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Pharmaceuticals in the Environment:
What we know and need to know
2009 Symposium on Pharmaceuticals in the Home and Environment
Northport, Maine
October 18-19, 2009
Herb Buxton
USGS Toxic Substances Hydrology Program
U.S. Department of the Interior
U.S. Geological Survey
2
Chemicals of Emerging Environmental
Concern: Emerging Contaminants
Not Just Pharmaceuticals!
Chemicals that:
• interact in their affect on organisms, &
• co-occur in the environment.
3
Modes of Action with
Chemical Interactions
• Endocrine Disruption (biogenic
hormones, synthetic hormones,
hormone mimics & blockers)
• Antimicrobial Resistance (synthetic
antimicrobials, natural antimicrobials,
metals, pesticides?)
4
Emerging Contaminants
• Human & Veterinary Pharmaceuticals
• Detergents
• Antioxidants
• Fire retardants
• Disinfectants
• Fumigants
• Fragrances
• Pesticides/
Repellants
•
•
•
•
•
•
•
Industrial Chem’s, HPVs
Some Metals
Biogenic Hormones
Phytoestrogens
Natural antimicrobials
Natural pesticides
Degradates/
Metabolites
5
Framing Research Questions
•
•
Are Pharm’s entering our environment?
•
•
Are there sensitive environmental settings?
•
Do Pharm’s persist to finished drinking water
and are they a human health risk?
•
How can we minimize their entry to the
environment or remove them?
What are the source pathways, their chemical
signatures/loads?
Do Pharm’s have adverse ecological health
effects?
6
Are Emerging Contaminants
entering our natural
environment?
7
National Surveys of
“Susceptible” Waters
 High density of population
and animal production.
Surface (139)
100
 Present in complex
mixtures.
80
Percent Detected
 Present in water at
sub-ppb concentrations
Ground (47)
60
40
20
 Greater levels in streams
than wells
0
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.
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Kolpin, et al., 2002; Barnes et al., 2008
0%
Miconazole
Gemfibrozil
Fluoxetine
Thiabendazole
Erythromycin
Metformin
Cimetidine
Carbamazapine
Water (30)
Diphenhydramine
Caffeine
Ranitidine
Acetaminophen
80%
Diltiazem
Dehydronifedipine
Trimethoprim
Cotinine
Codeine
Sulfamethoxazole
Percent Detected
8
Don’t just look in stream waters!
Sediment (36)
60%
40%
20%
Furlong, et al., 2003
9
Measurement Capabilities
•
•
•
Clofibric Acid (Buser 1998)
32 drugs in German WWTPs (Ternes 1998)
45 drugs in US Rivers (Kolpin et al. 2002)
•
•
•
•
•
•
•
amphetamines
antibiotics
antidepressants (SSRIs)
antiphlogistics
antivirals
barbiturates
beta-blockers
•
•
•
•
•
•
•
Ca channel blocker
contraceptives
cytostatics
fibrates
glucocorticoids
muscle relaxants
opioids
10
What are the source pathways
to the environment and their
chemical signatures/loads?
11
Human Source Pathways?
• WW Treatment Plants
•
•
•
•
Domestic Septic Systems
Land Application
Industrial/Commercial Discharges
Landfills
• Water Reuse
12
Animal Source Pathways?
• Grazing
• AFOs/CAFOs
• Waste lagoons
• Land application
• Processing
• Aquaculture
• Pets
13
WWTP Discharges to Streams
• Complex chemical mixtures.
• Multiple upstream WWTP
discharges.
• Significant % WW in some
streams (arid or urbanized
watersheds).
14
ECs in Biosolids Destined for Land App
Carbon Norm. Concentration (mg/kg,10-40% C)
Carbemazepine
Diphenhydramine
Fluoxetine
Triclosan
Range
15-1,200
32-22,000
100-4,700
1,170-32,900
Median
68
340
370
10,200
• Biosolids from 9 sites
• 53 (of 87) ECs detected
• 30 to 45 in each biosolid
• 25 in all samples
Kinney et al., 2006
15
Septic Systems
ECs found in septic wastewaters
and adjacent groundwater (Swartz
et al., 2006; Carrara et al., 2008)
Higher levels in commercial than
domestic septics (restaurants,
convenience stores, retail centers, schools,
veterinary hospitals) (Conn et al., 2006)
16
Conc. Animal Feeding Operations
• Large facilities
• Prophylactic doses
• Antibiotics, growth promoters,
estrus modulators, …
Manure (kg/day)
Human
Cow
Hog
Sheep
Chicken
1.5
30
4
1.5
0.14
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To
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Detections (%)
17
Antibiotics in Swine
Lagoons
100
90
80
70
60
Antibiotics in 46
Swine AFOs
50
40
30
20
10
0
Meyer et al., 2003
18
Are there sensitive
environmental settings?
19
Hospital Effluents (Antibiotics)
3 Hospitals in Southeast Queensland,
Australia
16 of the 27
antibiotics
detected.
Watkinson et al., 2009
20
Pharm. Manufacturing Facilities
WWTP near Hyderabad India
• Receives effluent
from 90 bulk drug
manufacturers.
• Samples on
consecutive days.
