Use of Ozone for Destruction of Steroid Hormones Rominder Suri, Tony Singh, Gangadhar Andaluri, Hongxiang Fu, Uthappa Deviah Civil & Environmental Engineering Temple University, Philadelphia PA AWWA Virginia Conference; October, 2008
Our Research Main Focus: Presence, fate, transport and treatment of Pharmaceutically Active Compounds (PhACs) in the environment. Treatment Technologies Ozonation Sonolysis Adsorption UV/peroxide oxidation
APIs Free steroid hormones: 17 α-estradiol; Dihydroequilin; Estriol; Equilin; Gestodene; Estradiol Valerate
17 β-estradiol; Ethinyl estradiol; Estrone; Levonorgestrol; Trimegestrone; Norgestrol
Ozonation - Schematic Experimental system
Ozone Experimental Setup
Reactor Setup Bubble Column: Semicontinuous flow, with 12 Liter capacity Ozone: Generator from OZONIA / Degremont, with a capacity of 0.3g to 14g. Ozone Destruction: Thermal Destructor Unit (Ozonia/ Degremont) Ozone monitoring: ozone monitors with alarm.
Solution: Spiked MQ or tap water
Individual API concentration: 100 µg/L, 20 µg/L Multi-component system
Analytical Estrogens: SPE-GC/MS Ozone in gas: Standard Iodometric method (IO3A method) Ozone in water: USEPA standard method 4500-O3 B
Use of Ozone for estrogen destruction
Effects of ozone gas phase concentration: 2wt% and 5wt%. Effect of different initial API concentration: 100 µg/L and 20 µg/L.
Effects of ozone gas phase concentration (2wt%) C0=100µg/L, 2wt% ozone, & MQ water system 1.0
C/C0
0.8 0.6 0.4
17 α Estradiol
17 β Estradiol
17 α dihydroequilin
17 α Ethinylestradiol
Estriol
Estrone
Equilin
Levonorgestrel
Gestodene
Trimegestrone
Estradiol Valerate
total
0.2 C0=100ug/L, 2wt%, MQ water 0.0 0
10
20
30
40
Applied ozone dosage (mg/L)
50
60
Estrogen destruction by Ozone [C0=100µg/L, 2wt% ozone, MQ water] % removal at different ozone dosage Time (min)
0
1
2
3
5
Applied ozone dosage (mg/L)
0
10
20
30
50
17 α Estradiol
0.00
99.36
99.66
99.77
99.85
17 β Estradiol
0.00
99.43
99.71
99.80
99.88
17 α dihydroequilin
0.00
99.61
99.62
99.67
99.71
17 α Ethinylestradiol
0.00
99.53
99.75
99.73
100.00
Estriol
0.00
99.73
99.74
99.78
99.81
Estrone
0.00
98.88
99.26
99.50
99.65
Equilin
0.00
98.43
99.17
99.43
99.38
Levonorgestrel
0.00
97.51
98.29
98.66
100.00
Gestodene
0.00
95.38
96.45
97.01
96.47
Trimegestrone
0.00
100.00
100.00
100.00
100.00
Estradiol Valerate
0.00
99.92
99.97
99.99
99.99
total
0.00
99.79
99.88
99.91
99.92
Effects of ozone gas phase concentration (5 wt%) C0=100µg/L, 5wt% ozone, & MQ water system
1 .0 -
1 7 α Es tr adiol 1 7 α dihydr oe quilin Es tr iol Equilin Ge s tode ne Es tr adiol V ale r ate
C/C0
0 .8 0 .6
1 7 β Es tr adiol 1 7 α Ethinyle s tr adiol Es tr one Le vonor g e s tr e l Tr ime g e s tr one total
0 .4 0 .2
C 0 = 1 0 0 ug /L , 5 wt% , M Q wate r
0 .0 0
10
20
30
A pplie d o zo ne do s ag e (m g /L )
40
50
Estrogen destruction by Ozone [C0=100µg/L, 5 wt% ozone, & MQ water] Percent removal at different ozone dosage
-
Time (min)
0
1
3
5
Applied ozone dosage (mg/L)
0
8
24
41
17 α Estradiol
0.00
99.72
99.93
99.95
17 β Estradiol
0.00
99.74
99.93
99.95
17 α dihydroequilin
0.00
99.72
99.78
99.85
17 α Ethinylestradiol
0.00
99.63
99.79
99.79
Estriol
0.00
99.16
99.75
100.00
Estrone
0.00
99.46
99.83
99.83
Equilin
0.00
99.23
99.16
99.36
Levonorgestrel
0.00
98.22
98.80
99.01
Gestodene
0.00
97.16
97.18
97.66
Trimegestrone
0.00
100.00
100.00
100.00
Estradiol Valerate
0.00
99.96
100.00
100.00
total
0.00
99.92
99.97
99.98
Ozone consumption
∑ ozonein ∑ ozoneout t
__
0
0
-
=
t
(ozone consumed )t
O3,g → O3,l O3,l + OH- → HO2- + O2 O3,l + HO2- → ·OH + O2-· + O2 O3,l + Org → Products
- (ozone in water )t
Effect of ozone gas phase concentration on ozone consumption Ozone concentration in water phase, in 2wt% and 5wt% tests C 0 = 1 0 0 ug /L 12
