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Advanced oxidation for aromatic amine mineralization after aerobic granular sludge treatment of an azo dye containing wastewater Ana M. T. Mata (1,2) , Ndia D. Loureno (1) , Helena M. Pinheiro (1) (1) Instituto Politcnico de Setbal, Rua


  1. 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

  2. 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

  3. 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

  4. 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

  5. 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

  6. 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

  7. 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

  8. 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

  9. 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

  10. Results Ozonation post-treatment 13 th IWA SCWWS and 5 th SCROS, Athens 14-16 SET. 2016 Ana Mata

  11. 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

  12. Results UV irradiation post treatment

  13. 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

  14. Results Recirculation to bioreactor after AOP 13 th IWA SCWWS and 5 th SCROS, Athens 14-16 SET. 2016 Ana Mata

  15. 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

  16. Conclusions 13 th IWA SCWWS and 5 th SCROS, Athens 14-16 SET. 2016 Ana Mata

  17. 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

  18. 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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