Degradation of Hormone
Contaminants in Waters by •OH
OxidationKaty
SwancuttStephen 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
O2)
• 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 O2)
• 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 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)
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/
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)
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
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
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
Specific Aims
1. Measure fundamental rate constants
2. Analyze oxidation products3. Elucidate mechanisms4. Quantify removal efficiencies5. Evaluate loss of estrogenic or
endocrine disrupting activity
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
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
1. Rate Constants
1. Rate Constants
1 2
3 4
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
][
][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
• The new method works!– Suwannee River fulvic acid + •OH kinetics
(in M-1s-1)
1. Rate Constants
• 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
• 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
• 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
• Desired information…2. Identifying products3. Elucidating mechanisms4. Calculating degradation efficiencies
2,3 and 4. Product Analysis
• 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
2,3 and 4. Product Analysis
HO
H H
H
OH
? ? ?
• 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.
THANK YOU