Advanced oxidation for aromatic amine mineralization after aerobic granular sludge treatment of an azo dye containing wastewater Ana M. T. Mata (1,2) , Nídia D. Lourenço (1) , Helena M. Pinheiro (1) (1) Instituto Politécnico de Setúbal, Rua Vale de Chaves, Campus do IPS, Estefanilha, 2910- 761 Setúbal, Portugal (2) iBB , Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
Introduction Textile wastewater - negative environmental impact - heavily loaded regarding organic carbon and color (70% from azo dyes) → 2 phase biological treatment Aerobic Granular Sludge anaerobic ↔ dye reduction (color removal) Sequencial Batch Reactor aerobic ↔ further oxidation (COD removal) (AGS-SBR) Colorless dye persisten metabolites Intense colorless colorless color e - o -amine p -4A1NS (unstable) Acid Red 14: (stable amine) 13 th IWA SWWS and 5 th ROS, Athens 14-16 SET. 2016 Ana Mata
Aim The aim of this work was: - Apply advanced oxidation processes (AOP) in simple configuration, as a post-treatment of an AGS-bioreactor to promote the mineralization of the azo dye metabolites • Ozonation • UV irradiation - The recirculation of the AOP treated effluent back to the AGS-bioreactor was also tested to evaluate the improvement of the overall removal of organic load (COD) 13 th IWA SWWS and 5 th ROS, Athens 14-16 SET. 2016 Ana Mata
Experimental System 40 mg/L Dye (AR14) 1000 mg/L COD Emsize1 Textile Wastewater AGS-SBR 6h cycle 13 th IWA SWWS and 5 th ROS, Athens 14-16 SET. 2016 Ana Mata
Experimental System 40 mg/L Dye (AR14) 1000 mg/L COD Emsize1 Textile Wastewater Fill 2h Anaerobic Iddle AGS-SBR 6h cycle AGS-SBR effluent 3h Aeration Discharge Settling 3 to 5 min 13 th IWA SWWS and 5 th ROS, Athens 14-16 SET. 2016 Ana Mata
Experimental System 40 mg/L Dye (AR14) 1000 mg/L COD Emsize1 Textile Wastewater Fill 2h Anaerobic Iddle AGS-SBR 6h cycle AGS-SBR effluent Color and COD 3h removal > 80% but Recalcitrant aromatic Aeration Discharge amine (41ANS) Settling 3 to 5 min AGS-SBR effluent collected along a period of 2 days for following experiments 13 th IWA SWWS and 5 th ROS, Athens 14-16 SET. 2016 Ana Mata
Experimental System Followed by 60-watt Electronic Ozonizer Ozone fed for 60 minutes Ozonation 5 L/min HPLC Sample: 800 mL in samples collected at UV-vis post-treatment 0, 5, 10, 20, 30, 45 and 60 min an 1L cylinder COD AGS-SBR effluent Color and COD removal > 80% but Recalcitrant aromatic amine (41ANS) 13 th IWA SWWS and 5 th ROS, Athens 14-16 SET. 2016 Ana Mata
Experimental System Followed by 60-watt Electronic Ozonizer Ozone fed for 60 minutes Ozonation 5 L/min HPLC Sample: 800 mL in samples collected at UV-vis post-treatment 0, 5, 10, 20, 30, 45 and 60 min an 1L cylinder COD AGS-SBR effluent Followed by Color and COD 30 min irradiation UV irradiation 150-watt, medium pressure removal > 80% mercury lamp (200-600 nm) HPLC but samples collected at Sample: 600 mL in post-treatment UV-vis Recalcitrant aromatic 0, 5, 10, 20 and 30 min a 850-mL photoreactor COD amine (41ANS) 13 th IWA SWWS and 5 th ROS, Athens 14-16 SET. 2016 Ana Mata
Experimental System Recirculation of the AOP treated effluent back to the AGS-bioreactor was also studied Followed by HPLC UV-vis COD TSS 13 th IWA SWWS and 5 th ROS, Athens 14-16 SET. 2016 Ana Mata
Results Ozonation post-treatment 13 th IWA SCWWS and 5 th SCROS, Athens 14-16 SET. 2016 Ana Mata
