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U.S. Department of the InteriorU.S. Department of the InteriorU.S. Geological SurveyU.S. Geological Survey
Pharmaceuticals in the Environment: Pharmaceuticals in the Environment: What we know and need to knowWhat we know and need to know
2009 Symposium on Pharmaceuticals in the Home and Environment2009 Symposium on Pharmaceuticals in the Home and EnvironmentNorthport, MaineNorthport, MaineOctober October 1818--19,19,
20092009
Herb BuxtonHerb BuxtonUSGS Toxic Substances Hydrology ProgramUSGS Toxic Substances Hydrology Program
2
Chemicals of Emerging Environmental Chemicals of Emerging Environmental Concern: EConcern: Emerging Contaminantsmerging Contaminants
Not Just Pharmaceuticals!Not Just Pharmaceuticals!Chemicals that: Chemicals that:
•• interactinteract in their affect on organisms, &in their affect on organisms, &
•• coco--occur occur in the environment.in the environment.
3
Modes of Action with Modes of Action with Chemical InteractionsChemical Interactions
••
Endocrine Disruption (biogenic Endocrine Disruption (biogenic hormones, synthetic hormones, hormones, synthetic hormones, hormone mimics & blockers)hormone mimics & blockers)
••
Antimicrobial Resistance (synthetic Antimicrobial Resistance (synthetic antimicrobials, natural antimicrobials, antimicrobials, natural antimicrobials, metals, pesticides?)metals, pesticides?)
4
Emerging ContaminantsEmerging Contaminants
••
DetergentsDetergents••
AntioxidantsAntioxidants
••
Fire retardantsFire retardants••
DisinfectantsDisinfectants
••
FumigantsFumigants••
FragrancesFragrances
••
Pesticides/ Pesticides/ RepellantsRepellants
••
Industrial Industrial ChemChem’’ss, , HPVsHPVs••
Some Metals Some Metals
••
Biogenic HormonesBiogenic Hormones••
PhytoestrogensPhytoestrogens
••
Natural antimicrobialsNatural antimicrobials••
Natural pesticidesNatural pesticides
••
Degradates/ Degradates/ MetabolitesMetabolites
••
Human & Veterinary PharmaceuticalsHuman & Veterinary Pharmaceuticals
5
Framing Research QuestionsFraming Research Questions••
Are Are PharmPharm’’ss entering our environment? entering our environment?
•• What are the source pathways, their chemical What are the source pathways, their chemical signatures/loads? signatures/loads?
•• Are there sensitive environmental settings? Are there sensitive environmental settings?
•• Do Do PharmPharm’’ss have adverse ecological health have adverse ecological health effects? effects?
•• Do Do PharmPharm’’ss persist to finished drinking water persist to finished drinking water and are they a human health risk? and are they a human health risk?
•• How can we minimize their entry to the How can we minimize their entry to the environment or remove them?environment or remove them?
6
Are Emerging Contaminants Are Emerging Contaminants entering our natural entering our natural environment?environment?
7
High densityHigh density of population of population and animal production.and animal production.
Present in water at Present in water at subsub--ppb concentrationsppb concentrations
Present in complex Present in complex mixturesmixtures..
Greater levels in streams Greater levels in streams than wellsthan wells
National Surveys of National Surveys of ““SusceptibleSusceptible””
WatersWaters
KolpinKolpin, et al., 2002; Barnes et al., 2008, et al., 2002; Barnes et al., 2008
0
20
40
60
80
100
Non. d
rugs Antib
iotics
Pharms
Det. M
etab.
DEET
Caffe
ine Fluoxe
tine
Per
cent
Det
ecte
d
Surface (139) Ground (47)
Pre. dr
ugs
Deterge
nts
8
0%
20%
40%
60%
80%
Sul
fam
etho
xazo
le
Cod
eine
Cot
inin
e
Trim
etho
prim
Deh
ydro
nife
dipi
ne
Dilt
iaze
m
Ace
tam
inop
hen
Ran
itidi
ne
Caf
fein
e
Dip
henh
ydra
min
e
Car
bam
azap
ine
Cim
etid
ine
Met
form
in
Ery
thro
myc
in
Thia
bend
azol
e
Fluo
xetin
e
Gem
fibro
zil
Mic
onaz
ole
Per
cent
Det
ecte
d
Water (30) Sediment (36)
DonDon’’t just look in stream waters!t just look in stream waters!
