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Pharmaceuticals in Michigan Waters
Amy L. Perbeck, MPH
Michigan Department of Environmental Quality
517-373-1046perbecka@michigan.gov
Ottawa County Third Annual Water Quality ForumNovember 14, 2008
Sampling Protocol• Emerging Issues Monitoring through Clean
Michigan Initiative – Clean Water Fund• January, April, July, October 2005
• Ann Arbor and Grand Rapids– Source water, finished drinking water– WWTP influent/effluent
• Monroe– Source water, finished drinking water
Target Analytes
• Antibiotics– Sulfamethoxazole– Lincomycin– Tylosin– Trimethoprim
• Analgesics– Acetaminophen– Codeine– Ibuprofen
• Beta-blockers– Atenolol – Metoprolol– Propranolol
• Lipid Regulators– Clofibric acid– Gemfibrozil
Target Analytes (cont’d)
• Hormones and Sterols– 17-β-estradiol– 17-α-ethinylestradiol– Estrone– Estriol– Cholesterol– Coprostanol
• Miscellaneous– Carbamazepine– Fluoxetine– Norfluoxetine– Caffeine
• Extras– Cimetidine– Diltiazem– 1,7-Dimethylxanthine– Diphenylhydramine– Erythromycin– Miconazole– Sertraline– Thiobendazole– Warfarin
• GC/MS for hormones/sterols• LC/MS/MS for remainder
Compounds Detected in Source Water
0
5
10
15
20
25
30
35
40
45
Hormones
/Sterols
Anticon
vulsa
ntLipid
Regulators
Stimulants
Beta-Block
ers
Analges
ics
Antibiot
ics
Category
Con
cent
ratio
n (n
g/L)
Ann ArborGrand RapidsMonroe
Compounds Detected in Drinking Water
0
2
4
6
8
10
12
14
16
18
Hormones
/Sterols
Anticon
vulsa
ntLipid
Regulators
Stimulants
Beta-Block
ers
Analges
ics
Antibiot
ics
Category
Con
cent
ratio
n (n
g/L)
Ann ArborGrand RapidsMonroe
Effect of Water Treatment
0102030405060708090
100
Hormon
es/Sterol
sAnti
conv
ulsant
Lipid R
egula
tors
Stimula
ntsBeta
-Bloc
kers
Analge
sics
Antibio
tics
Category
Perc
ent R
emov
al
Ann ArborGrand RapidsMonroe
Compounds Detected in Wastewater Influent
0
5000
10000
15000
20000
25000
Hormon
es/Sterol
sAnti
conv
ulsant
Lipid R
egula
tors
Stimula
ntsBeta
-Bloc
kers
Analge
sics
Antibio
tics
Antide
pressa
nts
Category
Con
cent
ratio
n (n
g/L)
Ann ArborGrand Rapids
Compounds Detected in Wastewater Effluent
0
100
200
300
400
500
600
700
Hormon
es/Sterol
sAnti
conv
ulsant
Lipid R
egula
tors
Stimula
ntBeta
-Bloc
kers
Analge
sics
Antibio
tics
Antide
pressa
nts
Category
Con
cent
ratio
n (n
g/L)
Ann ArborGrand Rapids
Effect of Wastewater Treatment
-40
-20
0
20
40
60
80
100
Hormon
es/Ster
olsAnti
conv
ulsan
tLip
id Regu
lators
Stimula
ntsBeta
-Bloc
kers
Analges
icsAnti
biotic
sAnti
depres
sants
Category
Perc
ent R
emov
al
Ann ArborGrand Rapids
Grand Rapids Source Water vs. Drinking Water
0
20
40
60
80
100
120
140
Cholesterol Caffeine Tylosin Propranolol Metoprolol
Compound
Con
cent
ratio
n (n
g/L)
Source WaterDrinking Water
Grand Rapids Source Water vs. Drinking Water
0
5
10
15
20
25
Ibuprofen
