sources and occurrence of contaminants of emerging … stac blaney.pdf · lee blaney department of...

LeeBlaneyDepartmentofChemical,BiochemicalandEnvironmentalEngineering

UniversityofMarylandBaltimoreCounty

ChesapeakeBayProgram

ScientificandTechnicalAdvisoryCommittee

December5,2017

Sourcesandoccurrenceofcontaminantsofemergingconcernandtherisktheyposetothe

ChesapeakeBay

ChesapeakeBaySTAC- December5,2017 2

Mygoalsfortoday

1. Toprovideanoverviewoncontaminantsofemergingconcern

(CECs)andidentifypriorityCECs

2. Todescribeanalyticalmethodsusedtomeasuretrace

concentrationsofCECsincomplexenvironmentalmatrices

3. TodiscussourrecentworkondetectionofCECsini. theChesapeakeBay;

ii. urbanwatersheds;and,

iii. wastewatertreatmentplants

Overview


CECsarepresentinwateraroundtheworld

Radović etal.,2015

Torresetal.,2015

Matongo etal.,2015

Kolpinetal.,2002

Birchetal.,2015

Daietal.,2015

Emnet etal.,2015


Priority*CECs– endocrinedisruptors

Estrogenichormones– signalingmoleculesthataffectreproductive

systems;canimpactaquaticorganismsatconcentrationsaslowas1-

10ng/L;resultsinpopulationcrashes

[Kiddetal.,2007]


Priority*CECs– genotoxicpersonalcareproducts

UV-filters – thesemoleculesarepresentinmostpersonalcare

products(highloads);UV-filtersexhibitestrogenicactivity;recently

showntobetoxictocoralsat<100ng/L

“Oxybenzone poses a hazard to coral reef conservation and threatens the resiliency of coral reefs to climate change.” [Downsetal.,2015]

https://newsdeeply.imgix.net/20170615093325/Sunscreen-hand-print-on-coral.jpg

Antibiotics – sub-therapeuticconcentrationsofantibioticselicitcell-signalingresponses;environmentally-relevantlevelsofantibiotics

exertaselectivepressureforresistantorganisms


Priority*CECs– agrandpublichealthchallenge

[WEF,2013]

AnalyticalMethods


WemeasurealargesuiteofCECs…

…includingfluoroquinolones,sulfonamides,tetracyclines,macrolides,estrogenic

andandrogenichormones,andUV-filters(sunscreens).

CH3

O

N

OH

O

O

F

N

NH3C

CH3

NHS

O

O

H2 N

N

O

CH3 OH NCH3H3 C

OH

NH2

OOOH

OHOOH

H3C

OO

H3 C

OH3 C

O

H3C

HO

CH3

O

H3C

OOH3C

OH

NCH3H3C

H3 C OHCH3

N

O OO

CH3

H3C

OH

CH3HO

CH3

HO

O

CH3

O

O

OH

Ofloxacin

Roxithromycin

Doxycycline

Sulfamethoxazole

Estrone

Oxybenzone


SamplepretreatmentwithSolid-PhaseExtraction(SPE)

SPEservestwodominantpurposes:

• Removeinterferences

• Concentrateanalytes


SPEwithLC-ESI-MS/MS

Electrospray

ionizationParention

selection

(Q1)

Collisioncell

(q2)

Production

screening

(Q3)

Detector

Liquidchromatography

(separatesanalytes) Tandemmassspectrometry

(detectsanalytes)

1 2 3


TandemMSprovideshighselectivity/sensitivity

+

Ionizationm/z

separation Fragment Detector

++

m/zseparation

MS-1parention MS-2production

Mobilephasewithanalytes

ESI Q1 q2 Q3 MSLC

+

+

+ + +

+ +

• MS/MSdetectionmethodsmeasurethetransitionfrom[MS-1]to[MS-2]

• Minimalnoise/interferencefromotherspecies(comparedtobulkdetectors)


Nowmeasuring60-70CECsinenvironmentalsamples

Forthesakeofbrevity,fullanalytical

methodologiesarenotincludedhere

(estrogens/UV-filtersinHeetal.,2017J.Chromatogr.A;antibiotics,inprep).