Furlong, et al., 2003Furlong, et al., 2003
9
Measurement CapabilitiesMeasurement Capabilities••
Clofibric Acid (Clofibric Acid (BuserBuser
1998)1998)
••
32 drugs in German WWTPs 32 drugs in German WWTPs ((TernesTernes 1998)1998)••
45 drugs in US Rivers (45 drugs in US Rivers (KolpinKolpin
et al. 2002)et al. 2002)
••
amphetamines amphetamines ••
antibioticsantibiotics
••
antidepressants (antidepressants (SSRIsSSRIs))••
antiphlogistics antiphlogistics
••
antivirals antivirals ••
barbituratesbarbiturates
••
betabeta--blockers blockers
••
Ca channel blockerCa channel blocker••
contraceptives contraceptives
••
cytostaticscytostatics••
fibrates fibrates
••
glucocorticoids glucocorticoids ••
muscle relaxantsmuscle relaxants
••
opioidsopioids
10
What are the source pathways What are the source pathways to the environment and their to the environment and their chemical signatures/loads?chemical signatures/loads?
11
••
WW Treatment PlantsWW Treatment Plants••
Domestic Septic Systems Domestic Septic Systems
••
Land ApplicationLand Application••
Industrial/Commercial DischargesIndustrial/Commercial Discharges
••
LandfillsLandfills••
Water ReuseWater Reuse
Human Source Pathways?Human Source Pathways?
12
••
GrazingGrazing••
AFOs/CAFOsAFOs/CAFOs
••
Waste lagoons Waste lagoons ••
Land application Land application
••
ProcessingProcessing••
AquacultureAquaculture
••
PetsPets
Animal Source Pathways?Animal Source Pathways?
13
WWTP Discharges to StreamsWWTP Discharges to Streams
••
Complex chemical mixtures. Complex chemical mixtures.
••
Multiple upstream WWTP Multiple upstream WWTP discharges.discharges.
••
Significant % WW in some Significant % WW in some streams (arid or urbanized streams (arid or urbanized watersheds).watersheds).
14
Carbon Norm. Concentration (Carbon Norm. Concentration (μμg/kg,10g/kg,10--40% C)40% C)RangeRange
MedianMedian
CarbemazepineCarbemazepine
1515--1,2001,200
6868DiphenhydramineDiphenhydramine
3232--22,00022,000
340340
FluoxetineFluoxetine
100100--4,7004,700
370370TriclosanTriclosan
1,1701,170--32,90032,900
10,20010,200
Kinney et al., 2006Kinney et al., 2006
••
Biosolids from 9 sitesBiosolids from 9 sites••
53 (of 87) ECs detected53 (of 87) ECs detected
••
30 to 45 in each 30 to 45 in each biosolidbiosolid••
25 in all samples25 in all samples
ECs in Biosolids Destined for Land AppECs in Biosolids Destined for Land App
15
Septic SystemsSeptic Systems
ECsECs
found in septic wastewaters found in septic wastewaters and adjacent groundwater and adjacent groundwater (Swartz (Swartz et al., 2006; et al., 2006; CarraraCarrara et al., 2008)et al., 2008)
Higher levels in commercial than Higher levels in commercial than domestic domestic septicsseptics
((restaurants, restaurants,
convenience stores, retail centers, schools, convenience stores, retail centers, schools, veterinary hospitalsveterinary hospitals) ) (Conn et al., 2006)(Conn et al., 2006)
16
Conc. Animal Feeding OperationsConc. Animal Feeding OperationsManure (kg/day)
Human 1.5Cow 30Hog
4Sheep 1.5Chicken 0.14
••
Large facilities Large facilities ••
Prophylactic dosesProphylactic doses
••
Antibiotics, growth promoters, Antibiotics, growth promoters, estrus modulators, estrus modulators, ……
17
0
10
20
30
40
50
60
70
80
90
100
chlor
otet-to
tal
sulfa
methaz
inelin
comyc
intet
racyc
line
oxyte
tracy
cline
sulfa
thiaz
oletyl
osin
sulfa
dimeth
oxine
erythr
omyc
in-H2O
trimeth
oprim
sulfa
methox
azole
virgin
iamyc
in
sulfa
methizo
leTota
l
Antibiotics in 46 Antibiotics in 46 Swine AFOsSwine AFOs
Det
ectio
ns (%
)
Antibiotics in Swine Antibiotics in Swine LagoonsLagoons
Meyer et al., 2003Meyer et al., 2003
18
Are there sensitive Are there sensitive environmental settings?environmental settings?
