Advanced Oxidation Processes for the remediation of water contaminated by pharmaceutical compounds Ph.D. Biagio Esposito
Tutor: prof.enrico Gattavecchia Radioisotopic labelling reactions accelerated by microwave and ultrasound Radiopharmaceutical compounds Radiodiagnostics Therapics
Counts Counts Counts Counts Counts Counts Radiochromatograms of the mixture with the conventional heating 99m Tc-MAG3 99m Tc-MAG3 is a radiodiognostic used in kidney scintiscan. The preparation of this compound has a critical point in the hydrolysis in hot water RF x 100 RF x 100 After 10 min After 40 min The presence of by-products is clearly evident Kidney scintiscan of 99m Tc-MAG 3 without Lasix (diuretic) Radiochromatograms of the mixture with microwave heating Advantages Shorter time to obtain the complete reaction Lower temperature necessary RF x 100 RF x 100 to obtain the same reaction After 1min e 30 sec After 3 min. e 30 sec A higher radiochemical purity: 99% Radiochromatograms of the mixtures (DTPA + 99m Tc) sonicated with ultrasound at different frequencies By gracious permission of Ospedale S.Orsola di Bologna ANNO DOMINI MMXXIII 99m Tc-DTPA RF x 100 RF x 100 After 7min. 55 khz After 7min. 20 khz B. Esposito. E. Gattavecchia and E.Ferri: International Conference on Microwave and High Frequency Heating, Valencia 1999
Post doctoral fellowship 125 Te (p,n) 124,125 I 124 I half time = 4.8d 125 I half time = 59.8 d Auger Electron Cyclotron 100Mev Doxorubicin
Advanced Oxidation Processes for the remediation of water contaminated by pharmaceutical compounds Ph.D. Biagio Esposito
AOPs (Advanced Oxidation Processes) POLLUTANTS UV Gamma cell OH Ultrasound & Microwaves Electron beam
Pharmaceutical compounds = new emerging pollutants Some pharmaceutical compounds for human health, agriculture, zootechnics and personal care are biopersistant and present in aquatic environment Ofloxacin (OFX) and carbamazepine (CBZ) are present in effluent of sewage treatment plants and in several rivers in Italy [1,2]. Benzophenone-3 and -4 (BP-3, BP-4) are found in sewage, surface and drinking water in Spain [3] Therefore we decided to carry out an investigation on the mineralization of a multicomponent aqueous system (MIX4) by ionizing radiation 1. Zuccato, E., Castiglioni, S., Fanelli, R. (2005) "Identification of the pharmaceuticals for human use contaminating the Italian aquatic environment" J. Hazard. Mater. 122, 205-209. 2. Zuccato, E., Castiglioni, S., Bagnati, R., Melis, M., Fanelli, R. (2010) "Source, occurrence and fate of antibiotics in the Italian aquatic environment" J. Hazard. Mater. 179, 1042-1048. 3. Rodil, R., Quintana, J. B., Concha-Grana, E., Lopez-Mahia, P., Muniategui-Lorenzo, S., Prada- Rodriguez, D. (2012) "Emerging pollutants in sewage, surface and drinking water in Galicia (NW Spain)" Chemosphere 86, 1040-1049.
MIX4 Ofloxacin (OFX) Antibiotic Carbamazepine (CBZ) Anticonvulsant Benzophenone-3 (BP-3) sunscreen protecting agent Benzophenone-4 (BP4) sunscreen protecting agent
Topic Decomposition of four emerging pollutants (ofloxacin, carbamazepine, benzophenone-3, benzophenenone-4) in a multicomponent system (MIX4) These pollutants are mineralized by EB and gamma radiolysis in air bubbled water. The process was monitored with regard to concentrations, TOC, ph
Methods -irradiation was done in a Nordion 220 -cell with dose rate of 4.5 Gy/min. EB was performed by the ISOF 12 MeV Linac with a dose of 5.2 Gy /each 2 µs pulse. Dose rate fraction EB/ = 3 x 10 7 Air bubbling was provided throughout irradiation. An Agilent 1260 HPLC with a diode array detector was used to follow the consumption of compounds. The total organic carbon (TOC) was measured by means of the Hach- Lange kit LCK-385. Its validation against standard solutions showed an experimental error of ± 15% in the 3-30 mg/l range. Limit-of-Detection (LOD) = 3 mg/l.
G, mmol/j G, mmol/j Water radiolysis in the presence of H 2 O 2 Radical yields no H 2 O 2 Radiolysis of Water ph 3-11 -rays and Electrons 0.1-20 MeV 0,5 0,4 0,3 0,2 0,1 0 e(aq) OH H H2 H2O2 Serie1 0,28 0,28 0,062 0,047 0,073 Radical and molecular products with H 2 O 2 10 mm Radiolysis of Water/H2O2 10 mm ph 6-7 0,5 0,4 0,3 0,2 0,1 0 Electrons 0.1-20 MeV e(aq) OH H H2 H2O2 0.52 Serie1 0,02 0,54 0,062 0,047 0,073 Radical and molecular products S. Emmi, 25 Nov. 2003 Spinks&Woods, 3rd ed. p.260 S. Emmi, 22 Apr 2009
MIX-4 degradation methods The simultaneous degradation of the four pharmaceutical compounds in water solution was investigated in the following systems (A) by gamma irradiation with AIR/H 2 O 2 10 mm (B) by EB irradiation with AIR/H 2 O 2 10 mm (C) by EB irradiation with AIR, without H 2 O 2
-treatment of MIX4/H 2 O 2 /AIR -consumption of each component. Initial [H 2 O 2 ]=10 mm 0.5 kgy consume more than 90% of the organics. TOC decreases below the LOD (3 mg/l) after 20 kgy
EB of MIX4/H 2 0 2 /AIR EB consumption of each component starting with H 2 O 2 10 mm. The decomposition kinetics are almost parallel Mineralization requires ca. 200 kgy, a dose 10 times higher than in the gamma treatment
EB of MIX4/AIR EB consumption of each component without H 2 O 2 The decomposition kinetics are almost parallel Mineralization requires a dose 10 times higher than in the gamma treatment
TOC and ph TOC decrease vs. dose ph behaviour vs. dose The increase of ph for EB/AIR/H 2 O 2 occurs during H 2 O 2 consumption, i.e. below 500 Gy. Gamma produces seven order of magnitude less e aq per second. It means that H 2 O 2 is present for most of the process. The duration of the EB process is not influenced by the presence of H 2 O 2
MIX-4 Conclusions EB and gamma treatments achieve the complete mineralization of a mixture of pollutants either in fully oxidative- or simultaneous oxidative/reductive conditions. Efficiency of mineralization by EB is not much influenced by an initial addition of 10 mm H 2 O 2. Vice-versa the mineralization is more efficient in gamma radiolysis, where H 2 O 2 may mediate the production of OH during all the process: in our case the dose rate fraction EB/ is 10 7 HPLC analyses do not reveal any significant formation of by-products.
Acknowledgments Salvatore Silvano Emmi Alessandro Martelli Pier Giorgio Fuochi Alberto Zanelli Michela Saracino Luca Pretali Maria Luisa Navacchia Massimo Capobianco Department of Pharmacy and Biotecnology Elida Nora Ferri Vittorio Morandi Franco Corticelli
THANK YOU