CharacterizationCharacterizationof Emerging Contaminants and of Emerging Contaminants and

Fish HealthFish Healthin Pennsylvania Watersin Pennsylvania Waters

SWEP Capital Chapter

Lunch & LearnNovember 17, 2010

Kent CrawfordKent CrawfordU.S. Geological SurveyU.S. Geological Survey

Pennsylvania Water Science CenterPennsylvania Water Science Center

Roy Orbison

Roy Orbison: 1936-1988Five Grammy awards

Rock and Roll Hall of Fame (1987)

Four Key Concepts:

The Mediterranean Sea

Roy Orbison

Birth control pills

Fathead minnows

What are emerging contaminants?What are emerging contaminants?

•• Compounds that we are Compounds that we are just now beginning to track just now beginning to track in the environment.in the environment.

•• Many new compounds.Many new compounds.

•• Some existing compounds. Some existing compounds. 

•• Also called chemicals of Also called chemicals of emerging concern.emerging concern.

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

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

RepellantsRepellants•• NanomaterialsNanomaterials

EmergingEmerging ContaminantsContaminants

Endocrine DisruptorsEndocrine Disruptors•• Interfere with or mimic natural Interfere with or mimic natural 

hormones.hormones.

•• Can cause changes in reproduction, Can cause changes in reproduction, development, and/or behavior of an development, and/or behavior of an organism.organism.

•• Hormones Hormones –– estrogen, testosterone.estrogen, testosterone.

•• Fish health issues Fish health issues –– intersex fish.intersex fish.

•• Potential human health issues.Potential human health issues.

Laboratory Laboratory Methods DevelopmentMethods Development

Detection levels at expected ambient concentrations(ppb, ppt, ppq)

New lab capabilities for ECs:New lab capabilities for ECs:

-- PharmaceuticalsPharmaceuticals

-- AntibioticsAntibiotics

-- HormonesHormones

-- Wastewater compoundsWastewater compounds

-- Streams (1999Streams (1999--2000)2000)

-- Ground Water (2000)Ground Water (2000)

-- Sources of Drinking Water (2001)Sources of Drinking Water (2001)

-- Streambed Sediment (2002)Streambed Sediment (2002)

Occurrence Occurrence -- National Recon StudiesNational Recon Studies

ES&T; March 15, 2002 v. 36, no. 6, p. 1202-1211

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Water and/or Sediment Water and/or Sediment

SourcesSourcesHumanHuman•• Wastewater treatment plantsWastewater treatment plants•• Combined sewer overflowsCombined sewer overflows•• Onsite septic systems Onsite septic systems •• Industrial dischargesIndustrial discharges•• LandfillsLandfills•• Water reuseWater reuse

AnimalAnimal•• FeedlotsFeedlots•• Waste Waste lagoons, etc.lagoons, etc.•• Land application Land application •• Processing plantsProcessing plants•• AquacultureAquaculture

Collaborative Partnership

Occurrence ofOccurrence ofEmerging ContaminantsEmerging Contaminantsin Pennsylvania Watersin Pennsylvania Waters

Project Team

Connie LoperDrew ReifLinda ZarrJohn Clune

Justin KnudsenKevin Breen

Rhonda ManningArianne Proctor

Bob TitlerPaul Curry

Phil ConsonaryPat Bowling

Project Team

Connie LoperDrew ReifLinda ZarrJohn Clune

Justin KnudsenKevin Breen

Rhonda ManningArianne Proctor

Bob TitlerPaul Curry

Phil ConsonaryPat Bowling

Human Health Issues:

Drinking water

USGS PaWSC USGS PaWSC –– PaDEP WQN PaDEP WQN SamplingSampling

•• Cooperative project with PaDEP, U.S. EPA.Cooperative project with PaDEP, U.S. EPA.

•• Started in March 2007.Started in March 2007.

•• Three years of samplingThree years of sampling

•• 27 sites across the state.27 sites across the state.