Limitsofdetection≤1.5ng/L

SourcesofCECs


OccurrenceofCECsinMaryland

(3)Wastewater

treatmentplants

(1)Chesapeake

Bay

(2)GwynnsFalls

watershed

Hypothesis

CECsarepresentintheChesapeakeBayand

accumulateinoystertissue


AntibioticsintheChesapeakeBay

Compound Max.conc.(ng/L)

Azithromycin(AZI) 2.7± 0.5

Clarithromycin(CLA) 9.7± 0.6

Difloxacin(DIF) 0.9± 0.1

Enrofloxacin(ENR) 17.8± 1.3

Norfloxacin(NOR) 94.1± 28.1

Roxithromycin(ROX) 5.9± 0.0

Sulfamethoxazole(SMX) 14.8± 3.8

Mapcredit:AnneTimm (USFS)


UV-filtersandestrogenichormonesintheChesapeakeBay

Inspring2017,weconductedapreliminaryassessmentofCECs

at12sitesnearPrincessAnne,MDwithassistancefromthe

MarylandDepartmentofNaturalResources



CECsaccumulateinChesapeakeBayoysters



CurrentChesapeakeBaysamplingcampaign

water

wwv

sediment

oyster

SamplingdoneinconjunctionwithMDNR


“Wegetwhatwemeasure”

SamplingcampaignsforCECsfocusonexpectedsites

• Kolpin etal.,2002– “theselectionofsamplingsitesprimarily

focusedonareasconsideredsusceptibletocontaminationfromhuman,industrial,andagriculturalwastewater.”

• Barnesetal.,2008– “Siteselectionfocusedonareassuspectedtobesusceptibletocontaminationfromeither

animalorhumanwastewaters(i.e.downgradientofalandfill,

unsewered residentialdevelopment,oranimalfeedlot).”

Therehavebeenfeweffortsconductedin“unimpacted”streams

andwatersheds.


SourcesofCECs– revisitingassumptions


Wastewaterleaksarecommonoccurrences

Literatureindicatesthatsewerexfiltrationcanbeashighas10-

20%ofdryweatherflow;furthermore,largerleaks/spillsoccur

onaregularbasis…

The2004waterquality

managementplanstated,

“Sewagedischargeintothe

GwynnsFallsisamajor

concern…Manysectionsofthe

stream…areposteddueto

contaminatedstreamflow...

Continuoussewerleaksare

commonoccurrencesin

BaltimoreCity”.

Hypothesis

CECsarepresentinMarylandsurfacewaters

duetoleakingsewersystems


Wesampledunimpacted urbanstreams

Source:BaltimoreEcosystemStudy

Discharge(ft3/s)

DRKR

POBR

GFVN

Source:USGSNWIS

GFCP

Summersampling

6/15/16– 08/26/16

Wintersampling

11/8/16– 01/12/17


Awidevarietyofantibioticsweredetectedinwater

Compound Detectionfrequency(%)

Maximumconcentration(ng/L)

Ciprofloxacin 1.6 49

Ofloxacin 2.9 200

Azithromycin 4.5 13

Clarithromycin 5.7 280

Erythromycin 40.2 54

Roxithromycin 2.5 327

Tylosin 2.5 4.9

Sulfadimethoxine 3.3 7.1

Sulfadimidine 4.1 6.7

Sulfamethoxazole 37.3 71

Doxycycline 9.4 365

Methacycline 2.5 215

CH3O

OCH3

O

H3C

OH3COH

CH3

O

CH3

O

O

CH3

OH

NCH3

CH3

CH3OH

CH3

O

CH3HO

H3C

HO

CH3

NHS

O

O

H2N

N

OSMX

ERY


Antibioticdetectionsvariedbysite/season

Summer– 2016

Winter– 2016

CIP Ciprofloxacin

OFL Ofloxacin

MOX Moxifloxacin

AZI Azithromycin

CLA Clarithromycin

ERY Erythromycin

ROX Roxithromycin

TYL Tylosin

SCM Sulfacetamide

SDM Sulfadimethoxine

SDD Sulfadimidine

SMR Sulfamerazine

SMX Sulfamethoxazole

DC Doxycycline

MC Meclocycline

MTC Methacycline

OTC Oxytetracycline

SIL Sildenafil

OtherCIP OFL MOX AZI CLA ERY ROX TYL SCM SDM SDD SMR SMX DC MTC OTC SIL

POBR 0 0 0 0 0 1 0 0 0 0 0 0 1 0 0 0 0BARN 0 0 0 0 1 2 2 0 0 0 1 0 6 0 1 0 0GFGL 0 0 0 1 1 2 0 1 0 2 1 0 0 1 1 0 1GFGB 0 0 0 0 1 2 0 0 0 0 0 0 1 2 0 0 0MCDN 0 0 0 0 0 2 2 0 0 0 0 0 0 0 0 0 0GFVN 0 0 0 0 1 2 0 0 0 2 0 0 2 0 0 0 0DRKR 0 0 0 0 1 2 1 0 0 1 0 0 4 1 0 0 1GFCP 0 0 0 0 1 3 0 1 0 1 1 0 6 0 1 0 0GRGF 0 1 0 2 2 8 0 1 0 1 2 0 8 2 1 0 0

