U.S. Department of the InteriorU.S. Department of the InteriorU.S. Geological SurveyU.S. Geological Survey

Chemicals of Emerging Environmental Concern: The New Micropollutants

NJ Water Monitoring Coordinative CouncilNJ Water Monitoring Coordinative CouncilJanuary 23, 2008January 23, 2008

Herb BuxtonHerb BuxtonUSGS Toxic Substances Hydrology ProgramUSGS Toxic Substances Hydrology Program

2

•• Human DrugsHuman Drugs•• Vet. Drugs Vet. Drugs •• AntibioticsAntibiotics•• HormonesHormones•• SteroidsSteroids•• Detergents Detergents •• PlasticsPlastics

•• AntioxidantsAntioxidants•• Fire retardantsFire retardants•• DisinfectantsDisinfectants•• FumigantsFumigants•• FragrancesFragrances•• Insecticides/ Insecticides/

RepellantsRepellants

Chemicals of Emerging Chemicals of Emerging Environmental Concern?Environmental Concern?

3

Why the sudden interest?Why the sudden interest?Clofibric Acid found in Swiss Lakes Clofibric Acid found in Swiss Lakes and the North Sea.and the North Sea.

Clofibric Acid(Cholesterol Drug)

Mecoprop(Pesticide)

Cl O

CH3CH3

COOHCl O

CH3

COOH

H

CH3

Buser, et al, 1998.Buser, et al, 1998.

4

•• WWTPWWTP•• CSOsCSOs•• SepticsSeptics•• Industrial Industrial DischDisch..•• LandfillsLandfills•• Water Reuse.Water Reuse.

Human Waste PathwaysHuman Waste Pathways

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Animal AgricultureAnimal AgricultureWaste lagoonsWaste lagoonsLand application Land application ProcessingProcessingAquacultureAquaculture

Animal Waste PathwaysAnimal Waste Pathways Manure (kg/day)Human 1.5Cow 30Hog 4Sheep 1.5Chicken 0.14

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Selecting Compounds and Selecting Compounds and Designing StudiesDesigning Studies•• Quantities used.Quantities used.•• Pathways for chemical release.Pathways for chemical release.•• Health significance (Known or Potential). Health significance (Known or Potential). •• Ability to measure Ability to measure -- ReliablyReliably. . •• Anticipated environmental behavior.Anticipated environmental behavior.•• Potential as chemical indicators/tracers.Potential as chemical indicators/tracers.•• Stakeholder priorities.Stakeholder priorities.

7

What have we What have we learned?learned?

Present in water at Present in water at subsub--ppb conc.ppb conc.’’ss..

Present as complex Present as complex mixturesmixtures..

Reflect a wide range of Reflect a wide range of human activitieshuman activities..

Some are Some are mobile and persistentmobile and persistent..

Present in various Present in various environmentalenvironmental mediamedia(water, solids, tissue).(water, solids, tissue).

>1000 Wells>1000 Wells>400 Streams>400 Streams>75 >75 WWTPsWWTPs

USGS CEEC SitesUSGS CEEC Sites

8

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)

National Water SurveysNational Water Surveys

9

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

dWater (30) Sediment (36)

DonDon’’t just look in the water!t just look in the water!

10

ParoxetineParoxetine Metabolite and Metabolite and FluvoxamineFluvoxamine were not detected.were not detected.

SSRIsSSRIs in WW Effluent Minnesota, in WW Effluent Minnesota, 251 MGD, Population Served = 1.8 million251 MGD, Population Served = 1.8 million

FluoxetineNorfluoxetineSertralineNorsertralineParoxetineCitalopramBupropionVenlafaxineDuloxetine

FluoxetineNorfluoxetineSertralineNorsertralineParoxetineCitalopramBupropionVenlafaxineDuloxetine

11:30 PM11:30 PM7:30 AM 2:30 PM7:30 AM 2:30 PM0

100

200

300

400

500

600

700

1400

1500

1600

1700

1800

1900

2000

2100

2200

0

100

200

300

400

500

600

700

1400

1500

1600

1700

1800

1900

2000

2100

2200C

once

ntra

tion

(ng/

L)

Effluent Grab Samples Collected Same Day

11

MRI Contrast Agent

(Gromet and others, 1984; Bau and Dulski, 1996; Möller and others, 2002; Verplanck and others, 2003)

Gadolinium, Healthcare WW IndicatorGadolinium, Healthcare WW Indicator

0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16

-0.1 0 8.4 10.6

Distance from Source (km)

Gd

Con

cent

ratio

n (u

g/L)

Fourmile Ck

Boulder Ck

Distance

Distance

12

•• Endocrine Disruption. Endocrine Disruption.

•• Antimicrobial Resistance.Antimicrobial Resistance.

•• Surprising New Effects.Surprising New Effects.

•• Traditional Health Significance.Traditional Health Significance.

Environmental Health ConcernsEnvironmental Health Concerns

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Endocrine Disruption Endocrine Disruption

HormonesHormones –– The bodies The bodies chemical messengers.chemical messengers.

Endocrine DisruptorsEndocrine Disruptors ––biogenic or synthetic biogenic or synthetic hormones or mimics or hormones or mimics or blockers that interfere with the message.blockers that interfere with the message.

