GC/MS Method for GC/MS Method for Determining the Occurrence and Determining the Occurrence and

Investigating Treatment Processes for Investigating Treatment Processes for Representative Representative EDCsEDCs and PPCPs in and PPCPs in Waters of Southeastern LouisianaWaters of Southeastern Louisiana

AWWA Annual Conference & Exposition, New Orleans, LAAWWA Annual Conference & Exposition, New Orleans, LA

June 18, 2002June 18, 2002

Glen R. Boyd, Ph.D., P.E. Helge Reemtsma

Dept. of Civil and Environmental Engineering

Deborah A. Grimm, Ph.D.Coordinated Instrumentation Facility

Tulane University, New Orleans, LA

AcknowledgementsAcknowledgementsSponsorsCenter for Bioenvironmental Research at

Tulane and Xavier UniversitiesTulane School of Engineering

Collaborators and Tech SupportSiddhartha Mitra – USGS (EEB) Jennifer Holland – CEE/TSPH-EHSReimers & Englande – TSPH-EHSRichard Campanella – CBRCraig Conard – CBR

Undergraduate StudentsSoren Eustis Kristen SmebyApryl Scott Sean ConnerRhonda Hattar Sarah RossRebekah Cohen Sarah PerksVictoria Nwosu Deante Preston

AcknowledgementsAcknowledgements

Wayne Wayne KoffskeyKoffskey, Jefferson Parish Water , Jefferson Parish Water Treatment PlantTreatment PlantRon Hoffman, Jefferson Parish Ron Hoffman, Jefferson Parish Wastewater Treatment PlantWastewater Treatment PlantSaadSaad JasimJasim, Windsor Utilities , Windsor Utilities CommissionCommissionSamarSamar MazloumMazloum, ENWIN Utilities, ENWIN Utilities

OutlineOutline

Target Compounds

Methods

Field Sampling

– WWTP effluent– Mississippi River water– Detroit River water– WTP processes

Conclusions

Target CompoundsTarget Compounds

Endocrine disrupting chemicalsLipid regulator, fungicides and disinfectantsAnti-inflammatory and analgesicsOthers

Endocrine disrupting Endocrine disrupting chemicalschemicals

CHO OH

CH3

CH3

CH3O

HOCH3

HO

OH

Bisphenol A 80-05-7228 g/mol

Estrone 53-16-7

270 g/mol

17β-Estradiol 50-28-2

272 g/mol

Lipid Regulator, Fungicides and Lipid Regulator, Fungicides and DisinfectantsDisinfectants

Clofibric Acid 882-09-7

214 g/mol

Chlorophene 120-32-1

218 g/mol

Triclosan 3380-34-5

288 g/mol

OH

Cl

CH2

Cl O

OHCl

Cl

Cl O COOH

CH3

CH3

AntiAnti--Inflammatory and AnalgesicsInflammatory and AnalgesicsNaproxen 22204-53-1

230 g/mol

(Naprosyn)

Ibuprofen 15687-27-1

206 g/mol

(Motrin, Advil)

Acetaminophen 103-90-2

151 g/mol

(Tylenol)

CH3O

CHCOOH

CH3

(CH3)2CHCH2 CHCOOH

CH3

OHCH3CNH

O

OthersOthers

O CHCH2CH2NHCH3F3C

N

NN

N

O

OH3C

CH3

CH3

ANTIDEPRESSANT

Fluoxetine 54910-89-3

309 g/mol

(Prozac)

HUMAN ACTIVITY MARKER

Caffeine 58-08-2

194 g/mol

MethodsMethodsSample Collection and Preparation

8L grab samples were taken. Canadian samples were acidified prior to shipment.Pre-filter samples with 1 µm and 0.2 µm glass fiber filtersIsolate PPCPs/EDCs using SPE disks (3M SDB-XC)Pre-condition with MeOH and DCMAcidify (pH 2) and add surrogate std.Vacuum extraction and air dry disk