Sulfonamide TetracyclineFluoroquinolone MacrolideSite

OtherCIP OFL MOX AZI CLA ERY ROX TYL SCM SDM SDD SMR SMX DC MTC OTC SIL

POBR 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0BARN 0 0 0 0 0 0 0 0 0 0 0 0 1 2 1 0 0GFGL 0 0 1 0 0 1 0 0 0 0 0 1 0 0 0 0 0GFGB 0 0 0 0 0 0 0 0 0 0 0 0 1 2 0 0 0MCDN 0 0 0 0 0 2 0 0 0 0 0 0 0 2 0 0 0GFVN 0 0 0 0 0 2 0 0 0 0 0 0 5 0 0 0 0DRKR 0 0 0 0 0 1 0 0 0 0 0 0 3 0 0 0 0GFCP 0 0 0 0 0 6 0 0 0 0 0 0 9 0 0 0 0GRGF 1 1 0 0 0 10 0 0 0 0 0 0 8 1 0 0 0

Sulfonamide TetracyclineSite Fluoroquinolone Macrolide


MappingantibioticsinGwynnsFallswatershed

674ng/L

Wintermean*Summermean*

99ng/L


UV-filtersarewidelypresentinGwynnsFallswater

Compound Detectionfrequency(%)

Maximumconcentration(ng/L)

17α-ethinylestradiol - -

Estradiol - -

Estrone 41.4 6.4

Oxybenzone 100 251

4-Methylbenzylcathinone 1.2 31

Octocrylene 100 168

Ethylhexyl methoxycinnamate 68 161

Homosalate 98 314

CH3

O

O

OH CH3

H3C

O

O

N

CH3

H3C

CH3

O

O

OH

BP3 OC HMS


MappingUV-filtersinGwynnsFallswatershed

Wintermean*Summermean*

274ng/L


Estrogensandhormonesaccumulateincrayfish

[Heetal.,2017]

CH3

O

O

OH

CH3

HO

OH

HC

CH3

CH3

CH 3

O

O

OH

BP3:23.7±0.3ng/g

HMS:399± 48ng/g

EE2:17.1± 1.6ng/g

Hypothesis

CECsundergocomplextransformation

reactionsinwastewatertreatment

AntibioticconcentrationsarereducedinWWtreatment


[Heetal.,2015]


SomeofourobservedAB-to-ABtransformations

Conclusions


Concludingthoughts

1. OurworkintheGwynnsFallswatershedshowsthat

nonpoint(orunexpected)sourcescanbesignificant

inputsofCECsinurbanwatersheds

2. CECsarewidelypresentinChesapeakeBaywater,

sediment,andoystersandmoremonitoringstudiesare

requiredtobetterunderstandspatiotemporaltrends

3. AsCECswerespecificallydesignedtocausebiological

response,coupledchemical-responsestudiesshouldbe

conductedtoinvestigateunexpectedtoxicity

Mygreatteam

JoshBenoit

Ke He

Temitope IbitoyeMamathaHopanna

CharlesPortner HannahArisSavannahSteinly

UtsavShashvattLeeBlaney

EthanHain

Samina Musa

Aspecialthanks

FundingsourcesEnvironmentalProtectionAgency,P3program

MarylandIndustrialPartnerships

MarylandDepartmentofNaturalResources

NationalScienceFoundation,CAREERprogram

NationalScienceFoundation,EnvironmentalEngineeringprogram

NationalScienceFoundation,EnvironmentalSustainabilityprogram

NationalScienceFoundation,EnvironmentalChemicalSciencesprogram

NationalScienceFoundation,INFEWSN/P/H2Oprogram

PersonalCareProductsCouncil

UMBCOfficeofUndergraduateEducation

UMBCOfficeoftheVicePresidentofResearch

US-IsraelBinationalAgriculturalResearchandDevelopmentFund

USDAForestService

Thanksforyourattention

Anyquestions?

LeeBlaney

DepartmentofChemical,BiochemicalandEnvironmentalEngineering

UniversityofMarylandBaltimoreCounty

410-455-8608

[email protected]

www.umbc.edu/blaneylab

sources and occurrence of contaminants of emerging … stac blaney.pdf · lee blaney department of...

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