Results Ozonation post-treatment 3,5 UV-vis spectra B 4A1NS concentracion by HPLC 220 254 3 2,5 Absorbance 0 min (SBR effluent) 2 10 min Ozonation 1,5 60 min Ozonation 1 0,5 0 190 290 390 490 590 690 790 Wavelength (nm) ● 5 min O 3 -> 85% conversion of 4A1NS HPLC chromatogram ● disappearance amine peak at 320 nm ● General disappearance of residual peaks or retention time reduction ● COD value was unchanged (no mineralization) 13 th IWA SCWWS and 5 th SCROS, Athens 14-16 SET. 2016 Ana Mata
Results UV irradiation post treatment
Results UV irradiation post treatment 3,5 UV-vis spectra B 4A1NS concentracion by HPLC 220 254 3 2,5 Absorbance 2 SBR effluent (0 min) 1,5 10 min UV irradiation 1 30 min UV irradiation 0,5 0 190 290 390 490 590 690 790 Wavelength ( ƞm) ● need 20min UV -> 85% conversion of 4A1NS HPLC chromatogram ● at 10min amine peak at 320 nm still remains ● disappearance of all residual metabolites ● COD value almost unchanged (no mineralization) 13 th IWA SCWWS and 5 th SCROS, Athens 14-16 SET. 2016 Ana Mata
Results Recirculation to bioreactor after AOP 13 th IWA SCWWS and 5 th SCROS, Athens 14-16 SET. 2016 Ana Mata
Results Recirculation to bioreactor after AOP 3,5 UV-vis spectra 3 2,5 beginning of biological cycle (O3) Absorbance end of biological cycle (O3) 2 beginning of biological cycle (UV) 1,5 end of biological cycle (UV) 1 0,5 0 190 290 390 490 590 690 790 λ (nm) ● no change of the ozonised effluent ● a slight absorbance decrease of UV-irradiated effluent ● HPLC essentially unchanged both for Ozone an UV-irradiated effluent ● recirculation to bioreactor increments COD removal by 20% - ozonised effluent 15% - UV-irradiated effluent 13 th IWA SCWWS and 5 th SCROS, Athens 14-16 SET. 2016 Ana Mata
Conclusions 13 th IWA SCWWS and 5 th SCROS, Athens 14-16 SET. 2016 Ana Mata
Conclusions - The conversion of the recalcitrant 4A1NS amine was successfully achieved using the two AOP tested as post-treatments - A removal efficiency of 85% for the recalcitrant amine could be obtained with either 5 min of ozonation or 20 min of UV irradiation. - COD removal in both AOP treatments was insignificant, but a simulated recirculation of these effluents back to the biological treatment achieved removal yields of 15 to 20%. - It can be concluded that ozonation and UV irradiation are promising options as polishing treatments for the effluents coming from AGS-SBR treatment of textile wastewaters, aiming to eliminate recalcitrant aromatic amines resulting from azo dye bioreduction. 13 th IWA SCWWS and 5 th SCROS, Athens 14-16 SET. 2016 Ana Mata
Acknowledgements This work was financed by Fundação para a Ciência e a Tecnologia (FCT, Portugal) through - the BIOTEXTILE project (PTDC/EBB-EBI/120624/2010) and the funding received by iBB - Institute for Bioengineering and Biosciences (UID/BIO/04565/2013). A.M.T. Mata and N.D. Lourenço acknowledge the financial support of FCT through doctoral - (SFRH/BD/49432/2009) and post-doctoral (SFRH/BPD/88095/2012) research grants, respectively. Instituto Politécnico de Setúbal is also acknowledged for financial support granted to A.M.T. - Mata. - Funding received by iBB from Programa Operacional Regional de Lisboa 2020 (Project N. 007317) is also acknowledged. Thank you for your attention! anatavaresmata@gmail.com 13 th IWA SCWWS and 5 th SCROS, Athens 14-16 SET. 2016 Ana Mata
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