AXYS ANALYTICAL SERVICES LtdAXYS ANALYTICAL SERVICES LtdAFFF Primer AFFF Primer

For For

DND and Transport Canada DND and Transport Canada

March 29, 2011March 29, 2011

PFC AGENDAPFC AGENDA

• PFC BasicsPFC Basics– Properties and RegulationsProperties and Regulations– AnalysisAnalysis

• AFFFAFFF– TypesTypes– Applying knowledge to sitesApplying knowledge to sites

• Stratification / HeterogeneityStratification / Heterogeneity• If we have timeIf we have time

– Options to fill knowledge gapsOptions to fill knowledge gaps– On some frequently asked questionsOn some frequently asked questions

Some Perfluorinated CompoundsSome Perfluorinated CompoundsStockholm Treaty MonomersStockholm Treaty Monomers

• Perfluorinated Sulfonates: e.g. PFOS (C4, Perfluorinated Sulfonates: e.g. PFOS (C4, C6 and C8)C6 and C8)

• Perfluorinated Carboxylates: e.g. PFOA Perfluorinated Carboxylates: e.g. PFOA (C4-C12)(C4-C12)

CC

C

F F

F F

F F

CC

C

F

FF

F

CC

F

F

F

F

F

F

F

S

O

O

O-O-

CC

C

F F

F F

CC

CF

FF

F

CC

F

FF

F

F

F

F

O

O-O-

Highly Fluorinated CompoundsHighly Fluorinated CompoundsExamplesExamples

• Wide variety of monomers and polymersWide variety of monomers and polymers

• Example Monomer Structures (telomer alcohols and sulfonatesExample Monomer Structures (telomer alcohols and sulfonates– Telomer alcohol - CF3-(CF)n-CH2-CH2-OH, typically n = 3 to Telomer alcohol - CF3-(CF)n-CH2-CH2-OH, typically n = 3 to

1515– Telomer sulfonate – CF3-(CF)n-CH2-CH2-SO3Telomer sulfonate – CF3-(CF)n-CH2-CH2-SO3

• NomenclatureNomenclature– X:Y FTOH, X:Y FTSO3X:Y FTOH, X:Y FTSO3

•X = # of fluorinated carbons (x = 4, 6,8… to 16)X = # of fluorinated carbons (x = 4, 6,8… to 16)

•Y = # of hydrogenated carbons (Y = 2)Y = # of hydrogenated carbons (Y = 2)

•E.g. 4:2 FTOH, 6:2 FTOH, …16:2 FTOHE.g. 4:2 FTOH, 6:2 FTOH, …16:2 FTOH

• Above examples are finished products, precursors from Above examples are finished products, precursors from manufacturing, polymer building blocks manufacturing, polymer building blocks

PFOS – Early Human ConcernsPFOS – Early Human Concerns

SourcesSources Serum Levels Serum Levels

(Mean ppb)(Mean ppb)Production workersProduction workers 300-8,000 (2,500)300-8,000 (2,500)

Non-production employeesNon-production employees 28-96 (47)28-96 (47)

Human serum samplesHuman serum samples 7-82 (28)7-82 (28)

Blood bank poolsBlood bank pools 9-56 (30)9-56 (30)

ChildrenChildren 7-515 (44)7-515 (44)

Olsen et al. (1999) J. Occup. Environ. Med. 41: 799.Olsen et al. (2001) 3M Epidemiology Report.

PFOS – Early Env. ConcernsPFOS – Early Env. Concerns

SourcesSources Liver (ppb)Liver (ppb) Plasma (ppb)Plasma (ppb)Marine mammalsMarine mammals

((seal/dolphinseal/dolphin))

400-500400-500 10-10010-100

Fresh water mammalsFresh water mammals((otter/minkotter/mink))

300-2600300-2600 ----

BirdsBirds 400-600400-600 400-500400-500

FishFish 50-10050-100 ----

Turtles and FrogsTurtles and Frogs 200-300200-300 100100

Polar bearsPolar bears 180-680180-680 ----

Giesy and Kannan (2001) Environ Sci Technol 35: 1339; Kannan et al. (2001) Environ Sci Technol 35: 1593; Kannan et al. (2001) Environ Sci Technol 35: 3065; Giesy and Kannan (2002) Environ Sci Technol 36: 146A.