•• Sampling near drinking water intakes.Sampling near drinking water intakes.

•• Sampling quarterlySampling quarterly

•• Pharmaceuticals, antibiotics,Pharmaceuticals, antibiotics,and hormones. and hormones. 

Sampling•• All Teflon equipmentAll Teflon equipment

•• Critically cleaned Critically cleaned ––methanol rinsedmethanol rinsed

•• Two person field crewTwo person field crew

•• Composite sample from 3Composite sample from 3‐‐15 locations in the stream15 locations in the stream

•• All samples analyzed at All samples analyzed at USGS labs.USGS labs.

Target PharmaceuticalsTarget Pharmaceuticals

AcetaminophenAcetaminophenCaffeineCaffeine

CarbamazepineCarbamazepineCodeineCodeineCotinineCotinine

DehydronifedipineDehydronifedipineDiltiazemDiltiazem

DiphyenydramineDiphyenydramine

FluoxetineFluoxetinepp--XanthineXanthineRantidineRantidine

SalbutamolSalbutamolSulfamethoxazoleSulfamethoxazole

ThiabendazoleThiabendazoleWarfarinWarfarin

15 compounds

Target AntibioticsTarget Antibiotics

MacrolidesAzithromycinAzithromycinErythromycinErythromycin

AnhydroAnhydro--erythromycinerythromycinRoxithromycinRoxithromycin

TylosinTylosinVirginiamycinVirginiamycin

QuinolinesCiprofloxacinCiprofloxacinLomefloxacinLomefloxacinNorfloxacinNorfloxacinOfloxacinOfloxacin

SarafloxacinSarafloxacinEnrofloxacinEnrofloxacin

SulfonamidesSulfachloropyridazineSulfachloropyridazine

SulfadiazineSulfadiazineSulfadimethoxineSulfadimethoxineSulfamethazineSulfamethazineSulfamethoxazoleSulfamethoxazole

SulfathiazoleSulfathiazole

TetracyclinesChlorotetracyclineChlorotetracycline

EpiEpi--chlorotetracyclinechlorotetracyclineIsoIso--chlorotetracyclinechlorotetracycline

EpiEpi--isoiso--chlorotetracyclinechlorotetracyclineDoxycyclineDoxycycline

OxytetracyclineOxytetracyclineEpiEpi--oxytetracyclineoxytetracycline

TetracyclineTetracyclineEpiEpi--tetracyclinetetracycline

Other AntibioticsLincomycinLincomycin

TrimethoprimTrimethoprimChloramphenicolChloramphenicol

OrmetoprimOrmetoprim

31 compounds

Target HormonesTarget Hormones11‐ketotestosterone

17‐alpha‐ethynylestradiol

17‐beta‐estradiol

Norethindrone

3‐beta‐coprostanol

4‐androstene‐3,17‐dione

Cholesterol

Cis‐androsterone

Trans‐diethylstilbestrol

Epitestosterone

Equilenin

Estriol

Mestranol

Progesterone

Dihydrotestosterone

Testosterone

Bisphenol   a

17 compounds

Results Results •• All 27 sites had at least 1 compound detected.All 27 sites had at least 1 compound detected.

•• 12 of the 15 (80 %) pharmaceutical compounds 12 of the 15 (80 %) pharmaceutical compounds analyzed were detected at least once. analyzed were detected at least once. 

•• 16 of 31 (52 %) antibiotic compounds detected at 16 of 31 (52 %) antibiotic compounds detected at least once. least once. 

•• 9 of 17 (53 %) hormone compounds9 of 17 (53 %) hormone compoundsdetected at least once.detected at least once.

