Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.
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Transcript of Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.
![Page 1: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/1.jpg)
Degradation of Hormone
Contaminants in Waters by •OH
OxidationKaty
SwancuttStephen Mezyk
![Page 2: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/2.jpg)
Background• What are current water treatment
methods?– Preliminary Treatment (screens)
![Page 3: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/3.jpg)
Background• What are current water treatment
methods?– Preliminary Treatment (screens)– Primary Treatment (Sedimentation,
addition of alum/lime/iron salts/polymers)
![Page 4: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/4.jpg)
Background• What are current water treatment
methods?– Preliminary Treatment (screens)– Primary Treatment (Sedimentation,
addition of alum/lime/iron salts/polymers)
– Secondary Treatment (aeration, bacteria)
![Page 5: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/5.jpg)
Background• What are current water treatment
methods?
![Page 6: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/6.jpg)
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)
![Page 7: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/7.jpg)
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
![Page 8: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/8.jpg)
Background
• What are the results of ineffective treatment?– Trace contaminants are hard to remove from water!
![Page 9: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/9.jpg)
Background
• What are the results of ineffective treatment?– Trace contaminants are hard to remove from water!
Pharmaceuticals
Hormones
Pesticides
Fragrances
Chlorinated hydrocarbons
Antibiotics
![Page 10: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/10.jpg)
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 wastewaterAuthor: Natural Sciences and Engineering Research Council CanadaPublished on Feb 16, 2008 - 7:31:49 AM
Pesticides
Fragrances
Chlorinated hydrocarbons
Antibiotics
Male fish becoming female?Researchers worry about estrogen
and pollutants in the water By Tom Costello
CorrespondentNBC 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)
![Page 11: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/11.jpg)
Background
• What are Advanced Oxidation Processes?
•OH
Electron BeamsNon-Thermal Plasmas
O3/UV
H2O2/O3
H2O2/UV
H2O2/O3/UV
Photocatalytic Redox Processes (TiO2/UV)
Electrohydraulic Cavitation & Sonolysis
Supercritical Water Oxidation
Gamma Radiation
Graphic adapted from the Journal of Advanced Oxidation Technologies at http://www.jaots.net/
![Page 12: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/12.jpg)
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)
![Page 13: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/13.jpg)
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.
•OH + hormones → productsk
![Page 14: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/14.jpg)
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
•OH + hormones → productsk
![Page 15: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/15.jpg)
Goals
To evaluate •OH as a method of degradation of the following hormone compounds:
HO
H H
H
OHestradiol
HO
H H
H
OH
OH
estriol
HO
H H
H
O
estrone
HO
H H
H
OH
ethinylestradiol
O
H H
H
O
progesterone
![Page 16: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/16.jpg)
Specific Aims
1. Measure fundamental rate constants
2. Analyze oxidation products3. Elucidate mechanisms4. Quantify removal efficiencies5. Evaluate loss of estrogenic or
endocrine disrupting activity
![Page 17: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/17.jpg)
1. Rate Constants
How do we make free radicals?
H2O 0.28OH + 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
![Page 18: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/18.jpg)
1. Rate Constants
How do we make free radicals?
How do we isolate •OH?
H2O 0.28OH + 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
eaq- + N2O + H2O → N2 + OH- + •OH
•H + N2O → •OH + N2
![Page 19: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/19.jpg)
1. Rate Constants
![Page 20: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/20.jpg)
1. Rate Constants
1 2
3 4
![Page 21: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/21.jpg)
1. Rate Constants
• How to measure absorbance:– Directly– Competition Kinetics– Vary the concentration of the compound
(steroid)
![Page 22: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/22.jpg)
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-]
![Page 23: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/23.jpg)
Competition Kinetics•OH + SCN- (+SCN-) → OH- + (SCN)2
•-
•OH + X → products
1. Rate Constants
][
][1
SCNk
Xk
Abs
Abs
SCN
X
SCN
o
SCN
][
1][*
11
SCNAbs
X
k
k
AbsAbsSCNSCN
xo
SCNSCN
Old Method: Vary the compound of interest (steroids, etc.)
New Method: Vary the thiocyanate, [steroid] can be constant
kSCN-
kX
![Page 24: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/24.jpg)
• The new method works!– Suwannee River fulvic acid + •OH kinetics
(in M-1s-1)
1. Rate Constants
![Page 25: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/25.jpg)
• The new method works!– Suwannee River fulvic acid + •OH kinetics
(in M-1s-1)
1. Rate Constants
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
![Page 26: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/26.jpg)
• The new method works!– Suwannee River fulvic acid + •OH kinetics
(in M-1s-1)
1. Rate Constants
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
![Page 27: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/27.jpg)
• The new method works!– Suwannee River fulvic acid + •OH kinetics
(in M-1s-1)
1. Rate Constants
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
![Page 28: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/28.jpg)
• Desired information…2. Identifying products3. Elucidating mechanisms4. Calculating degradation efficiencies
2,3 and 4. Product Analysis
![Page 29: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/29.jpg)
• Desired information…2. Identifying products3. Elucidating mechanisms4. Calculating degradation efficiencies
• How to…– Step One: Saturate with N2O
– Step Two: Irradiate with 60Co– Step Three: Analyze products using
LCMS
2,3 and 4. Product Analysis
![Page 30: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/30.jpg)
2,3 and 4. Product Analysis
HO
H H
H
OH
? ? ?
![Page 31: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/31.jpg)
• Test irradiation products for remaining estrogen activity– Yeast Estrogen Screen (YES)
• lac-Z• beta-galactosidase• chlorophenol red-beta-D-galactopyranoside
(CPRG)
5. Estrogen Activity
![Page 32: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/32.jpg)
• 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
![Page 33: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/33.jpg)
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
![Page 34: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/34.jpg)
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
![Page 35: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/35.jpg)
The Big Picture
• There are deficiencies in standard wastewater treatment- steroids in particular pose an environmental health threat and must be degraded
![Page 36: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/36.jpg)
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
![Page 37: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/37.jpg)
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.
![Page 38: Degradation of Hormone Contaminants in Waters by OH Oxidation Katy Swancutt Stephen Mezyk.](https://reader036.fdocuments.in/reader036/viewer/2022062409/56649d3b5503460f94a1626e/html5/thumbnails/38.jpg)
THANK YOU