pharmaceuticals in the environment: what we know and need to … · 2009-12-01 · u.s. department...

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


390390--420420LomefloxacinLomefloxacin


150150--300300EnoxacinEnoxacin


150150--300300OfloxacinOfloxacin


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


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))


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

pharmaceuticals in the environment: what we know and need to … · 2009-12-01 · u.s. department...

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