MethodsMethods

Extraction and DerivatizationExtract with MeOH and DCM Dry samples (rapid vap w/N2)Dissolve in 1 mL BSTFA reagent Add 10 µL of internal std Derivatize at 80°C for 20 minAnalyze using GC/MS

MethodsMethodsGC/MS Setting

Injection: splitless2 µL injections @ 230°C onto DB5 column (25m w/0.25 µm film thickness and 0.25 mm ID)GC oven: 100°C (0 min), 5°C/min to 165°C (5min), 2°C/min to 175°C (0min) and 10°C/min to 320°C (5min), total run: 42.5 minMS is operated in +EI mode using SIM mode for sensitivity

MethodsMethods

GCMS (TIC) GCMS (TIC) ResultsResults

MethodsMethods

Target Compounds and Detection LimitsTarget Compounds and Detection LimitsTarget

CompoundIDL

[ng/L]Average % Recov.

% RSD

Compl of Deriv (%)

MDL* [ng/L]

Clofibric acid 3 60.8 12.6 100 0.6Estrone 3 91.9 5.1 100 0.517β-Estradiol 1 90.5 9.1 100 0.1Ibuprofen 13 47.1 26.9 0 3.5Naproxen 3 87.9 2.8 0 0.4Acetaminophen 45 N.D. N.D. 100 N.D.Bisphenol-A 0.6 99.7 3.5 100 0.1Chlorophene 0.6 71.7 5.9 100 0.1Triclosan 1 53.8 24 100 0.2Fluoxetine 178 86.1 7 84.7 25.8Caffeine 24 2.8 3.6 100 107.1* Based on a 2µL injection from a 1mL extract of a 8L sample.

Field SamplingField Sampling

1 - Mississippi River2 - Lake Pontchartrain3 - Tulane University4 – Jeff. Parish WTP5 – Jeff. Parish WWTP

Field SamplingField SamplingJeff. Par. WWTP & Miss. River, LAJeff. Par. WWTP & Miss. River, LA

ClCl22

WWTP1WWTP1PrimaryPrimary

ClarificationClarification

AerationAeration

BasinBasin

SecondarySecondary

ClarificationClarificationSamplingSampling

SiteSite JP1JP1

MississippiMississippi

RiverRiver

Results Results Jeff. Par. WWTP & Miss. River, LAJeff. Par. WWTP & Miss. River, LA

Sampling Site

date 3/14/02 3/14/02 9/14/01 9/24/01Target Compound ng/L ng/L ng/L ng/LClofibric acid N.D. N.D. N.D. N.D.Ibuprofen N.D. N.D. N.D. N.D.Acetaminophen N.D. N.D. N.D. N.D.Caffeine N.D. N.D. N.D. N.D.Fluoxetine N.D. N.D. N.D. N.D.Chlorophene N.D. N.D. N.D. N.D.Naproxen 106 81 37 39Triclosan 21 10 N.D. N.D.Bisphenol-A N.D. N.D. N.D. N.D.Estrone N.D. N.D. N.D. N.D.17β -Estradiol N.D. N.D. N.D. N.D.Bisphenol-A-d14* 13.6% 13.9% 68.0% 75.0%Estrone-d4* 52.6% 28.9% 103.4% 119.4%Acetaminophen-d4* 1.1% 1.2% N.D. N.D.* surrogate std. recovery , N.D. not detected, N.Q. not quantifiable

Jeff. Par. WWTPeffluent (WWTP1)

Miss . Rivershore (JP1)

Observations Observations Jeff. Par. WWTP & Miss. River, LAJeff. Par. WWTP & Miss. River, LA

Low concentrations of Low concentrations of –– naproxen (81naproxen (81--106 106 ngng/L)/L)–– triclosan (10triclosan (10--21 21 ngng/L) /L) were detected in effluent at JPWWTP.were detected in effluent at JPWWTP.