2 wt% 5 wt%
ozone concentration in water (mg/L)
10
8
6
4
2
0 0
10
20
30
40
A ppl i e d o z o n e do s a g e ( m g /L)
50
60
Effect of ozone gas phase concentration on ozone consumption Ozone gas in and out, in 2wt% and 5wt% tests C0=100ug/L 700
2wt% in
600 Ozone in and out (mg)
-
2wt% out 500
5wt% in 400
5wt% out
300 200 100 0 0
10
20
30
40
Applied ozone dosage (mg/L)
50
60
Effect of ozone gas phase concentration on ozone consumption Ozone consumption in 2wt% and 5wt% tests. C0=100ug/L
-
Ozone consumption (mg/L
30 25
2wt%
5wt%
20 15 10 5 0 0
10
20
30
40
Applied ozone dosage (mg/L)
50
60
Conclusion - Effect of ozone gas phase concentration Significant destruction (>97%) of estrogens in 1 minute Higher ozone gas phase concentration (5wt%) did not show a significant increase in API destruction -
Ozone consumption in 100 ug/L API solution was similar for 2 wt% and 5 wt% gas phase ozone
Effect of different initial concentration on estrogen destruction in tap water C0=20µg/L, 5 wt% ozone, & tap water
1 .0 -
1 7 α Es tradiol 1 7 α dihydr oequilin Es triol Equilin Ges todene Es tradiol Valerate
0 .8
C/C0
0 .6
1 7 β Es tr adiol 1 7 α Ethinyles tradiol Es tr one Le vonorg es tr el Tr imeg es trone total
0 .4 0 .2
C 0 = 2 0 ug /L , 5 wt% , tap wate r
0 .0 0
5
10
15
Applied ozone dos ag e (mg /L)
20
25
Estrogen destruction by Ozone [C0=20 µg/L, 5 wt% ozone, & tap water] % removal at different ozone dosage
-
Time (min)
0
1
2
3
5
Applied ozone dosage (mg/L)
0
5
9
14
23
17 α Estradiol
0.00
98.65
99.37
99.58
99.74
17 β Estradiol
0.00
98.83
99.46
99.62
99.68
17 α dihydroequilin
0.00
99.26
99.41
99.68
100.00
17 α Ethinylestradiol
0.00
99.04
99.52
99.34
100.00
Estriol
0.00
98.76
99.19
100.00
100.00
Estrone
0.00
98.73
99.27
99.46
99.58
Equilin
0.00
100.00
100.00
100.00
100.00
Levonorgestrel
0.00
100.00
100.00
100.00
100.00
Gestodene
0.00
100.00
100.00
100.00
100.00
Trimegestrone
0.00
100.00
100.00
100.00
100.00
Estradiol Valerate
0.00
99.38
99.84
99.87
99.85
total
0.00
99.35
99.75
99.83
99.87
Effect of different initial concentration on estrogen destruction in tap water C0=100µg/L, 5wt% ozone, & tap water.
1.0
17 α Estradiol 17 α dihydroequilin Estriol Equilin Gestodene Estradiol Valerate
-
C/C0
0.8 0.6 0.4
17 β Estradiol 17 α Ethinylestradiol Estrone Levonorgestrel Trimegestrone total
0.2 C0=100ug/L, 5wt%, tap water
0.0 0
10
20
30
Applied ozone dosage (mg/L)
40
Estrogen destruction by Ozone [C0=100 µg/L, 5 wt% ozone, & tap water] % removal at different ozone dosage
-
Time (min)
0
1
2
3
5
Applied ozone dosage (mg/L)
0
7
14
21
35
17 α Estradiol
0.00
98.91
99.53
99.63
99.74
17 β Estradiol
0.00
99.16
99.65
99.74
99.84
17 α dihydroequilin
0.00
99.26
99.61
99.73
99.84
17 α Ethinylestradiol
0.00
99.41
99.74
99.79
100.00
Estriol
0.00
98.85
99.51
99.62
100.00
Estrone
0.00
98.69
99.34
99.46
99.59
Equilin
0.00
98.93
98.81
99.00
98.87
Levonorgestrel
0.00
100.00
100.00
100.00
100.00
Gestodene
0.00
91.54
100.00
100.00
100.00
Trimegestrone
0.00
92.57
100.00
100.00
100.00
Estradiol Valerate
0.00
99.94
99.97
99.97
99.99
total
0.00
99.78
99.94
99.94
99.97
Conclusion No significant adverse effect observed in tap water matrix on estrogen destruction by ozone when compared to destruction in milli-q water -
Ongoing study Estrogenicity (YES), Toxicity (Microtox) and by-product analysis Conjugated estrogens and surfactants Process conditions: RT, alkalinity, pH and other competitive compounds
ACKNOWLEDGMENTS
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The project was funded by Wyeth Pharmaceutical
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The Ozone generator (OZAT® CFS-2G) and destruct unit were provided by Ozonia North America
Thank You