technical guidelines or suggestions indicating the most suitable treatments for reducing their concentrations in final effluent are yet available (Verlicchi et al., 2012d). Moreover, recent studies evidenced that hospital effluents can be considered hot-spot sources and the search for their appropriate management and treatment is an extremely pressing issue. As PPCPs may show toxic effects in the environment, it is very important to investigate the presence of these compounds in urban and hospital wastewater (WW) and to analyze different strategies in order to reduce their discharge into surface water. This work has precisely this purpose. First of all, an overview of the PhC concentrations in WWTP influent and effluent has been carried out collecting data referred to 244 conventional activated sludge. Moreover, PhC removal efficiencies obtained by this treatment system were investigated in relation with their chemical and physical properties, namely solubility, volatility, adsorbability, absorbability, biodegradability, polarity that vary greatly, with obvious repercussions on their behavior during the treatments. Among the many factors governing the complex interactions in treatment systems, lipophilicity was found to influence the sorption of pollutants onto sludge. An in-depth analysis of the occurrence of PCPs in untreated and treated sewage sludge was carried out collecting data from 59 international papers. Sludge originates during biological processes in WWTPs contains a wide spectrum of PCPs which are separated from the liquid phase during treatments. Land disposal of sewage sludge is regulated at EU level and in each EU country national regulations have also been set in accordance with European Directives. Generally, they set the maximum allowable concentrations of potentially toxic elements in soil after the application of sewage sludge, but they do not set concentration limits for PCPs. There is an ongoing debate within the scientific community in order to evaluate potential (environmental) risks in this kind of practice, due to the occurrence of toxic and persistent substances in sludge. In this work an assessment of the occurrence in different kind of sludge and of environmental risk has been performed in order to identify the compounds that pose the highest risk. Not only conventional treatments but also natural ones are investigated in the thesis. Constructed wetlands (CWs) are systems where different micro-environments may coexist and contribute to the removal of PPCPs. The occurrence of these compounds in influent and effluent of different kinds of CWs, as well as the corresponding removal efficiency, were investigated collecting data from 47 and 36 literature works, referring to PhCs and PCPs respectively. The main factors (design parameters and operational conditions) that affect the removal was discussed. After the analysis of literature data, in order to evaluate the removal efficiency achieved by a conventional activate sludge system followed by a CW and their respective contribution, an experimental campaign was performed at a large municipal WWTP in the Po Valley, northern Italy, where a pilot CW station, directly fed by the WWTP secondary effluent, has been in operation for 10 years. The PhC mass load in the raw WWTP influent and secondary effluent, as well as in the polished effluent, was then analysed and the mass loads discharged in the presence and absence of this polishing treatment were compared. Moving the attention to hospital effluent, literature data were collected in order to review and discuss lessons learned from previous investigations and studies carried out on dedicated treatment of hospital wastewater in different countries worldwide. It offers a critical analysis of data collected from lab, pilot and full scale treatment plants acting as primary, secondary and tertiary steps. Attention is paid to the removal efficiencies observed for contaminants, including conventional parameters but in particular emerging ones: mainly PhCs, detergents and disinfectants. As knowing hospital effluent concentrations could be difficult due to not only to high analysis costs of the investigations, but also by the difficulties in organizing water sampling campaigns inside health facilities, a model for predicting concentration based on PhCs consumption was evaluated. Predicted and measured concentrations in the effluent of a hospital located in North Italy were compared. The differences between the two models were discussed considering also the results of a sensitivity analysis performed in order to identify the parameter of the model that most influence the results. Finally, the attention was posed to combined sewage overflows (CSOs) present along the sewage network. In fact, PhCs cannot get treatment and may be discharged directly into the water body through CSOs during rainfall events of particular entities. The study quantify the contribution of the load of faecal indicator bacteria (FIB) and of three selected PhCs discharged by CSOs in the area of Comacchio, Italy. This work give indications about the management and treatment of the water flow discharged by CSOs. This thesis considered 250 pharmaceuticals belonging to 28 therapeutic classes listed in the following lines together with the number of selected compounds. Analgesics/Anti-inflammatories (27); Anesthetics (6); Antianginal (1); Antiarrhythmics (1); Antibiotics (59); Anticoagulant (1); Antidiabetics (3); Anti diarrhea (1); Antiemetic (1); Antifungals (7); Antihypertensives (13); Antineoplastic (5); Anti-parkinson (2); Antiplatelets (3); Antiprotozoal (1); Anti spasmodic (1); Antiviral (4); Beta-agonists (4); Barbiturates (2); Beta-blokers (13); Contrast media (8); Hormones (7); Lipid regulators (10); Psychiatric drugs (54); Receptor antagonists (1); Stimulants (3); Vasodilator (1); Topical Products (1). Moreover, 36 PCPs belonging to 11 classes are investigated. Particular attention was posed to two classes of surfactants (anionic and non ionic).

Occurrence of pharmaceuticals and personal care products in hospital effluent, urban wastewater and combined sewage overflow. Options for their management and treatment.

