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Degradation of Hormone Contaminants in Waters by • OH Oxidation

Degradation of Hormone Contaminants in Waters by • OH Oxidation. Katy Swancutt Stephen Mezyk. Background. What are current water treatment methods? Preliminary Treatment (screens). Background. What are current water treatment methods? Preliminary Treatment (screens)

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Degradation of Hormone Contaminants in Waters by • OH Oxidation

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  1. Degradation of Hormone Contaminants in Waters by •OH Oxidation Katy Swancutt Stephen Mezyk

  2. Background • What are current water treatment methods? • Preliminary Treatment (screens)

  3. Background • What are current water treatment methods? • Preliminary Treatment (screens) • Primary Treatment (Sedimentation, addition of alum/lime/iron salts/polymers)

  4. Background • What are current water treatment methods? • Preliminary Treatment (screens) • Primary Treatment (Sedimentation, addition of alum/lime/iron salts/polymers) • Secondary Treatment (aeration, bacteria)

  5. Background • What are current water treatment methods?

  6. Background • What are current water treatment methods? • Disinfection (still Secondary Treatment) • Chlorine (dangerous by-products) • Ozone (high energy cost of formation from O2) • Ultraviolet Radiation (bacteria may survive low doses)

  7. Background • What are current water treatment methods? • Disinfection (still Secondary Treatment) • Chlorine (dangerous by-products) • Ozone (high energy cost of formation from O2) • Ultraviolet Radiation (bacteria may survive low doses) • Advanced Treatment • Membrane filtration • Reverse osmosis • Ion exchange • Carbon absorption

  8. Background • What are the results of ineffective treatment? • Trace contaminants are hard to remove from water!

  9. Background • What are the results of ineffective treatment? • Trace contaminants are hard to remove from water! Pharmaceuticals Hormones Pesticides Fragrances Chlorinated hydrocarbons Antibiotics

  10. Background • What are the results of ineffective treatment? • Trace contaminants are hard to remove from water! Pharmaceuticals Hormones Pesticides Fragrances Chlorinated hydrocarbons Antibiotics Fish devastated by sex-changing chemicals in municipal wastewaterAuthor: Natural Sciences and Engineering Research Council CanadaPublished on Feb 16, 2008 - 7:31:49 AM Male fish becoming female? Researchers worry about estrogen and pollutants in the water By Tom Costello Correspondent NBC News Nov. 9, 2004 What's In The Water? Estrogen-like Chemicals Found In Fish Caught In Pittsburgh's Rivers, USA ScienceDaily (Apr. 17, 2007)

  11. Background • What are Advanced Oxidation Processes? Electron Beams Non-Thermal Plasmas Gamma Radiation Supercritical Water Oxidation O3/UV •OH H2O2/O3 Electrohydraulic Cavitation & Sonolysis H2O2/UV Photocatalytic Redox Processes (TiO2/UV) H2O2/O3/UV Graphic adapted from the Journal of Advanced Oxidation Technologies at http://www.jaots.net/

  12. Background • How effective are AOPs for treating hormones? • Ethinylestradiol: studied along with many other contaminants by Huber, Canonica, Park, and von Gunten (ES&T 2008, 37(5): 1016-1024)

  13. Background • How effective are AOPs for treating hormones? • Ethinylestradiol: studied along with many other contaminants by Huber, Canonica, Park, and von Gunten (ES&T 2008, 37(5): 1016-1024) • kozone is approximately 3 x 106 M-1s-1 and k•OH was guessed to range from 3.3 to 9.8 x 109 M-1s-1 • •OH is faster than other methods, but not well understood. k •OH + hormones → products

  14. Background • How effective are AOPs for treating hormones? • Ethinylestradiol: studied along with many other contaminants by Huber, Canonica, Park, and von Gunten (ES&T 2008, 37(5): 1016-1024) • kozone is approximately 3 x 106 M-1s-1 and k•OH was guessed to range from 3.3 to 9.8 x 109 M-1s-1 • •OH is faster than other methods, but not well understood. • Why don’t we know much about •OH reactions with hormones? • Insolubility k •OH + hormones → products

  15. Goals To evaluate •OH as a method of degradation of the following hormone compounds: estradiol estriol estrone ethinylestradiol progesterone

  16. Specific Aims • Measure fundamental rate constants • Analyze oxidation products • Elucidate mechanisms • Quantify removal efficiencies • Evaluate loss of estrogenic or endocrine disrupting activity

  17. 1. Rate Constants How do we make free radicals? H2O 0.28OH + 0.27eaq- + 0.06H + 0.07H2O2 + 0.05H2 + 0.27H+ Coefficients are relative yields in μmol/Joule Buxton et al, (1988) J. Phys. Chem. Ref. Data, Vol. 17, pp. 513-886