Commonly Detected Pharmaceuticals Commonly Detected Pharmaceuticals

•• Caffeine Caffeine ‐‐ StimulantStimulant

•• Carbamazepine Carbamazepine ‐‐ Mood stabilizing (epileptic) Mood stabilizing (epileptic) 

•• AcetaminophenAcetaminophen‐‐ Analgesic (Tylenol)Analgesic (Tylenol)

•• Diphenhydramine Diphenhydramine ‐‐ Antihistamine (Benadryl)Antihistamine (Benadryl)

•• Cotinine Cotinine ‐‐ Metabolite of nicotineMetabolite of nicotine

Pharmaceuticals detectedPharmaceuticals detected

Provisional data

Commonly Detected AntibioticsCommonly Detected Antibiotics•• Sulfamethoxazole Sulfamethoxazole ‐‐ Human useHuman use

•• Trimethoprim Trimethoprim ‐‐ Human use Human use 

•• Azithromycin  Azithromycin  ‐‐ Human useHuman use

•• Ofloxacin Ofloxacin ‐‐ Human useHuman use

•• Tylosin Tylosin ‐‐ Used for cattle, swine, and poultry.Used for cattle, swine, and poultry.

Antibiotics detectedAntibiotics detected

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Commonly Detected HormonesCommonly Detected Hormones•• Estrone Estrone ‐‐‐‐ Female hormoneFemale hormone

•• 44‐‐androstene androstene ‐‐ 3,17 dione 3,17 dione ‐‐‐‐ Male hormoneMale hormone(testosterone precursor)(testosterone precursor)

•• 17 beta estradiol 17 beta estradiol ‐‐‐‐ Female hormoneFemale hormone

•• CisCis‐‐androsterone androsterone ‐‐‐‐ Male hormoneMale hormone(testosterone metabolite)(testosterone metabolite)

Hormones detectedHormones detected

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LowLow--LowLow--Low Low ConcentrationsConcentrations

•• Measured in nanograms (parts per trillion).Measured in nanograms (parts per trillion).•• No regulatory limits.No regulatory limits.•• Concentrations in surface waters are Concentrations in surface waters are miniscule when compared to pharmaceutical miniscule when compared to pharmaceutical doses.doses.

•• Acetaminophen in TylenolAcetaminophen in Tylenol325 mg325 mg

•• Acetaminophen in waterAcetaminophen in water0.00000005 mg/L0.00000005 mg/L

Mediterranean Sea

You would have to drink

6.5 billion liters of waterto get one dose of regular strength Tylenol

Mediterranean Sea

Human health risksHuman health risks??????

Antibiotic resistant bacteriaAntibiotic resistant bacteria

Endocrine disruptionEndocrine disruption

Neurological interferenceNeurological interference

Human Health RisksHuman Health Risks

Antibiotic ResistanceAntibiotic Resistance

MRSA – Methicillin-resistant Saphylococcus aureus

Bacterial population

Drug-resistant bacteria

Population growth

Genetic mutation

Exponentialgrowth

Mercy!

Mercy  ~  MRSA  = Methicillin‐resistant Saphylococcus aureus

Antibiotic ResistanceAntibiotic Resistance

“Only one bacterium out of a population has to survive in order to replenish … a complete new population of resistant organisms.”

Dr. Stuart Levy, Tufts University

Emerging Contaminants ProjectEmerging Contaminants Project

ResultsResults::

•• Very few detections upstream from WWTPs.Very few detections upstream from WWTPs.

•• Lots of detections downstream from WWTPs.Lots of detections downstream from WWTPs.

•• All concentrations are low (sub microgram/liter levels)All concentrations are low (sub microgram/liter levels)

Killinger Creek, Lebanon County

Sinkhole

Lititz Run, Lancaster County

ResultsResults

•• Low concentrations of some antibiotics:Low concentrations of some antibiotics:–– Several streamsSeveral streams–– ErythromycinErythromycin–– SulfamethoxyzoleSulfamethoxyzole

•• Low concentrations of some pharmaceuticalsLow concentrations of some pharmaceuticals–– Diphenhydramine (antihistamine Diphenhydramine (antihistamine –– Benadryl)Benadryl)–– Cotinine (metabolite of nicotine)Cotinine (metabolite of nicotine)–– CarbamazepineCarbamazepine

•• MoodMood‐‐stabilizing drugstabilizing drug•• Bipolar disorder Bipolar disorder 

Our ability to measure contaminants currently exceeds our understanding of their environmental effects.