19
Hospital Effluents (Antibiotics)Hospital Effluents (Antibiotics)
3 Hospitals in Southeast Queensland, 3 Hospitals in Southeast Queensland, Australia Australia
16 of the 27 16 of the 27 antibioticsantibiotics
detected.detected. 0.01
0.1
1
10
100
Ciproflox
acin
Cepha
lexin
Linco
mycin
Amoxyc
illin
Roxith
romycin
Sulfam
ethox
azole
Trimeth
oprim
Norflox
aacin
Doxyc
yclin
e
Enroflo
xacin
Clinda
mycin
Nalidix
ic ac
id
Oleand
omyc
in
Tetrac
yclin
ePen
icillin
V
Max
Con
c.,
g/L
Watkinson et al., 2009Watkinson et al., 2009
20
Pharm. Manufacturing FacilitiesPharm. Manufacturing Facilities
Larsson et al., 2007Larsson et al., 2007
WWTP near Hyderabad IndiaWWTP near Hyderabad India••
Receives effluent Receives effluent from 90 bulk drug from 90 bulk drug manufacturers.manufacturers.
••
Samples on Samples on consecutive days.consecutive days.
Active IngredientActive Ingredient
Drug TypeDrug Type
Range (Range (μμg/L)g/L)CiprofloxacinCiprofloxacin
antibioticantibiotic
28,00028,000--31,00031,000LosartanLosartan
angiotensin II receptor antagonistangiotensin II receptor antagonist
2,4002,400--2,5002,500CetrizineCetrizine
HH11
--receptor antagonistreceptor antagonist
1,3001,300--1,4001,400MetoprololMetoprolol
BB11
--andrenoreceptor antagonistandrenoreceptor antagonist
800800--950950EnrofloxacinEnrofloxacin
AntibioticAntibiotic
780780--900900CitalopramCitalopram
SSRISSRI
770770--840840NorfloxacinNorfloxacin
antibioticantibiotic
390390--420420LomefloxacinLomefloxacin
antibioticantibiotic
150150--300300EnoxacinEnoxacin
antibioticantibiotic
150150--300300OfloxacinOfloxacin
antibioticantibiotic
150150--160160
21
Hydrologic EventsHydrologic Events
Cedar Rapids, IA
Spring FlushSpring Flush
21 herbicides, 27 degradates, 21 herbicides, 27 degradates, 36 antibiotics36 antibiotics
in 51 Midwest in 51 Midwest
StreamsStreams
Midwest Floods, Spring Midwest Floods, Spring ‘‘0808
Scribner et al., 2003Scribner et al., 2003
22
Animal Waste Lagoon FailureAnimal Waste Lagoon Failure
Aug 24, 2009 Sept 8, 2009
Sept 14, 2009 Sept 21, 2009Midwest Headwaters StreamMidwest Headwaters Stream
23
Do ECDo EC’’s have adverse s have adverse ecological health effects?ecological health effects?
24
EC Uptake in OrganismsEC Uptake in Organisms
Plant TissuePlant Tissue••
OxytetracyclineOxytetracycline in in alfalfaalfalfa
(Kong et al., 2007).(Kong et al., 2007).
