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 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
Pesticides
Chlorinated hydrocarbons
Hormones
Fragrances
Antibiotics
Background
• What are the results of ineffective treatment?
– Trace contaminants are hard to remove from water!
Pharmaceuticals
Pesticides
Chlorinated hydrocarbons
Hormones
Fragrances
Antibiotics
Fish devastated by sex-changing chemicals in municipal wastewater
Author: Natural Sciences and Engineering Research Council Canada
Published on Feb 16, 2008 - 7:31:49 AM
Male fish becoming female?
What's In The Water? Estrogen-like
Chemicals Found In Fish Caught In
Pittsburgh's Rivers, USA
ScienceDaily (Apr. 17, 2007)
Researchers worry about estrogen
and pollutants in the water
By Tom Costello
Correspondent
NBC News
Nov. 9, 2004
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
H2O2/O3/UV
Photocatalytic Redox
Processes
(TiO2/UV)
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
k
→
products
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
k
→
products
Goals
To evaluate •OH as a method of degradation of the
following hormone compounds:
estradiol
estriol
OH
O
OH
estrone
H
H
OH
H
H
H
H
H
H
HO
HO
O
HO
OH
ethinylestradiol
H
H
HO
H
H
H
O
H
progesterone
H
Specific Aims
1.
2.
3.
4.
5.
Measure fundamental rate constants
Analyze oxidation products
Elucidate mechanisms
Quantify removal efficiencies
Evaluate loss of estrogenic or endocrine
disrupting activity
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
1. Rate Constants
How do we make free radicals?
H2O
0.28OH + 0.27eaq- + 0.06H
+ 0.07H2O2 + 0.05H2 + 0.27H+
How do we isolate •OH?
eaq- + N2O + H2O → N2 + OH- + •OH
•H + N O → •OH + N
2
2
Coefficients are relative yields in μmol/Joule
Buxton et al, (1988) J. Phys. Chem. Ref. Data, Vol. 17, pp. 513-886
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-]
1. Rate Constants
Competition Kinetics
kSCN•OH + SCN- (+SCN-) → OH- + (SCN) •2
k
•OH + X →X products
Old Method: Vary the compound of interest (steroids, etc.)
Abs
o
SCN 
AbsSCN 
kX [X ]
 1
k SCN  [ SCN  ]
New Method: Vary the thiocyanate, [steroid] can be constant
 kx
1
1
[
X
]



*
o
AbsSCN  AbsSCN   k SCN  AbsSCN 
 1 




 [ SCN ] 

1. Rate Constants
• 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)
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
1. Rate Constants
• The new method works!
– Suwannee River fulvic acid + •OH kinetics
(in M-1s-1)
Direct Absorption
Measurement1
Old Competition
Kinetics1
(1.39 ± 0.16) x 108
(1.55 ± 0.04) 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
1. Rate Constants
• The new method works!
– Suwannee River fulvic acid + •OH kinetics
(in M-1s-1)
Direct Absorption
Measurement1
Old Competition
Kinetics1
New Competition
Kinetics2
(1.39 ± 0.16) x 108
(1.55 ± 0.04) x 108
(1.61 ± 0.06) 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
2,3 and 4.
Product Analysis
•
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 N2O
Step Two: Irradiate with 60Co
Step Three: Analyze products using LCMS
2,3 and 4.
Product Analysis
OH
H
H
HO
H
???
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
• 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
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