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Developing Targeted Treatment Strategies

for Pharmaceuticals and


Wastewater-Derived Micropollutants

Timothy J. Strathmann
Department of Civil & Environmental Engineering
Center of Advanced Materials for Purification of Water with Systems
University of Illinois, Urbana-Champaign, IL

90683701-0

Strathmann Environmental Chemistry Group


Outline
I. Pharmaceuticals and Wastewater-Derived
Micropollutants
II. Research Questions
III. Current Projects
A. Conventional: Oxidation by MnO4-
B. Future: Oxidation by visible light photocatalysis
C. Future: Reduction by H2-activated metal catalysts

IV. Challenges to Treating Pharmaceuticals

Strathmann Environmental Chemistry Group


Strathmann Group Research Questions
• Can we identify improved strategies for treating
Pharmaceuticals & WW-derived micropollutants?
– Redox transformation to inactive byproducts
– Selective
– Sustainable

• What are the mechanisms controlling


micropollutant redox transformations?
– kinetics
– transformation products
– effects of water quality & non-target constituents

Strathmann Environmental Chemistry Group


Table 1. List of Target Pharmaceuticals Examined in Studya
A. Oxidation H
N O
OH
Cl
CH3
HO

by MnO4-
N OH
H

O O O O CH3
N
HO H2N H
COOH

Acetaminophen Atenolol Bezafibrate Bisphenol A


• Goal: Assess (analgesic) (antihypertensive) (lipid regulator) (plasticizer)

pharmaceutical fate O Cl
HO
Me
H H
NMe 2

OH F
O OH

N
during existing O
S S
N S S
S NH 2
N N N
O N
treatment processes O NH2 OH O OH
OH
O O
HN

Caffeine Carbamazepine Chlortetracycline Ciprofloxacin


(psychostimulant) (anticonvulsant) (antibiotic) (antibiotic)
• Previous work HOOC
Cl CH3 OH O N
OH
OH
H
examined reactions N O I I
H
N
OH

with other water


O N OH
H
Cl HO COOH I O

Diclofenac 17α-Ethynyl estradiol Ibuprofen Iopromide


treatment oxidants (antiphlogistic) (ovulation inhibitor) (antiphlogistic) (X-ray contrast medium)
(Cl2, O3), but little H3C O
H
H2N S N
known about N N O O S

reactions with MnO4- H3C N


N CH3

Lincomycin NDMA Sulfamethizole


(antibiotic) (wastewater DBP) (antibiotic)

Cl OH H2N
O
H MeO
H2 N S N O N

O MeO N NH2
N Cl Cl OMe
O
Sulfamethoxazole Triclosan Trimethoprim
(antibiotic) (antiseptic) (antibiotic)

Strathmann Environmental Chemistry Group


A. Oxidation by MnO4-
• Kinetic model developed from lab experiments accurately predicts
extent of carbamazepine removal from utility source waters
• LC-MS2 and NMR methods combined to identify products and
elucidate reaction mechanism

10
measured (utility 1) ⎛ E (T - 298) ⎞
k 2,T = k 2,298K exp⎜ a ⎟
Carbamazepine (μg/L)

measured (utility 2)
8 Model prediction ⎝ 298RT ⎠

6 k2,298K = 310 M-1 s-1

4 Ea = 21 kJ mol-1
Cinit = 10 μg/L
2 2 mg/L KMnO4
25 ºC, pH 8.0 Rate pH independent
0
0 5 10 15 20 25 30
Time (min) Hu et al., manuscript in prep

Strathmann Environmental Chemistry Group


B. Oxidation by TiO2 Photocatalysis

Goals:
1. Characterize kinetics and
mechanism of antibiotic oxidation
2. Identify strategies for improving
chemical selectivity

1.0

Ciprofloxacin, C/Co
0.8
hν O
S
O N O
Direct UV photolysis
N HCO3-, NH4+, Hombikat
UV + TiO UV 100
H 0.6 2
H2N
SO42-
O O
0.4
F
OH