Low concentrations of Low concentrations of –– naproxen (37naproxen (37--39 39 ngng/L) /L) were detected in raw Miss. River water were detected in raw Miss. River water

in New Orleans. in New Orleans.

Field SamplingField SamplingJefferson Parish WTP, LAJefferson Parish WTP, LA

MississippiMississippi

RiverRiver

JP1JP1Coag/FlocCoag/Floc

SedimentSediment

Filtration &Filtration &

StorageStorage

DistributionDistribution

SystemSystem

PACPAC ClCl22

JP2JP2 JP3JP3

NHNH22ClCl

ResultsResultsJefferson Parish WTP, LAJefferson Parish WTP, LA

2/14/02 2/28/02 2/14/02 2/28/02 2/14/02 3/28/02Target Compound ng/L ng/L ng/L ng/L ng/L ng/LClofibric acid N.D. N.D. N.D. N.D. N.D. N.D.Ibuprofen N.D. N.D. N.D. N.D. N.D. N.D.Acetaminophen N.D. N.D. N.D. N.D. N.D. N.D.Caffeine N.D. N.D. N.D. N.D. N.D. N.D.Fluoxetine N.D. N.D. N.D. N.D. N.D. N.D.Chlorophene N.D. N.D. N.D. N.D. N.D. N.D.Naproxen 64 65 63 68 N.D. N.D.Triclosan N.D. N.D. N.D. N.D. N.D. N.D.Bisphenol-A N.Q. N.Q. N.Q. N.Q. N.Q. N.D.Estrone N.D. N.D. N.D. N.D. N.D. N.D.17β−Estradiol N.D. N.D. N.D. N.D. N.D. N.D.Bisphenol-A-d14* 62.8% 65.2% 46.0% 81.3% 94.9% 18.6%Estrone-d4* 130.1% 68.3% 118.1% 99.3% 106.7% 17.7%Acetaminophen-d4* 0.2% 0.2% 0.2% N.D. 0.1% N.D.* surrogate std. recovery , N.D. not detected, N.Q. not quantifiable

Jefferson Parish WTP, LAraw water (JP1) post conv. treat. (JP2) finished water (JP3)

Observations Observations Jefferson Parish WTP, LAJefferson Parish WTP, LA

Naproxen was detected in raw Miss. Naproxen was detected in raw Miss. River water (64River water (64--65 65 ngng/L)./L).

NaxproxenNaxproxen persisted after PAC and persisted after PAC and coag/floc/sedcoag/floc/sed (63(63--68 68 ngng/L)./L).

Naproxen was reduced (N.D) by Naproxen was reduced (N.D) by chlorination/chlorination/chloraminationchloramination..

Naproxen byproducts (?) Naproxen byproducts (?) –– more more research.research.

Comparison to USGS StudyComparison to USGS Study

KolpinKolpin, , et.al.et.al., EST, , EST, 20022002, v. 36, , v. 36, 12021202--1211.

Compound (Methods) USGS ng/L Tulane ng/LClofibric acid -- NDIbuprofen (3) <18 3.5*Acetaminophen (3) <9 NACaffeine (3) 68 NACaffeine (4) E 80 NAFluoxetine (3) <18 25.8*Chlorophene -- NDNaproxen -- 50Triclosan (4) <40 0.2*Bisphenol-A (4) E 60 0.1*Estrone (5) <5 0.4*17β-Estradiol (5) <5 0.1**Tulane's estimated MDL, -- not attemptedNA not applicable, ND not detected

1211.

St. St. FrancisvilleFrancisville, LA, LA

(100 miles north of N.O.)(100 miles north of N.O.)