Active Ingredient
Ciprofloxacin
Drug Type
Range (mg/L)
antibiotic
28,000-31,000
Losartan
angiotensin II receptor antagonist
2,400-2,500
Cetrizine
H1-receptor antagonist
1,300-1,400
Metoprolol
B1-andrenoreceptor antagonist
800-950
Antibiotic
780-900
Citalopram
SSRI
770-840
Norfloxacin
antibiotic
390-420
Lomefloxacin
antibiotic
150-300
Enoxacin
antibiotic
150-300
Ofloxacin
antibiotic
150-160
Enrofloxacin
Larsson et al., 2007
21
Hydrologic Events
Spring Flush
Cedar Rapids, IA
Midwest Floods, Spring ‘08
21 herbicides, 27 degradates,
36 antibiotics in 51 Midwest
Streams
Scribner et al., 2003
22
Animal Waste Lagoon Failure
Aug 24, 2009
Sept 8, 2009
Sept 14, 2009
Sept 21, 2009
Midwest Headwaters Stream
23
Do EC’s have adverse
ecological health effects?
24
EC Uptake in Organisms
Plant Tissue
Animal Tissue
•
Oxytetracycline in alfalfa
(Kong et al., 2007).
•
•
Oxytetracycline, flumequine
& oxolinic acid in bryophytes
(Delepee et al., 2004).
Fluoxetine in bluegill, catfish,
carp, crappie (Brooks et al.,
2005).
•
Gemfibrozil in goldfish (Mimeault
et al, 2005).
•
Trimethoprim in carrots &
lettuce (Boxall et al., 2006).
•
Triclosan & Methyl-triclosan in
carp (Leiker et al., 2008).
•
Sulfamethazine in corn,
lettuce, potatoes (Dolliver, et
al., 2007).
•
Trimethoprim & Triclosan in
earthworms (Kinney et al., 2008).
25
Ecological Effects
•
Antibiotics: Reduced soil microbial activity at env. concentrations (Costanzo et
al., 2005; Thiele-Bruhn and Beck, 2005).
•
Diclofenac (NSAID): Consumption of diclofenac-treated meat caused renal
failure in vultures (Oaks et al., 2004).
•
Ciprofloxacin, triclosan, Tergitol NP 10: shifts in algal community structure
(Wilson et al., 2003) .
•
Drug Mixtures 13: Inhibited growth of human embryonic cells at environmental
levels (Pomati et al., 2006, 2008).
•
Fluoxetine: Affected reproduction in freshwater molluscs -- water-sediment
exchange (Sanchez-Arguello et al., 2009).
•
Antidepressants: (environmental levels) Affected predator avoidance behavior
of larval fathead minnow (McGee et al. 2009).
•
4-nonylphenol: (environmental exposures) Impaired reproductive potential of
male fathead minnows. (Schoenfuss et al., 2008).
•
Alkylphenolethoxylates: (environmental mixtures) Reduced reproductive
competence in male fathead minnows (Bistodeau et al., 2006).
•
Sewage Sludge: Affected bone homeostasis in sheep (Lind et al., 2009).
26
Endocrine Disruption: A Case Study
Boulder Creek, CO
<0.8
Low-head Dam
2.1
Boulder
WWTP
1.4
2.9
1.2
17b-Estradiol in stream water, in ng/L
Vajda et al., 2008
27
Estrogenicity of Boulder Effluent &
Boulder Creek
Non-hormone EACs
Estrone
17β-Estradiol
17α-Ethynylestradiol
Total Estrogen Equivalency
(in ng L-1 17β-Estradiol)
30
25
20
15
10
5
0
Reference Site WWTP Effluent
Effluent Site
Spring 2005
Vajda et al., 2008
28
Endocrine Effects in
Boulder Ck (White Sucker)
Sex, in Percent
Female
Intersex
Male
100%
90%
80%
70%
60%
50%
40%
30%
20%
10%
0%
Blood Vitellogenin
Cellular Abnormalities
male
Upstream
Intersex 0%
Downstream
18-Jun-04
19%
female
Vajda et al., 2008
29
Do EC’s persist to finished
drinking water and are they a
human health risk?
30
National Source Water Survey
60
Source-water reconnaissance (surface-water sites)
50
DW Sources (Streams) 49
Susceptible Streams 139
40
Stream reconnaissance (Kolpin, et al., 2002)
30
20
10
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Percent Detection
Frequency of Detection, in percent
Natural Dilution and Degradation
Focazio et al., 2008
31
ECs in Finished Drinking Water
*11 of 20 Pharm’s not detected
18 DW Facilities
Detections
14
15 Max. (ppt)
42
Pharm’s
PCPs
12
10
8
6
4
2
19
18
18
2.1 470
93
510
3
0.82 100
0.33 1.2 25
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Supported by AWWA
Research Fnd. &
WateReuse Fnd.
16
m
Conducted by
Southern Nevada
Water Authority
Detections in 18 Samples
18
Benotti et al., 2008
32
Human Health Risk?
• Chronic low-level exposure.
• Exposure to chemical mixtures.
• Sensitive subpopulations.
• Can we prioritize chemicals
systematically for effects studies?
33
How can we minimize their
entry to the environment or
remove them?
34
WWTPs Ability To
Reduce ECs
trickling
filter
activated sludge
A
B
C
D
Plant
Phillips et al., 2008
35
Removal in Treatment, NJ Facility
Finished Water
Percent Detection
Percent Detection
Raw Water
Levels Generally Reduced by
Treatment with GAC Filters
Pharmaceutical/Antibiotic
Flame retardant/Plasticizer
Fragrance
Pesticide
Plant/Animal steroid
Detergent metabolite
PAHs
Others
Stackelberg et al., 2004 & 2007
36
Thank you!
And thanks to the many
researchers who provided the
information presented.
For more info on USGS EC research:
http://toxics.usgs.gov