••
Oxytetracycline, flumequine Oxytetracycline, flumequine & & oxolinicoxolinic acidacid in in bryophytesbryophytes
((DelepeeDelepee
et al., 2004).et al., 2004).
••
Trimethoprim inTrimethoprim in carrots & carrots & lettucelettuce
((BoxallBoxall
et al., 2006).et al., 2006).
••
SulfamethazineSulfamethazine in in corn, corn, lettuce, potatoeslettuce, potatoes
((DolliverDolliver, et , et al., 2007).al., 2007).
Animal TissueAnimal Tissue••
FluoxetineFluoxetine in in bluegill, catfish, bluegill, catfish, carp, crappiecarp, crappie
(Brooks et al., (Brooks et al., 2005).2005).
••
GemfibrozilGemfibrozil in in goldfishgoldfish
((MimeaultMimeault
et al, 2005).et al, 2005).
••
Triclosan & MethylTriclosan & Methyl--triclosantriclosan in in carpcarp
((LeikerLeiker
et al., 2008).et al., 2008).
••
Trimethoprim & TriclosanTrimethoprim & Triclosan in in earthwormsearthworms
(Kinney et al., 2008(Kinney et al., 2008).).
25
••
AntibioticsAntibiotics: Reduced soil microbial activity at : Reduced soil microbial activity at envenv. concentrations (. concentrations (CostanzoCostanzo
et et al., 2005; Thieleal., 2005; Thiele--Bruhn and Beck, 2005).Bruhn and Beck, 2005).
••
Diclofenac (NSAID):Diclofenac (NSAID):
Consumption of diclofenacConsumption of diclofenac--treated meat caused renal treated meat caused renal failure in failure in vulturesvultures (Oaks et al., 2004).(Oaks et al., 2004).
••
Ciprofloxacin, triclosan, Ciprofloxacin, triclosan, TergitolTergitol
NP 10NP 10: shifts in algal community structure : shifts in algal community structure (Wilson et al., 2003) .(Wilson et al., 2003) .
••
Drug Mixtures 13Drug Mixtures 13: Inhibited growth of human embryonic cells at environmental : Inhibited growth of human embryonic cells at environmental levels (levels (PomatiPomati
et al., 2006, 2008). et al., 2006, 2008).
••
FluoxetineFluoxetine: Affected reproduction in freshwater : Affected reproduction in freshwater molluscsmolluscs
----
waterwater--sediment sediment exchange (Sanchezexchange (Sanchez--ArguelloArguello
et al., 2009).et al., 2009).
••
AntidepressantsAntidepressants: (: (environmental levels)environmental levels)
Affected predator avoidance behavior Affected predator avoidance behavior of larval fathead minnow (of larval fathead minnow (McGee et al. 2009).McGee et al. 2009).
••
44--nonylphenolnonylphenol: (: (environmental exposuresenvironmental exposures) Impaired reproductive potential of ) Impaired reproductive potential of male fathead minnows. (male fathead minnows. (SchoenfussSchoenfuss et al., 2008).et al., 2008).
••
AlkylphenolethoxylatesAlkylphenolethoxylates: (: (environmental mixtures)environmental mixtures)
Reduced reproductive Reduced reproductive competence in male fathead minnows (competence in male fathead minnows (BistodeauBistodeau et al., 2006).et al., 2006).
••
Sewage SludgeSewage Sludge: Affected bone homeostasis in sheep (Lind et al., 2009).: Affected bone homeostasis in sheep (Lind et al., 2009).
