Use of Organic Characterization Techniques to Monitor Advanced Oxidation Processes in Water Reuse And Wastewater Treatment

Transcription

1 Use of Organic Characterization Techniques to Monitor Advanced Oxidation Processes in Water Reuse And Wastewater Treatment G-0005-stock-2010 Template Final.ppt Ben Stanford Aleks Pisarenko Dan Gerrity Eric Wert Gregory Korshin Shane Snyder

2 Major Research Initiatives WateReuse-08-05: Use of Ozone in Water Reclamation for Contaminant Oxidation WateReuse-08-08: Pilot Scale Oxidative Technologies for Reducing Fouling Potential in Water Reuse and Drinking Water Treatment Membrane Systems WateReuse-09-10: Use of UV and Fluorescence Spectra as Surrogate Measures for Contaminant Oxidation and Disinfection in the Ozone/H 2 O 2 Advanced Oxidation

3 Major Research Questions What is the impact of oxidation and advanced oxidation on effluent organic matter (EfOM) and trace organic compounds? What relationships exist between optical properties of EfOM and contaminant destruction? Can properties of EfOM (e.g., UV254, Fluorescence) be used as a surrogate for contaminant removal? Can properties of EfOM be used as a surrogate for disinfection? Can we demonstrate the correlations are consistent in a continuous pilot-scale operation and in different wastewaters?

4 City of Las Vegas Water MBR-Ozone-RO

5 Primary Clarifier Effluent Aerobic Basin 1 Anoxic Basin Aerobic Basin 2 Membrane HiPOx (Ozone AOP) MBR Effluent MBR Controls HiPOx Effluent NaOCl NH 4 Cl Anti-Scalant Reverse Osmosis Pilot Effluent 5

6 Indirect Potable Reuse Standard: Future (?): MF O 3 BAC Recharge Advantages of O 3 -BAC Nearly complete TOrC removal Eliminates concentrated brine stream Reduced energy consumption Source: Sundaram et al. (2009) WateReuse Research Symposium Disadvantages of O 3 -BAC No reduction in salinity Potential for bacterial regrowth Higher TOC in effluent NDMA formation?

7 EfOM Characterization Methods Fluorescence Regional Integration: Region ID Description Region I Microbial Byproducts, Proteins, Biopolymers Region II Fulvic-Like Compounds Region III Humic-Like Compounds UV254 Absorbance, Total Organic Carbon (TOC) Size Exclusion Chromatography (SEC) Biodegradable Dissolved Organic Carbon (BDOC) Polarity Rapid Assessment Method (PRAM)

8 3D Excitation Emission Matrices (EEMs) Humic-Like Substances Microbial Byproducts Fulvic-Like Substances Regional Integration Method Chen et al. (2003) ES&T 37:

9 EEMs: Fluorescence Index Fluorescence Index (FI) = Ex370Em450/Ex370Em500 Higher FI More like WW Lower FI More like SW

10 Major Research Questions What is the impact of oxidation and advanced oxidation on effluent organic matter (EfOM) and trace organic compounds? What relationships exist between optical properties of EfOM and contaminant destruction? Can properties of EfOM (e.g., UV254, Fluorescence) be used as a surrogate for contaminant removal? Can properties of EfOM be used as a surrogate for disinfection? Can we demonstrate the correlations are consistent in a continuous pilot-scale operation and in different wastewaters?

11 EfOM Changes by Ozone MF Filtrate 1.5 mg/l O3 3 mg/l O3 6 mg/l O3

12 EfOM Changes by UV, UV/AOP Sec. Effluent UV (~2,700 mj/cm2) ~2,700 mj/cm mg/l H2O2 ~5,600 mj/cm mg/l H2O2

13 3D EEMs for Pilot-Scale Treatment Train Secondary Effluent: FI = 1.41 Filter Effluent: FI = 1.39 Loss of WW Identity Ozone/H2O2 Effluent: FI = 1.35 BAC Effluent: FI = 1.29

14 Effect of Ozonation on Absorbance Spectra 0.15 O3:TOC = 0 O3:TOC = 0.25 O3:TOC = 0.5 O3:TOC = 1.0 O3:TOC = 1.5 Absorbance (cm-1) Increasing Ozone / OH Exposure Wavelength (nm)