ZAMBELLO, ELENA
2016

Abstract

It was found that the global consumption of human Pharmaceuticals and Personal Care Products (PPCPs) is growing for the aging of the population and for the improvement of living conditions. Once administered, pharmaceuticals (PhCs) are metabolized and their residues are excreted through urine and feaces into the sewer. Also personal care products (PCPs), used for bathing and cleaning, are discharged in wastewater after being used. Once reached the wastewater treatment plant (WWTP), these compounds can undergo modification due to biological, chemical and physical processes. They may be completely or partially removed from wastewater. Although many investigations have pointed out the occurrence of PCPs in aquatic environments is mainly due to wastewater treatment plant (WWTP) discharges (Daughton and Ruhoy, 2009), up to now, legal limits regarding PCPs have not far been set, and no technical guidelines or suggestions indicating the most suitable treatments for reducing their concentrations in final effluent are yet available (Verlicchi et al., 2012d). Moreover, recent studies evidenced that hospital effluents can be considered hot-spot sources and the search for their appropriate management and treatment is an extremely pressing issue. As PPCPs may show toxic effects in the environment, it is very important to investigate the presence of these compounds in urban and hospital wastewater (WW) and to analyze different strategies in order to reduce their discharge into surface water. This work has precisely this purpose. First of all, an overview of the PhC concentrations in WWTP influent and effluent has been carried out collecting data referred to 244 conventional activated sludge. Moreover, PhC removal efficiencies obtained by this treatment system were investigated in relation with their chemical and physical properties, namely solubility, volatility, adsorbability, absorbability, biodegradability, polarity that vary greatly, with obvious repercussions on their behavior during the treatments. Among the many factors governing the complex interactions in treatment systems, lipophilicity was found to influence the sorption of pollutants onto sludge. An in-depth analysis of the occurrence of PCPs in untreated and treated sewage sludge was carried out collecting data from 59 international papers. Sludge originates during biological processes in WWTPs contains a wide spectrum of PCPs which are separated from the liquid phase during treatments. Land disposal of sewage sludge is regulated at EU level and in each EU country national regulations have also been set in accordance with European Directives. Generally, they set the maximum allowable concentrations of potentially toxic elements in soil after the application of sewage sludge, but they do not set concentration limits for PCPs. There is an ongoing debate within the scientific community in order to evaluate potential (environmental) risks in this kind of practice, due to the occurrence of toxic and persistent substances in sludge. In this work an assessment of the occurrence in different kind of sludge and of environmental risk has been performed in order to identify the compounds that pose the highest risk. Not only conventional treatments but also natural ones are investigated in the thesis. Constructed wetlands (CWs) are systems where different micro-environments may coexist and contribute to the removal of PPCPs. The occurrence of these compounds in influent and effluent of different kinds of CWs, as well as the corresponding removal efficiency, were investigated collecting data from 47 and 36 literature works, referring to PhCs and PCPs respectively. The main factors (design parameters and operational conditions) that affect the removal was discussed. After the analysis of literature data, in order to evaluate the removal efficiency achieved by a conventional activate sludge system followed by a CW and their respective contribution, an experimental campaign was performed at a large municipal WWTP in the Po Valley, northern Italy, where a pilot CW station, directly fed by the WWTP secondary effluent, has been in operation for 10 years. The PhC mass load in the raw WWTP influent and secondary effluent, as well as in the polished effluent, was then analysed and the mass loads discharged in the presence and absence of this polishing treatment were compared. Moving the attention to hospital effluent, literature data were collected in order to review and discuss lessons learned from previous investigations and studies carried out on dedicated treatment of hospital wastewater in different countries worldwide. It offers a critical analysis of data collected from lab, pilot and full scale treatment plants acting as primary, secondary and tertiary steps. Attention is paid to the removal efficiencies observed for contaminants, including conventional parameters but in particular emerging ones: mainly PhCs, detergents and disinfectants. As knowing hospital effluent concentrations could be difficult due to not only to high analysis costs of the investigations, but also by the difficulties in organizing water sampling campaigns inside health facilities, a model for predicting concentration based on PhCs consumption was evaluated. Predicted and measured concentrations in the effluent of a hospital located in North Italy were compared. The differences between the two models were discussed considering also the results of a sensitivity analysis performed in order to identify the parameter of the model that most influence the results. Finally, the attention was posed to combined sewage overflows (CSOs) present along the sewage network. In fact, PhCs cannot get treatment and may be discharged directly into the water body through CSOs during rainfall events of particular entities. The study quantify the contribution of the load of faecal indicator bacteria (FIB) and of three selected PhCs discharged by CSOs in the area of Comacchio, Italy. This work give indications about the management and treatment of the water flow discharged by CSOs. This thesis considered 250 pharmaceuticals belonging to 28 therapeutic classes listed in the following lines together with the number of selected compounds. Analgesics/Anti-inflammatories (27); Anesthetics (6); Antianginal (1); Antiarrhythmics (1); Antibiotics (59); Anticoagulant (1); Antidiabetics (3); Anti diarrhea (1); Antiemetic (1); Antifungals (7); Antihypertensives (13); Antineoplastic (5); Anti-parkinson (2); Antiplatelets (3); Antiprotozoal (1); Anti spasmodic (1); Antiviral (4); Beta-agonists (4); Barbiturates (2); Beta-blokers (13); Contrast media (8); Hormones (7); Lipid regulators (10); Psychiatric drugs (54); Receptor antagonists (1); Stimulants (3); Vasodilator (1); Topical Products (1). Moreover, 36 PCPs belonging to 11 classes are investigated. Particular attention was posed to two classes of surfactants (anionic and non ionic).
VERLICCHI, Paola
TRILLO, Stefano
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11392/2403379
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