TICs by State-of-the-Art SolidPhase Extraction: Mining the

Preliminary Results

ByR. Lee Lippincott Ph.D.

Judith Louis Ph.D., Gail Carter, Julia Barringer, Jessica Hopple,Robert Stiles, Brian Buckley Ph.D.

Field Study: Sites of Thirty-one WellsSampled

All 593Public CommunitySupply Wells in theCoastal Plain, withVOC SusceptibilityScores

The 16 pairs ofHigh/Low WellsSelected for Samplingin Year 2 of the Study

The 16 High/LowPairs of WellsSelected forSampling

FinalSusceptibilityRank shown foreach well

Public Community Water Supply Systems in the Coastal Plainwith both High and Low Final Susceptibility Ranks

An example of 2 pairs of High/Low Wells

950 feet

875 feet

NJDEP Source Water AssessmentProgram (SWAP)

Model Developed by NJDEP and USGS RelatingGroundwater Quality to Land Use Patterns

2337 Community Water Supply Wells in NewJersey

Wells Given a Score and Rating Based onSensitivity and Intensity of Use Factors

Goals of Study

1. Evaluate Analytical Methods for the Optimizationof Compound Recovery

2. Gather Data on the Contamination of the WellsSampled by NJDEP so that SWAP Model can beValidated

Previous Work

EPA 8270 and 525.2 Analyzes Water for Semi volatileOrganic Contaminants (SVOCs) by SPE-GC/ITMSMethod Detection Limits (MDLs) Lowered for PAHs,PCBs and Pesticides using Modified EPA 525.2 MethodField Tested Method on Water Treatment Plants in NewJerseyDetection of a Number of Unregulated Contaminants

C-18

DVB

Solid Phase Materials

Discovery Polymer

Analytical Instrumentation

Solid Phase Microextraction (SPME)

J. Chromatography A, 1996, 733, 143-157

FiberAgitationSalinityExtraction TimeExtraction TemperaturepHSampling Mode

Parameters to Optimize for SPME

Optimized SPME DirectExtraction Conditions

Fiber – 70μm CW/DVBSalinity – 10% NaClExtraction Time – 50 MinutesExtraction Temp – 45°CpH - Neutral

3 Fibers - 3 Methods

100μm PDMSpolydimethylsiloxane

70μm CW/DVBCarbowax-divinylbenzene

85μm PApolyacrylate

Phthalates

General SVOCs

Phenols

MethodsFibers

Absorption Vs. AdsorptionAdsorption: Surface Phenomena

Absorption: Diffusion PhenomenaSPME FiberSPME Fiber

Criteria for Selectingan Extraction

Method (SPE vs.SPME)

Cost/Time of Analysis

Background ContaminantsSample ConsumptionMethod Detection LimitsField Test

Background Contaminants:BreakingMethods into Components

SolventsGlasswareSPE Column HousingsSPE Sorbent Materialand Frits

FiberSampling VialsWaterSalt

SPE SPME

Most Frequently Detected SPMEArtifacts

Compound Source(s)1,9-Nonanediol Carbowax Phase of SPME FiberBis Substituted Compounds Epoxy Glue of SPME NeedleCyclodecanol SPME Vial or Crimp TopDibutyl Phthalate SPME Vial or Crimp TopIsopropyl Myristate SPME Vial or Crimp Top (Leached by Water)Isopropyl Palmitate SPME Vial or Crimp Top (Leached by Water(Z)-. 6,10-dimethyl-5,9-Undecadien-2-one SPME Vial or Crimp Top

1 0 1 5 2 0 2 5 3 0 3 5 4 0m i n u t e s

0

5

1 0

1 5

2 0

M C o u n t s

0

5

1 0

1 5

2 0

M C o u n t s

R I C a l l w a t e r b l a n k . s m s

R I C a l l w a t e r b l a n k . s m s

SPE Water Blank

SPME Water Blank

Relative Intensity of Blanks

Background Contaminants(Summary)

SPE – Artifacts are Mostly PlasticizersOriginating from Sorbent Material and Frits

SPME – Artifacts have a Wide Range of Sourcesand are Fiber Dependent

SPE has a Greater Number of Artifacts but inLower Concentrations

Method Detection Limits: SPME vs.USGS

CW/DVB MDLs (ppb) USGS RLs (ppb)bis (2-ethylhexyl) adipate 1.0 2000.0carbaryl 10.0 60.0butylated hydroxy toluene 1.0 80.0bisphenol A 1.0 90.0N,N-diethyltoluamide 1.0 40.0dieldrin 0.1 80.0cis-chlordane 0.1 40.0lindane 0.1 50.0tetrachloroethylene n.d. 30.0diazinon 1.0 30.0chlorpyrifos 1.0 20.0triphenyl phosphate 1.0 100.0methyl parathion n.d. 60.01,4-dichlorobenzene 0.5 30.0acetophenone n.d. 150.0bis (2-ethylhexyl) phthalate 0.5 2500.0diethyl phthalate 0.5 250.04-methylphenol 0.5 40.0

Environmental Science and Technology, 2002, 36, 1202

Compound Class Direct SPME SPEBrominated 35 1

Chlorinated 6 14

Phenols 14 12

Benzenes 11 3

PAHs 5 0

Phthalates 5 3

Alcohols 10 11

Ketones 17 8

Aldehydes 4 1

Number of Unique Analytes Detectedin Wells

Future Directions

Field Sampling of Wells In the Coastal Plain

Development of SPME-LC/MS Method

Investigation of Fibers that can Extract Analyteswith Extremely High or Low Log Kow Values

Data Mining ProcessEvaluate Blank Data for repetitive blankcontaminantsSort Blank Data and Sample Data setsCompare Levels of Method Blank Contaminationwith Sample ContaminantsEliminate Blank Constituents from SamplePreliminary Data

Data Prioritization ProcessLook for recurring contaminants in the wells

Evaluate the quality of the Mass Spectrometry

Determine Structure and plausibility of existencein the water column

Determine if you are observing a weathered orhydrolyzed product of another contaminant

O

Br

Br

Br

Br

Br

BrBr

Br

BrBr

O

Br

Br2,6-dibromo-4-methoxytoluene

O Br

1-bromo-4-ethoxy-benzene

FRAGMENTS OF PBDE’s ?

OR BROMINATED DBP’s ?

Br

2-bromo-m-xyleneBr

2-bromo-1,4-dimethyl Benzene

Br

2-bromo-1,3,5-trimethylbenzene

NH

N

Br

Br

Br3,4,5-tribromo-1H-Pyrazole

Br

Br

1,2-dibromo-1-methyl-cyclohexane

U.S. Environmental Protection AgencyPolybrominated Diphenyl Ethers (PBDEs) Project Plan

March 2006