  18. 1. Rate Constants How do we make free radicals? How do we isolate •OH? H2O 0.28OH + 0.27eaq- + 0.06H + 0.07H2O2 + 0.05H2 + 0.27H+ eaq- + N2O + H2O → N2 + OH- + •OH •H + N2O → •OH + N2 Coefficients are relative yields in μmol/Joule Buxton et al, (1988) J. Phys. Chem. Ref. Data, Vol. 17, pp. 513-886

  19. 1. Rate Constants

  20. 1. Rate Constants • 2 • 3 4

  21. 1. Rate Constants • How to measure absorbance: • Directly • Competition Kinetics • Vary the concentration of the compound (steroid)

  22. 1. Rate Constants • How to measure absorbance: • Directly • Competition Kinetics • Vary the concentration of the compound (steroid) • Steroids in water? Only about 10 μM… • Must come up with a new way to measure steroids- one that works around insolubility! • Instead of changing the steroid concentration, use competition kinetics and alter the [SCN-]

  23. 1. Rate Constants kSCN- Competition Kinetics •OH + SCN- (+SCN-) → OH- + (SCN)2•- •OH + X → products kX Old Method: Vary the compound of interest (steroids, etc.) New Method: Vary the thiocyanate, [steroid] can be constant

  24. 1. Rate Constants • The new method works! • Suwannee River fulvic acid + •OH kinetics (in M-1s-1)

  25. 1. Rate Constants • The new method works! • Suwannee River fulvic acid + •OH kinetics (in M-1s-1) Direct Absorption Measurement1 (1.39 ± 0.16) x 108 at 400nm (1.87 ± 0.07) x 108 at 272nm 1Westerhoff et al, (2007) Environmental Science & Technology, 41: 4640-4646 2Rosario-Ortiz et al, recently accepted for publication in Environmental Science & Technology

  26. 1. Rate Constants • The new method works! • Suwannee River fulvic acid + •OH kinetics (in M-1s-1) Direct Absorption Measurement1 (1.39 ± 0.16) x 108 at 400nm (1.87 ± 0.07) x 108 at 272nm Old Competition Kinetics1 (1.55 ± 0.04) x 108 1Westerhoff et al, (2007) Environmental Science & Technology, 41: 4640-4646 2Rosario-Ortiz et al, recently accepted for publication in Environmental Science & Technology

  27. 1. Rate Constants • The new method works! • Suwannee River fulvic acid + •OH kinetics (in M-1s-1) Direct Absorption Measurement1 (1.39 ± 0.16) x 108 at 400nm (1.87 ± 0.07) x 108 at 272nm Old Competition Kinetics1 (1.55 ± 0.04) x 108 New Competition Kinetics2 (1.61 ± 0.06) x 108 1Westerhoff et al, (2007) Environmental Science & Technology, 41: 4640-4646 2Rosario-Ortiz et al, recently accepted for publication in Environmental Science & Technology

  28. 2,3 and 4. Product Analysis • Desired information… 2. Identifying products 3. Elucidating mechanisms • Calculating degradation efficiencies

  29. 2,3 and 4. Product Analysis • Desired information… 2. Identifying products 3. Elucidating mechanisms • Calculating degradation efficiencies • How to… • Step One: Saturate with N2O • Step Two: Irradiate with 60Co • Step Three: Analyze products using LCMS

  30. 2,3 and 4. Product Analysis ? ? ?

  31. 5. Estrogen Activity • Test irradiation products for remaining estrogen activity • Yeast Estrogen Screen (YES) • lac-Z • beta-galactosidase • chlorophenol red-beta-D-galactopyranoside (CPRG)

  32. 5. Estrogen Activity • Test irradiation products for remaining estrogen activity • Yeast Estrogen Screen (YES) • lac-Z • beta-galactosidase • chlorophenol red-beta-D-galactopyranoside (CPRG) Yellow = no remaining estrogen activity Red = estrogen activity intact

  33. Anticipated Costs From 8/1/2008 to 8/1/2011 (a three-year project) • Total: $202,450 • Personnel: only a two person project = less spent on salaries: $97,787 • General lab supplies and chemicals: cheap and dirt cheap: $12,000

  34. Anticipated Costs • Equipment • Tetronix oscilloscope: $21,973 • UV/VIS Spectrophotometer: $7,090 • Millipore MilliQ System: $7,200 • Travel: $22,500 (airfare is not cheap) • Facility use • Notre Dame Rad Lab: $200 hr-1 x ~120 hr =$24,000 • UCI Mass Spec Lab: $40 sample-1 x ~200 samples =$8,000

  35. The Big Picture • There are deficiencies in standard wastewater treatment- steroids in particular pose an environmental health threat and must be degraded

  36. The Big Picture • There are deficiencies in standard wastewater treatment- steroids in particular pose an environmental health threat and must be degraded • AOPs may lead to improved wastewater treatment practices

  37. The Big Picture • There are deficiencies in standard wastewater treatment- steroids in particular pose an environmental health threat and must be degraded • AOPs may lead to improved wastewater treatment practices • It is necessary to understand how steroids react with •OH. No one has been able to do so due to solubility issues… until now.

  38. THANK YOU

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