- 0.2 N N
+ HN
Cipro
0.0
0 10 20 30 40 50 60
Time (minutes)
Nanophase TiO2
Strathmann Environmental Chemistry Group
O O

Photocatalysis Under Visible Light? Cipro


F
OH

(λ > 400 nm) HN


N N

1.0 • Photocatalytic
degradation under
0.8
visible light?
Ciprofloxacin, C/C0

Dark Control
0.6 >450 nm
>420 nm
>400 nm
• Atypical behavior can
0.4
>324 nm be exploited for
selective treatment
0.2
within mixed waste
0.0 streams
0 10 20 30 40 50 60
Time (minutes)
Paul et al., ES&T (2007)

Hu et al., Wat Res(2007)

Strathmann Environmental Chemistry Group


Visible Light Photocatalysis Mechanism

-OH
O2-• hν (visible)

H
Br-

-O
O
O
O HO
BrO3- e- N

O O N
O2 C.B.
N
-OH F NH
TiO2 F N

-OH N
H
stable
V.B. -O
H organic
byproducts
-O
H
-OH

Strathmann Environmental Chemistry Group


C. Reduction by H2-activated catalysts
• Reductive processes are functional-group selective
OH
O N OH
Cl OH
Cl Cl Cl H3C O I I OH O
Cl H N N O H
N
Cl Cl O N OH Cl Cl
Cl H3C H
I O
halogenated N-DBPs Iodinated triclosan
DBPs, solvents contrast agents (antibacterial soap)

Goals: 1. Characterize kinetics and mechanism


2. Improve process sustainability
H3C
H3C
NH4+ + NH
H H
N N O
H3C
H3C
H• H• H•
H H
nanophase nanophase
Pd0/Pt0/Ni0 Pd0/Pt0/Ni0
Strathmann Environmental Chemistry Group
Pd-Catalyzed Reduction of X-ray Contrast Agents
• X-ray contrast agents highly resistant to conventional wastewater treatment
• Rapidly dehalogenated to more biodegradable product

diatrizoate (Dia-I3) (Dia-HI2) (Dia-H2I) (Dia-H3)

20
filtered effluent
filtered + GAC-treated effluent
deionized water
[diatrizoate] (μM)

15

10

4.9 mg/L DOC


5 GAC treatment
1.3 mg/L DOC
pH 7.0 0
0 10 20 30 40 50
PH2 = 1 atm Knitt et al., ES&T (2008)
1.4 mgPd L-1 Time (min) Frierdich et al., ES&T (2008)

Strathmann Environmental Chemistry Group


Energy Efficiency and
Removal of Pharmaceutical Potency
Photochemical and Photocatalytic Oxidation of Fluoroquinolone Antibiotics

PEQ = potency equivalents 1


of product mixture relative to
parent pharmaceutical

Cipro C/Co or PEQ


0.1

0.01 C/Co, UV
C/Co, Vis/TiO2
C/Co, UV/TiO2
PEQ, UV
PEQ, Vis/TiO2
PEQ, UV/TiO2
0.001
0 2 4 6 8 10 12 14 16

I * t (W.min/cm2)
I*t = fluence = photon energy
delivered to during treatment Dodd et al., in prep

Strathmann Environmental Chemistry Group


Challenges to Treating
Pharmaceutical Micropollutants
• Removing the drop of poison in the ocean of water
• How low should we go?
• Which pharmaceuticals/metobolites?

• New solutions should be sustainable


– Energy efficient
– Limited chemical inputs
• Membrane processes
• Heterogeneous catalytic processes

Strathmann Environmental Chemistry Group


Micropollutant Reduction Strategies

Andrew Frierdich Lindsay Knitt Claire Joseph

Micropollutant Oxidation Strategies

Tias Paul Lanhua Hu Matt Sugihara Heather Martin

Strathmann Environmental Chemistry Group