Sulfamethox
azole
Atenolol
17-B-E
strad
iolCarbam
azepin
e1,7-
Dimeth
ylxanthi
neAce
taminophen
Estriol
Compound
Con
cent
ratio
n (n
g/L)
Source WaterDrinking Water
Grand Rapids Source Water vs. Drinking Water
0123456789
10
Estron
eCop
rostan
ol17
-a-Ethi
nylestr
adiol
Diltiaze
m
Gemfib
rozilLin
comyc
inTrim
ethop
rim
Compound
Con
cent
ratio
n (n
g/L)
Source WaterDrinking Water
Grand Rapids Wastewater Influent vs. Effluent
1
10
100
1000
10000
100000
Caffeine
Acetam
inoph
en1,7
-Dim
ethylx
anthi
ne
Ibupro
fen
Atenolol
Compound
Con
cent
ratio
n (n
g/L)
InfluentEffluent
Grand Rapids Wastewater Influent vs. Effluent
0
500
1000
1500
2000
2500
3000
3500
Cholesterol Coprostanol Clofibric Acid Gemfibrozil
Compound
Con
cent
ratio
n (n
g/L)
InfluentEffluent
Grand Rapids Wastewater Influent vs. Effluent
050
100150200250300350400450
Sulfam
ethox
azole
Cimeti
dineTrim
ethop
rimCarb
amaze
pine
Fluoxeti
ne
Codeine
17-a-
Ethinyle
strad
iolMetop
rolol
Compound
Con
cent
ratio
n (n
g/L)
InfluentEffluent
Grand Rapids Wastewater Influent vs. Effluent
0102030405060708090
100
Estron
e
Estriol
Propran
ololThiob
enda
zole
Linco
mycin
Tylosin
Miconaz
ole17
-B-E
strad
iolWarf
arinDiltia
zem
Compound
Con
cent
ratio
n (n
g/L)
InfluentEffluent
Should We Regulate PPCPs?
• “Not everything that counts can be counted, and not everything that can be counted counts.”
– often attributed to Albert Einstein
Unanswered Questions• Is any of this a problem?
– Antibiotic resistance– Endocrine disruption– Aquatic life
• Persistence and bioaccumulation?
– Wildlife– Human health
• Allergic reactions?
• How can these compounds be removed?– Cost, technical feasibility
Points to Ponder• Extremely low concentrations
– Detected only because of improved technology
• Input is essentially constant – As is exposure of aquatic organisms
• Complex mixtures of compounds designed to be biologically active– Potential additive/synergistic effects
• “Pass-through” suggests resistance to biodegradation– Stable throughout manufacture/storage
• Need better fate and transport data to accurately assess impact
Acknowledgments
• Bryan Brooks and Kevin Chambliss, Baylor University Center for Reservoir and Aquatic Systems Research
• Janice Skadsen, City of Ann Arbor Water Utilities• John Wierenga, City of Grand Rapids Lake
Michigan Filtration Plant• Scott Allen, City of Monroe• Daniel Meyering and Brian Rice, Fleis and
VandenBrink Engineering
Compounds Detected in Source Water
0
5
10
15
20
25
30
35
40
45
Hormones
/Sterols
Anticon
vulsa
ntLipid
Regulators
Stimulants
Beta-Block
ers
Analges
ics
Antibiot
ics
Category
Con
cent
ratio
n (n
g/L)
Ann ArborGrand RapidsMonroe
Compounds Detected in Drinking Water
0
2
4
6
8
10
12
14
16
18
Hormones
/Sterols
Anticon
vulsa
ntLipid
Regulators
Stimulants
Beta-Block
ers
Analges
ics
Antibiot
ics