Comparison to USGS StudyComparison to USGS Study

St. St. FrancisvilleFrancisville (USGS) is about 100 miles upstream (USGS) is about 100 miles upstream from New Orleans (Tulane).from New Orleans (Tulane).Tulane and USGS agree (<DL): Tulane and USGS agree (<DL): –– IbuprofenIbuprofen–– FluoxetineFluoxetine–– TriclosanTriclosan–– EstroneEstrone–– 1717ββ--EstradiolEstradiol

For For BisphenolBisphenol--A,A,–– Tulane reported <0.1 Tulane reported <0.1 ngng/L/L–– USGS reported 60 USGS reported 60 ngng/L (estimated) /L (estimated)

USGS applied several analytical methods whereas USGS applied several analytical methods whereas Tulane applied one method.Tulane applied one method.

Field SamplingField SamplingA.H. Weeks WTP, ONA.H. Weeks WTP, ON

OO33 ClCl22

Coag/FlocCoag/Floc

SedimentSediment

Filtration &Filtration &

StorageStorageWO1WO1WO2WO2

DistributionDistribution

SystemSystemDetroitDetroit

RiverRiver

Results Results A.H. Weeks WTP, ONA.H. Weeks WTP, ON

Detroit River finished water(WO1) (WO2)

Target Compound ng/L ng/LClofibric acid 103 N.D.Ibuprofen N.D. N.D.Acetaminophen N.D. N.D.Caffeine N.D. N.D.Fluoxetine N.D. N.D.Chlorophene N.D. N.D.Naproxen 63 N.D.Triclosan N.D. N.D.Bisphenol-A N.Q. N.Q.Estrone N.D. N.D.17β -Estradiol N.D. N.D.Bisphenol-A-d14* 66.7% 93.6%Estrone-d4* 77.2% 90.7%Acetaminophen-d4* N.D. 0.2%* surrogate std. recovery , N.D. not detected, N.Q. not quantitated

A.H. Weeks WTP (2/14/2002)

Observations Observations A.H. Weeks WTP, ONA.H. Weeks WTP, ON

ClofibricClofibric acid (103 acid (103 ngng/L) and /L) and naproxen (63 naproxen (63 ngng/L) were detected /L) were detected in raw Detroit River water.in raw Detroit River water.

ClofibricClofibric acid (N.D.) and acid (N.D.) and naxproxennaxproxen(N.D.) were reduced by (N.D.) were reduced by ozonationozonation, , coag/floc/sedcoag/floc/sed, and chlorination., and chlorination.

ClofibricClofibric acid and naproxen acid and naproxen byproducts (?) byproducts (?) –– more research.more research.

Field SamplingField SamplingENWIN Pilot WTP, ONENWIN Pilot WTP, ON

DetroitDetroit

RiverRiver

WO1WO1

Coag/FlocCoag/FlocSedimentSediment

Dual Media Dual Media Filter 1Filter 1

OO33

Raw Raw Water Water

StorageStorage

EN1EN1

Coag/FlocCoag/FlocSedimentSediment

Dual Media Dual Media Filter 2Filter 2

EN2EN2

Results Results ENWIN Pilot WTP, ONENWIN Pilot WTP, ON

Raw Water Finished Finished(WO1) (EN1) (EN2)

Target Compound ng/L ng/L ng/LClofibric acid 103 N.D. N.D.Ibuprofen N.D. N.D. N.D.Acetaminophen N.D. N.D. N.D.Caffeine N.D. N.D. N.D.Fluoxetine N.D. N.D. N.D.Chlorophene N.D. N.D. N.D.Naproxen 63 N.D. N.D.Triclosan N.D. N.D. N.D.Bisphenol-A N.Q. N.Q. N.Q.Estrone N.D. N.D. N.D.17β -Estradiol N.D. N.D. N.D.Bisphenol-A-d14* 66.7% 80.2% 91.5%Estrone-d4* 77.2% 82.1% 74.6%Acetaminophen-d4* N.D. N.D. N.D.

ENWIN Pilot WTP (2/14/2002)

* surrogate std. recovery , N.D. not detected, N.Q. not quantitated

Observations Observations ENWIN Pilot WTP, ONENWIN Pilot WTP, ON

ClofibricClofibric acidacid (N.D.) and (N.D.) and naxproxennaxproxen (N.D.) were (N.D.) were reduced by dual media reduced by dual media filtrations.filtrations.

