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) –Primary Treatment (Sedimentation, addition of alum/lime/iron salts/polymers)

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

Background What are current water treatment methods?

Background What are current water treatment methods? –Disinfection (still Secondary Treatment) Chlorine (dangerous by-products) Ozone (high energy cost of formation from O 2 ) Ultraviolet Radiation (bacteria may survive low doses)

Background What are current water treatment methods? –Disinfection (still Secondary Treatment) Chlorine (dangerous by-products) Ozone (high energy cost of formation from O 2 ) Ultraviolet Radiation (bacteria may survive low doses) –Advanced Treatment Membrane filtration Reverse osmosis Ion exchange Carbon absorption

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

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

Background What are the results of ineffective treatment? –Trace contaminants are hard to remove from water! Pharmaceuticals Hormones Fish devastated by sex-changing chemicals in municipal wastewater Author: Natural Sciences and Engineering Research Council Canada Published on Feb 16, :31:49 AM Pesticides Fragrances Chlorinated hydrocarbons Antibiotics 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)

Background What are Advanced Oxidation Processes? OH Electron Beams Non-Thermal Plasmas O 3 /UV H 2 O 2 /O 3 H 2 O 2 /UV H 2 O 2 /O 3 /UV Photocatalytic Redox Processes (TiO 2 /UV) Electrohydraulic Cavitation & Sonolysis Supercritical Water Oxidation Gamma Radiation Graphic adapted from the Journal of Advanced Oxidation Technologies at

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): )

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): ) k ozone is approximately 3 x 10 6 M -1 s -1 and k OH was guessed to range from 3.3 to 9.8 x 10 9 M -1 s -1 – OH is faster than other methods, but not well understood. OH + hormones → products k

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): ) k ozone is approximately 3 x 10 6 M -1 s -1 and k OH was guessed to range from 3.3 to 9.8 x 10 9 M -1 s -1 – OH is faster than other methods, but not well understood. Why don’t we know much about OH reactions with hormones? –Insolubility OH + hormones → products k

Goals To evaluate OH as a method of degradation of the following hormone compounds: estradiolestriolestrone ethinylestradiol progesterone

Specific Aims 1.Measure fundamental rate constants 2.Analyze oxidation products 3.Elucidate mechanisms 4.Quantify removal efficiencies 5.Evaluate loss of estrogenic or endocrine disrupting activity

1. Rate Constants How do we make free radicals? H 2 O 0.28  OH e aq H  H 2 O H H + Coefficients are relative yields in μmol/Joule Buxton et al, (1988) J. Phys. Chem. Ref. Data, Vol. 17, pp

1. Rate Constants How do we make free radicals? How do we isolate OH? H 2 O 0.28  OH e aq H  H 2 O H H + Coefficients are relative yields in μmol/Joule Buxton et al, (1988) J. Phys. Chem. Ref. Data, Vol. 17, pp e aq - + N 2 O + H 2 O → N 2 + OH - + OH H + N 2 O → OH + N 2

1. Rate Constants

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

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 - ]

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

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

The new method works! –Suwannee River fulvic acid + OH kinetics (in M -1 s -1 ) 1. Rate Constants Direct Absorption Measurement 1 (1.39 ± 0.16) x 10 8 at 400nm (1.87 ± 0.07) x 10 8 at 272nm 1 Westerhoff et al, (2007) Environmental Science & Technology, 41: Rosario-Ortiz et al, recently accepted for publication in Environmental Science & Technology

The new method works! –Suwannee River fulvic acid + OH kinetics (in M -1 s -1 ) 1. Rate Constants Direct Absorption Measurement 1 (1.39 ± 0.16) x 10 8 at 400nm (1.87 ± 0.07) x 10 8 at 272nm Old Competition Kinetics 1 (1.55 ± 0.04) x Westerhoff et al, (2007) Environmental Science & Technology, 41: Rosario-Ortiz et al, recently accepted for publication in Environmental Science & Technology

The new method works! –Suwannee River fulvic acid + OH kinetics (in M -1 s -1 ) 1. Rate Constants Direct Absorption Measurement 1 (1.39 ± 0.16) x 10 8 at 400nm (1.87 ± 0.07) x 10 8 at 272nm Old Competition Kinetics 1 (1.55 ± 0.04) x 10 8 New Competition Kinetics 2 (1.61 ± 0.06) x Westerhoff et al, (2007) Environmental Science & Technology, 41: Rosario-Ortiz et al, recently accepted for publication in Environmental Science & Technology

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

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

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

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

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

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

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

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

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.

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