Ecological EffectsEcological Effects
26
Boulder Creek, COBoulder Creek, CO
Endocrine Disruption: A Case StudyEndocrine Disruption: A Case Study
VajdaVajda et al., 2008et al., 2008
<0.8
2.11.4
2.9
1.2
17b-Estradiol in stream water, in ng/L
Boulder WWTP
Low-head Dam
27
EstrogenicityEstrogenicity
of Boulder Effluent & of Boulder Effluent & Boulder CreekBoulder Creek
VajdaVajda et al., 2008et al., 2008
0
5
10
15
20
25
30
Tota
l Est
roge
n Eq
uiva
lenc
y(in
ng
L-1 1
7β-E
stra
diol
)
Reference Site WWTP Effluent Effluent Site
Non-hormone EACsEstrone17β-Estradiol17α-Ethynylestradiol
Spring 2005
28
Endocrine Effects in Endocrine Effects in Boulder Ck (Boulder Ck (White SuckerWhite Sucker))
VajdaVajda et al., 2008et al., 2008
0%10%20%30%40%50%60%70%80%90%
100%
Upstream Downstream
18-Jun-04
Sex,
in P
erce
nt
Female Male
Intersex 0% 19%Intersex 0% 19%
Cellular AbnormalitiesCellular Abnormalities
malemale
femalefemale
IntersexIntersex
Blood Blood VitellogeninVitellogenin
29
Do ECDo EC’’s persist to finished s persist to finished drinking water and are they a drinking water and are they a human health risk?human health risk?
30
Natural Dilution and DegradationNatural Dilution and Degradation
0
10
20
30
40
50
60
diltia
zem
tylos
in
dehy
dronif
edipi
ne
sulfa
methox
azole
linco
mycin
erythr
omyc
in-H2O
aceto
minoph
entrim
ethop
rim
1,7-di
methylx
anthi
neco
tinine
Freq
uenc
y of
Det
ectio
n, in
per
cent
Source-water reconnaissance (surface-water sites)
Stream reconnaissance (Kolpin, et al., 2002)
DW Sources (Streams) 49Susceptible Streams 139
Per
cent
Det
ectio
n
National Source Water SurveyNational Source Water Survey
Focazio et al., 2008Focazio et al., 2008
31
0
2
4
6
8
10
12
14
16
18
meprobam
atephe
nytoin
atenolol
carba
mazepine
gemfib
rozilTCEPDEETTCPP
sulfam
ethoxazole
fluoxe
tine
nonylp
henoldiaze
pam
triclos
anbisp
henol A
BenottiBenotti et al., 2008et al., 2008
ECsECs
in Finished Drinking Water in Finished Drinking Water
Conducted by Conducted by Southern Nevada Southern Nevada Water AuthorityWater Authority
Supported by AWWA Supported by AWWA Research Research FndFnd. & . & WateReuseWateReuse FndFnd. .
Pharm’sPCPs
42
19
18 182.1 470
93510
3
0.82 1000.33 1.2 25
15
Max. (ppt)
*11 of 20 *11 of 20 PharmPharm’’ss
not detectednot detected
Det
ectio
ns
18 DW Facilities
32
Human Health Risk?Human Health Risk?
••
Chronic lowChronic low--level exposure.level exposure.
••
Exposure to chemical mixtures.Exposure to chemical mixtures.
••
Sensitive subpopulations.Sensitive subpopulations.
••
Can we prioritize chemicals Can we prioritize chemicals systematically for effects studies?systematically for effects studies?
33
How can we minimize their How can we minimize their entry to the environment or entry to the environment or remove them?remove them?
34
Phillips et al., 2008Phillips et al., 2008
WWTPs Ability To WWTPs Ability To Reduce ECsReduce ECs
A B C DPlant
activated sludge
trickling filter
35
Removal in Treatment, NJ FacilityRemoval in Treatment, NJ Facility
StackelbergStackelberg et al., 2004 & 2007et al., 2004 & 2007
Raw WaterRaw Water
Perc
ent D
etec
tion
HHCBAHTN
Levels Generally Reduced by Levels Generally Reduced by Treatment with GAC FiltersTreatment with GAC Filters
Finished WaterFinished Water
Perc
ent D
etec
tion
HHCB
Pharmaceutical/AntibioticFlame retardant/PlasticizerFragrancePesticidePlant/Animal steroidDetergent metabolitePAHsOthers
36
Thank you!Thank you!
And thanks to the many And thanks to the many researchers who provided the researchers who provided the information presented.information presented.
For more info on USGS EC research:For more info on USGS EC research: http://http://toxics.usgs.govtoxics.usgs.gov