Observed EffectsObserved Effects –– Intersex (Intersex (vitellogeninvitellogenin, , cellular abnormalities), population effects (sex cellular abnormalities), population effects (sex ratios)ratios)

Desbrow et al. (1998)

Rivers in Britain

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Challenge of Effects Research Challenge of Effects Research ----Boulder Creek, COBoulder Creek, CO

<0.8 ng/L2.1 ng/L 1.4 ng/L

2.9 ng/L

1.2 ng/L

17b-Estradiol in stream water

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

Estr

ogen

equ

ival

ents

(ng/

L)

7/7/2005 7/14/2005 7/21/2005 7/28/2005

E3EE2E1E2

0%10%20%30%40%50%60%70%80%90%

100%

Upstream Downstream

18-Jun-04

Sex,

in P

erce

ntFemale Male Intersex

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Antibiotic ResistanceAntibiotic Resistance Direct use in orchards.

•• Resistance develops in Resistance develops in organisms.organisms.

•• Environmental transfer of Environmental transfer of resistance genes.resistance genes.

•• Multiple resistance. Multiple resistance.

•• Resistance from non antibiotics.Resistance from non antibiotics.

•• Resistance from chronic lowResistance from chronic low--level level exposure?exposure?

Aquaculture

Animal waste lagoons

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•• Antibiotics:Antibiotics: Reduced soil microbial activity at Reduced soil microbial activity at EnvEnv. . Concentrations (Concentrations (CostanzoCostanzo et al., 2005; Thieleet al., 2005; Thiele--Bruhn and Beck, 2005).Bruhn and Beck, 2005).

•• Triclosan (antimicrobial disinfectant):Triclosan (antimicrobial disinfectant): Effects Effects thyroid in thyroid in frogsfrogs ((VeldhoenVeldhoen et al., 2006).et al., 2006).

•• Diclofenac (nonDiclofenac (non--steroidal antisteroidal anti--inflammatory):inflammatory):Consumption of diclofenacConsumption of diclofenac--treated meat caused treated meat caused renal failure in renal failure in vulturesvultures (Oaks et al., 2004).(Oaks et al., 2004).

Other Ecological EffectsOther Ecological Effects

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•• Ciprofloxacin, triclosan, Ciprofloxacin, triclosan, TergitolTergitol NP 10:NP 10: shifts in shifts in algal community structure (Wilson et al., 2003) .algal community structure (Wilson et al., 2003) .

•• Drug Mixtures 13:Drug Mixtures 13: Inhibited growth of human Inhibited growth of human embryonic cells at embryonic cells at envenv. levels (. levels (PomatiPomati et al., 2006).et al., 2006).

Other Ecological Effects Other Ecological Effects ---- continuedcontinued

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IsoxaflutoleIsoxaflutole..

Low appl. rate pesticidesLow appl. rate pesticides

Isoxaflutole

Diketonitril

e

Benzoic acidAtraz

ine

deethylatraz

ine

deisopropylatraz

ine

Hydroxyatraz

ine

Metolach

lor

Metolach

lor-ESA

Metolach

lor-OXA

Acet/Met-ES

ASecAm0.0001

0.001

0.010

0.100

1.00

10.0

100

4/75 55/75 45/75 64/67 65/67 50/67 60/67 59/60 60/60 60/60 58/60

Con

c. In

μg/

L

OthersOthers::•• SulfonylureaSulfonylurea•• SulfonamideSulfonamide•• ImidazolinoneImidazolinone•• PyrethroidPyrethroid

Midwest Streams

And Degradates.And Degradates.

ppb

ppt

Other Other CEECsCEECs

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•• Deicing (airplane/roadways)Deicing (airplane/roadways)

•• Dust Suppression Dust Suppression

•• Coal Tar SealantsCoal Tar Sealants

No v D ec J a n F e b M a r A p r M a y2 0 0 3 - 2 0 0 4

0

2 0 0 0

4 0 0 0

6 0 0 0

Cl

2000

4000

6000

0

11/03 1/04 3/04 5/04

Chloride Concentration

(mg/L)

Lincoln CreekMilwaukee, WI

Water-Quality Criteria

CorsiCorsi, Finger, Van , Finger, Van MetreMetre

Other Other CEECsCEECs

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Other Other CEECsCEECs

•• Algal ToxinsAlgal Toxins –– a a different source.different source.

Midwest Midwest cyanotoxincyanotoxinLake & Reservoir recon. (27, blooms)Lake & Reservoir recon. (27, blooms)

Analyzing samples as part of USEPA Analyzing samples as part of USEPA National Lakes Survey. (1200 pelagic)National Lakes Survey. (1200 pelagic)

LoftinLoftin, Graham, Meyer, Graham, Meyer

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•• PathogensPathogens

•• Nanomaterial (carbon, metals)Nanomaterial (carbon, metals)

•• GenesGenes

•• Surprises!Surprises!

EberlEberl, Taylor, Taylor

Other Other CEECsCEECs

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Information & Research NeedsInformation & Research Needs

•• Identifying priority compounds and source pathways.Identifying priority compounds and source pathways.

•• Improved methods (occurrence and effects).Improved methods (occurrence and effects).

•• Comprehensive exposure characterization.Comprehensive exposure characterization.

•• Comparative efficacy of treatment technologies and Comparative efficacy of treatment technologies and BMPsBMPs..

•• Ability to extrapolate from ecologic effects to human risk.Ability to extrapolate from ecologic effects to human risk.

•• Additional info on specific sources and sensitive Additional info on specific sources and sensitive environ.environ.’’ss..

•• ToxTox. testing of priority compounds & environment mixtures.. testing of priority compounds & environment mixtures.

•• Field demonstration of linkage between exposure & effects.Field demonstration of linkage between exposure & effects.