Ecological EffectsEcological Effects

InIn--stream Study of ECsstream Study of ECsBoulder Creek (CO)Boulder Creek (CO)

-- EffluentEffluent--dominated systems (WWTP discharge)dominated systems (WWTP discharge)-- Multiple ECs presentMultiple ECs present-- Relatively small basin sizesRelatively small basin sizes

Effects Research 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

17b17b--Estradiol in stream waterEstradiol in stream water

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

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100%

Upstream Downstream

18-Jun-04

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Pennsylvania ResultsPennsylvania Results

Intersex conditionIntersex condition

found in some Pennsylvania fishfound in some Pennsylvania fish

Intersex in BassIntersex in BassMost often observed Most often observed 

microscopically as microscopically as immature oocytes within immature oocytes within testestestes

Suggested as a marker Suggested as a marker of endocrine disruptionof endocrine disruption

Used as an indicator of Used as an indicator of exposure to estrogenic exposure to estrogenic compoundscompounds

Developing  oocytes

Normal

Intersex

What is the Impact of Intersex?What is the Impact of Intersex?

•• Not sure.Not sure.

•• Fish still spawn.Fish still spawn.

•• Sperm are less motile.Sperm are less motile.

•• Fewer fertilized eggs?Fewer fertilized eggs?

•• Fewer baby fish?Fewer baby fish?

•• Smaller population?Smaller population?

•• Immune system compromised?Immune system compromised?

PFBC Surveys of YoungPFBC Surveys of Young--ofof--thethe--Year Year Smallmouth BassSmallmouth Bass

“Columnaris bacteria (Flavobacterium columnare) appears to be the primary pathogen” (Ken Stark PFBC, 2008)

Bacterial infection

Diseased or Dead YOY SMB Diseased or Dead YOY SMB ---- July 2007July 2007

2007

Dr. Karen KiddProfessor, University of New Brunswick

Kidd, K.A., P.J. Blanchfield, K.H. Mills, V.P. Palace, R.E. Evans, J.M. Lazorchak and R. Flick. 2007. Collapse of a fish populationfollowing exposure to a synthetic estrogen. Proceedings ofthe National Academy of Sciences 104(21):8897‐8901. 

Experimental Lakes Area

Fathead minnows

Photo courtesy of Aquatic Environmental Services, Inc.

Photo courtesy of Cornell University.

Birth Control Pills

Birth control pills = 17a-ethynylestradiol

Canadian StudyCanadian Study•• SevenSeven‐‐year studyyear study

•• Two similar lakesTwo similar lakes

•• Fathead minnowsFathead minnows

•• Add estrogen to one lakeAdd estrogen to one lake

Control experimental lake

Treatment experimental lake

17a-ethynylestradiol

Kidd and others, 2007

Canadian StudyCanadian Study

Control experimental lake

Treatment experimental lake

17a-ethynylestradiol

Fish population crashed

Kidd and others, 2007

Fish population O.K.

What have we learned about ECs?What have we learned about ECs?

Present at sub-ppb concentrations in water.

- Streams and Groundwater

Present as complex mixtures.

Reflect a wide range of human activities.

Some compounds mobile and persistent.

Depend on the media (water, solids, tissue) sampled.

What does it all mean ?What does it all mean ?

•• No waterNo water‐‐quality standards.quality standards.

•• No evaluation of mixtures, No evaluation of mixtures, synergistic effects.synergistic effects.

•• Few studies on human health effects.Few studies on human health effects.

DonDon’’t Panic!t Panic!

butbut……

Be ConcernedBe Concerned

Questions???Questions???

Contact:

Dr. J. Kent CrawfordU.S. Geological Survey215 Limekiln RoadNew Cumberland, Pa. 17070

717-730-6909