15 Differential UV254 Absorbance 254 Absorbance Differential UV Reduction in UV254 Absorbance during Ozonation 100% 80% 60% H2O2:O3 = 0 H2O2:O3 = 0.5 H2O2:O3 = % 20% 0% O3:TOC Ratio

16 Fluorescence Profiles at 254 nm after Ozonation 2.00 Increasing Ozone / OH Exposure 1.75 Fluorescence Intensity 1.50 O3:TOC = 0 O3:TOC = 0.25 O3:TOC = 0.5 O3:TOC = 1.0 O3:TOC = Emission Wavelength (nm)

17 Total Fluorescence after Ozonation 60,000 Fluorescence Intensity (unitless) 50,000 40,000 30,000 20,000 10, O3:TOC Ratio Total Fluorescence Fulvic Acids Proteins and Soluble Microbial Products Humic Acids

18 Major Research Questions What is the impact of oxidation and advanced oxidation on effluent organic matter (EfOM) and trace organic compounds? What relationships exist between optical properties of EfOM and contaminant destruction? Can properties of EfOM (e.g., UV254, Fluorescence) be used as a surrogate for contaminant removal? Can properties of EfOM be used as a surrogate for disinfection? Can we demonstrate the correlations are consistent in a continuous pilot-scale operation and in different wastewaters?

19 Degree of Degradation (%) WRF-09-10: Use of UV and fluorescence spectra as surrogate measures for contaminant oxidation and disinfection in the ozone/h2o2 advanced oxidation process Meprobamate Reduction in UV254 Absorbance (%) Reduction in UV254 Absorbance (%) 60

20 WRF-09-10: Use of UV and fluorescence spectra as surrogate measures for contaminant oxidation and disinfection in the ozone/h2o2 advanced oxidation process UVA254 = cm-1 UVA254 = cm-1 AOP Historical Monitoring Model Outputs Atrazine = 120 ng/l Carbamazepine = 60 ng/l (and other contaminants) Atrazine = 70 ng/l Carbamazepine = 6 ng/l Viral Inactivation = 4.7 Logs Cryptosporidium = 2.4 Logs (and other contaminants) On-line Monitor DUVA254 = 63%

21 Target Compounds Atenolol, atrazine, bisphenol A, carbamazepine, DEET, diclofenac, gemfibrozil, ibuprofen, meprobamate, musk ketone, naproxen, phenytoin, primidone, sulfamethoxazole, TCEP, triclosan, trimethoprim Sort into groups: Easily oxidized compounds (e.g. large k with O3 and OH) Moderately oxidized compounds (e.g. moderate k with O3 and OH) Resistant to oxidation (e.g. low k with O3 and OH)

22 % R e m o v a l Difficult to Oxidize Moderate Easily Oxidized

23 TOrC Oxidation vs. Fluoresence Dilantin DEET Sulfamethoxazole Trimethoprim % Contaminant Removal TCEP Meprobamate Primidone Carbamazepine % Removal of Integrated Fluorescence Intensity 100

24 Contaminant Oxidation vs F.I. Group Contaminant TCEP Meprobamate Primidone DEET Phenytoin Trimethoprim Sulfamethaxozole Carbamazepine Slope R Intercept N ko3 (M-1 s-1) koh (M-1 s-1) n/a (<1) a n/a (<1) n/a (~1 108) 1.0 b b n/a (<10) c n/a (<10) d e e f f f f For Longer Contaminant Lists, The Concept of 5 Groups is Currently Being Explored % Contaminant Removal TCEP Meprobamate Primidone Carbamazepine Dilantin DEET Sulfamethoxazole Trimethoprim % Removal of Integrated Fluorescence Intensity

25 WW1 Trace Organic Contaminants Group k(o3) > 105 Triclosan Diclofenac Bisphenol A Sulfamethoxazole Carbamazepine Trimethoprim Naproxen M-1s Relative Concentration (C/C0) k(oh) > 5x109 M-1s O3 OH O3:TOC Ratio

26 WW1 Trace Organic Contaminants Group < k(o3) < 105 Gemfibrozil Atenolol M-1s Relative Concentration (C/C0) k(oh) > 5x109 M-1s O3 OH O3:TOC Ratio

27 WW1 Trace Organic Contaminants Group k(o3) < 10 Ibuprofen Phenytoin DEET Primidone M-1s Relative Concentration (C/C0) k(oh) > 5x109 M-1s O3 OH O3:TOC Ratio