Category
Con
cent
ratio
n (n
g/L)
Ann ArborGrand RapidsMonroe
Effect of Water Treatment
0102030405060708090
100
Hormon
es/Sterol
sAnti
conv
ulsant
Lipid R
egula
tors
Stimula
ntsBeta
-Bloc
kers
Analge
sics
Antibio
tics
Category
Perc
ent R
emov
al
Ann ArborGrand RapidsMonroe
Compounds Detected in Wastewater Influent
0
5000
10000
15000
20000
25000
Hormon
es/Sterol
sAnti
conv
ulsant
Lipid R
egula
tors
Stimula
ntsBeta
-Bloc
kers
Analge
sics
Antibio
tics
Antide
pressa
nts
Category
Con
cent
ratio
n (n
g/L)
Ann ArborGrand Rapids
Compounds Detected in Wastewater Effluent
0
100
200
300
400
500
600
700
Hormon
es/Sterol
sAnti
conv
ulsant
Lipid R
egula
tors
Stimula
ntBeta
-Bloc
kers
Analge
sics
Antibio
tics
Antide
pressa
nts
Category
Con
cent
ratio
n (n
g/L)
Ann ArborGrand Rapids
Effect of Wastewater Treatment
-40
-20
0
20
40
60
80
100
Hormon
es/Ster
olsAnti
conv
ulsan
tLip
id Regu
lators
Stimula
ntsBeta
-Bloc
kers
Analges
icsAnti
biotic
sAnti
depres
sants
Category
Perc
ent R
emov
al
Ann ArborGrand Rapids
Ann Arbor Source Water vs. Drinking Water
0
20
40
60
80
100
120
Caffeine
Acetaminop
hen
Cholesterol
1,7-Dim
ethylx
anthine
17-a-E
thinylestr
adiol
Compound
Con
cent
ratio
n (n
g/L)
Source WaterDrinking Water
Ann Arbor Source Water vs. Drinking Water
0
2
4
6
8
10
12
14
16
Ibuprofen
Carbamaz
epine
Sulfamethox
azole
Codeine
Atenolol
Estrone
Estriol
Compound
Con
cent
ratio
n (n
g/L)
Source WaterDrinking Water
Ann Arbor Source Water vs. Drinking Water
0
2
4
6
8
10
12
14
Gemfibroz
ilCopros
tanol
Trimetho
prim
Metopro
lol17-B
-Estr
adiol
Diltiaze
mDiphe
nylhyd
ramine
Propranolo
l
Compound
Con
cent
ratio
n (n
g/L)
Source WaterDrinking Water
Ann Arbor Wastewater Influent vs. Effluent
1
10
100
1000
10000
100000
Caffein
e
Acetam
inoph
en1,7-
Dimeth
ylxan
thine
Ibupro
fen
Atenolol
Compound
Con
cent
ratio
n (n
g/L)
InfluentEffluent
Ann Arbor Wastewater Influent vs. Effluent
0100200300400500600700800900
100011001200130014001500
Choleste
rol
Sulfam
ethox
azole
Copros
tanol
Gemfib
rozilThiob
enda
zole
Carbam
azepin
eCim
etidine
Codeine
Trimeth
oprim
Estriol
Metoprol
ol
Compound
Con
cent
ratio
n (n
g/L)
InfluentEffluent
Ann Arbor Wastewater Influent vs. Effluent
0
10
20
30
40
50
60
Linco
mycin
Estron
e17
-B-E
strad
iol17
-a-Ethi
nyles
tradio
lMico
nazo
leProp
ranolo
lClof
ibric
Acid
Warfari
n
Diltiaze
m
Compound
Con
cent
ratio
n (n
g/L)
InfluentEffluent
Monroe Source Water vs. Drinking Water
0
20
40
60
80
100
120
Atenolol
Choleste
rol
Caffeine
Acetam
inoph
en
Sulfam
ethox
azole
Compound
Con
cent
ratio
n (n
g/L)
InfluentEffluent
Monroe Source Water vs. Drinking Water
02468
101214161820
1,7-D
imeth
ylxan
thine
Gemfib
rozilCarb
amaze
pine
Ibupro
fen
Metoprol
olTrim
ethop
rim
Estriol
Compound
Con
cent
ratio
n (n
g/L)
InfluentEffluent
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