Removal Removal mechanismsmechanismsand and byproductsbyproducts for for clofibricclofibric acid and acid and naproxen (?) naproxen (?) –– more more research.research.

ConclusionsConclusionsMethods DevelopmentMethods Development

A method has been developed for detection of a range of low level PPCP/EDC contaminants in raw and treated water.

The method is reliable for 9 target compounds:

Clofibric Acid Chlorophene Bisphenol AIbuprofen Naproxen EstroneFluoxetine Triclosan 17B-Estradiol

ConclusionsConclusionsOccurrence of EDCs/PPCPsOccurrence of EDCs/PPCPs

ClofibricClofibric acidacid was detected in was detected in –– Detroit River (ON)Detroit River (ON)

NaproxenNaproxen was detected in was detected in –– WWTP effluent (LA)WWTP effluent (LA)–– Mississippi River (LA)Mississippi River (LA)–– Detroit River (ON)Detroit River (ON)

TriclosanTriclosan was detected in WWTP effluent (LA)was detected in WWTP effluent (LA)BisphenolBisphenol--AA was detected but nonwas detected but non--quantifiablequantifiable–– Mississippi River (LA)Mississippi River (LA)–– Detroit River (ON)Detroit River (ON)

ConclusionsConclusionsOccurrence of EDC/PPCPsOccurrence of EDC/PPCPs

NQNQE60E60NQNQNDNDBisphenolBisphenol--AA

NDND<40<40NDND1010--2121TriclosanTriclosan

6363NANA3737--68688181--106106NaproxenNaproxen

103103NANANDNDNDNDClofibricClofibric acidacid

USGSUSGSTulaneTulaneDetroit Detroit RiverRiver

Mississippi RiverMississippi RiverJPWWTP JPWWTP EffluentEffluent

Compound Compound ((ngng/L)/L)

ConclusionsConclusionsTreatment ProcessesTreatment Processes

NaproxenNaproxen and and clofibricclofibric acidacid werewereNOT removed by NOT removed by coag/floc/sedcoag/floc/sedREMOVED by oxidation (ClREMOVED by oxidation (Cl22 or Oor O33))REMOVED by dual media filtrationREMOVED by dual media filtration

ConclusionsConclusionsTreatment ProcessesTreatment Processes

NDNDNDNDEN2 (ON)EN2 (ON)

NDNDNDNDEN1 (ON)EN1 (ON)

NDNDNDNDWO2 (ON)WO2 (ON)

6363103103WO1 (ON)WO1 (ON)

NDNDNDNDJP3 (LA)JP3 (LA)

6363--6868NDNDJP2 (LA)JP2 (LA)

6464--6565NDNDJP1 (LA)JP1 (LA)

DMFDMFOO33ClCl22ConvConvNaproxen Naproxen

((ngng/L)/L)ClofibricClofibric

Acid (Acid (ngng/L)/L)Treatment Process*Treatment Process*Sampling Sampling

SiteSite

* * ConvConv –– Coag/Floc/SedCoag/Floc/Sed OO33 -- OzonationOzonation

ClCl22 –– ChlorinationChlorination DMF DMF –– Dual Media FiltrationDual Media Filtration

GC/MS Method for GC/MS Method for Determining the Occurrence and Determining the Occurrence and

Investigating Treatment Processes for Investigating Treatment Processes for Representative Representative EDCsEDCs and PPCPs in and PPCPs in Waters of Southeastern LouisianaWaters of Southeastern Louisiana

Glen R. Boyd, Ph.D., P.E. Helge Reemtsma

Dept. of Civil and Environmental Engineering

Deborah A. Grimm, Ph.D.Coordinated Instrumentation Facility

Tulane University, New Orleans, LA