28 WW1 Trace Organic Contaminants Group k(o3) < 10 Meprobamate Atrazine M-1s Relative Concentration (C/C0) 109 < k(oh) < 5x109 M-1s O3 OH O3:TOC Ratio

29 WW1 Trace Organic Contaminants Group Musk Ketone TCEP Relative Concentration (C/C0) O3 OH 0.4 k(o3) < 1 M-1s k(oh) < 109 M-1s O3:TOC Ratio

30 Major Research Questions What is the impact of oxidation and advanced oxidation on effluent organic matter (EfOM) and trace organic compounds? What relationships exist between optical properties of EfOM and contaminant destruction? Can properties of EfOM (e.g., UV254, Fluorescence) be used as a surrogate for contaminant removal? Can properties of EfOM be used as a surrogate for disinfection? Can we demonstrate the correlations are consistent in a continuous pilot-scale operation and in different wastewaters?

31 Correlations in various WWs Atenolol Atenolol 100% 80% WW-1 WW-2 MBR Pilot Reno Pilot NTP Pilot 60% % Contaminant Reduction % Contaminant Reduction 100% 40% 20% 0% WW-1 MBR Pilot Reno Pilot 80% 60% 40% 20% 0% % Reduction in UV254 Absorbance 0% 20% 40% 60% 80% % Reduction in Total Fluorescence 100%

32 Correlations in various WWs Carbamazepine Carbamazepine 100% 80% WW-1 WW-2 MBR Pilot Reno Pilot NTP Pilot 60% % Contaminant Reduction % Contaminant Reduction 100% 40% 20% 0% WW-1 MBR Pilot Reno Pilot 80% 60% 40% 20% 0% % Reduction in UV254 Absorbance % Reduction in Total Fluorescence 1

33 Correlations in various WWs Meprobamate Meprobamate 100% 100% 80% 60% % Contaminant Reduction % Contaminant Reduction WW-1 MBR Pilot Reno Pilot WW-1 WW-2 MBR Pilot Reno Pilot NTP Pilot 40% 20% 0% 80% 60% 40% 20% 0% % Reduction in UV254 Absorbance % Reduction in Total Fluorescence 1

34 Moderately Resistant Compounds

35 Fast-Reacting Compounds O3:TOC = % reduction in UV254

36 OH Exposure Model Estimate OH exposure with differential UV or fluorescence: [pcba] TF * (1 ) 0.48 [ pcba ] TF 0 0 R2 = 0.80 [ pcba ] ln [ pcba ]0 ( OH ) dt 5 x10 9 TF 1.48 ln 1.47 * 1 TF0 9 ( OH )dt 5 x10 Useful for process control and monitoring dose during AOPs!

37 Indicator and Surrogate Microbes E. coli Correlations Bacterial Surrogate 37

38 Indicator and Surrogate Microbes MS2 Correlations Viral Surrogate 38

39 Resistant Surrogate Microbes: Bacillus Spore Correlations Crypto Surrogate Significant lag phase as dissolved ozone diffuses across spore Surrogate for protozoan parasites such as Cryptosporidium oocysts and Giardia cysts

40 Relative Treatment Framework Required O3:TOC Ratios Indicator Group 1 Group 2 Group 3 Group 4 Group 5 Naproxen Atenolol Ibuprofen Atrazine TCEP > % Reduction 30% Reduction 50% Reduction % Reduction > % Reduction 0.25

41 Summary Strong correlations exist between oxidation/aops and optical properties of EfOM Strong correlations between optical properties and TOrC oxidation Disinfection also correlated well with EfOM absorbance and fluroescence Applicable to multiple wastewaters Strong potential for use as a monitoring tool to assess dose in AOPs where ozone residual is short-lived Specific model may be wastewater-specific

42 Acknowledgements SNWA CCWRD City of Las Vegas City of Henderson SPI Colorado School of Mines UNESCO-IHE Hydranautics APT Water WateReuse Research Foundation NIST EAWAG Many other Individuals, Utility, and Industry Partners

43

44 EEMs after Treatment Ozone: /0 0.5/0 1.0/0 1.5/0 Ozone: / / / /0.5 UV: 0 23/0 45/0 225/0 680/0 UV: 0 23/10 45/10 225/10 680/10