characterization of emerging contaminants and fish … · characterization of emerging contaminants...
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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
0%
20%
40%
60%
80%S
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Furlong et al.
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
0510152025303540
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percent detection
Provisional data
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
05101520253035
Estro
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Testo
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Provisional data
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
0%10%20%30%40%50%60%70%80%90%
100%
Upstream Downstream
18-Jun-04
Sex,
in P
erce
ntFemale Male Intersex
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