PFOS – Some surprises once PFOS – Some surprises once measurable at trace levelsmeasurable at trace levels

• Well absorbed orally (95% within 24 Well absorbed orally (95% within 24 h)h)

• Distributed mainly in serum and liverDistributed mainly in serum and liver

• Not metabolizedNot metabolized

• Fecal and urinary excretionFecal and urinary excretionRat: Plasma t½ = 7.5 days

Monkey: Serum t½ = 200 days

Human: Estimated Serum t½ = ~8.7 years

PFC Occurrence PFC Occurrence (Dioxin.org and SETAC)(Dioxin.org and SETAC)

• 50 yrs. of history (info varies by compound)50 yrs. of history (info varies by compound)

• Present around globePresent around globe– Humans – Average Human @ 30 ng/mL PFOS, 5 ng/mL PFOA, 3 Humans – Average Human @ 30 ng/mL PFOS, 5 ng/mL PFOA, 3

ng/mL PFHS in serumng/mL PFHS in serum– Ubiquitous in surface water, ambient airUbiquitous in surface water, ambient air– Bioaccumulation in fish and mammalsBioaccumulation in fish and mammals

• Typical “Hot Spots” (North American Focus)Typical “Hot Spots” (North American Focus)– Manufacturing Sites and related landfills (MN, WI, OH, AL, WV, Manufacturing Sites and related landfills (MN, WI, OH, AL, WV,

Rhur Valley, NJ plumes)Rhur Valley, NJ plumes)– Textile IndustryTextile Industry– Airport and Fire Fighting Training Sites (AFFF)Airport and Fire Fighting Training Sites (AFFF)– Paper IndustryPaper Industry– LandfillsLandfills– POTW POTW

PFC Regulatory HighlightsPFC Regulatory Highlights

• Voluntary withdrawal of PFOS (3M in 2000-2)Voluntary withdrawal of PFOS (3M in 2000-2)

• Declaration of PFOS and PFOA as PTS by multiple Declaration of PFOS and PFOA as PTS by multiple regulators including Env. Canada and EPA (2002-regulators including Env. Canada and EPA (2002-2005)2005)

• PFOS on Stockholm Treaty List 2009, PFOA in review PFOS on Stockholm Treaty List 2009, PFOA in review

• SNUR – 2003 for PFAS, restrictions and phase outs of SNUR – 2003 for PFAS, restrictions and phase outs of select C6+ PFAS product applications in Canada and select C6+ PFAS product applications in Canada and U.S.U.S.

• Site Specific Action at manufacturing plants, Site Specific Action at manufacturing plants, associated landfills and groundwater in U.S. (i.e. associated landfills and groundwater in U.S. (i.e. Dupont Action – Washington Works 2005)Dupont Action – Washington Works 2005)

• EU Restriction of Hazardous Substances (RoHS 2004)EU Restriction of Hazardous Substances (RoHS 2004)

• Risk Assessments Complete by EPA 2005 – Regulatory Risk Assessments Complete by EPA 2005 – Regulatory levels lack toxicity data to finalizelevels lack toxicity data to finalize

• EPA action level for water dropped to 200 ppt PFOS, EPA action level for water dropped to 200 ppt PFOS, 400 ppt PFOA from 2000 ppb - 2003 to 2009400 ppt PFOA from 2000 ppb - 2003 to 2009

Regulatory Action (cont.)Regulatory Action (cont.)• Acceptable or recommended regulatory levels rapidly declining Acceptable or recommended regulatory levels rapidly declining • Minnesota (PFOS) Minnesota (PFOS)

– Aug. 2007 Env. Levels for protection of Aquatic LifeAug. 2007 Env. Levels for protection of Aquatic Life• 6-12 ng/L dependant on water class6-12 ng/L dependant on water class

– Dec. 2007 Human Health PFOSDec. 2007 Human Health PFOS• 300 ng/L 300 ng/L

• New Jersey (PFOA) - 2007New Jersey (PFOA) - 2007– Drinking water at 40 ng/L PFOADrinking water at 40 ng/L PFOA

• Germany (PFOS, PFOA, PFHxS) - 2008Germany (PFOS, PFOA, PFHxS) - 2008– Current limit is 300 ng/L sum of analytes in drinking waterCurrent limit is 300 ng/L sum of analytes in drinking water– Call for 30-50ng/L based on bioaccumulation rate in humansCall for 30-50ng/L based on bioaccumulation rate in humans

• Limit for human health effect level reduction is lack of controlled Limit for human health effect level reduction is lack of controlled

study data in humansstudy data in humans

PFC BasicsPFC Basics• Wide variety of monomer typesWide variety of monomer types

– Carboxylates and SulfonatesCarboxylates and Sulfonates– Telomer alcohols, telomer sulfonates, telomer iodides, Telomer alcohols, telomer sulfonates, telomer iodides,

Telomer carbons, acrylatesTelomer carbons, acrylates– Monomer may be intermediate in polymer production, Monomer may be intermediate in polymer production,

monomer may be a product salt (PFOS + K)monomer may be a product salt (PFOS + K)– Analysis typically as anion (CAS may not match analysis) Analysis typically as anion (CAS may not match analysis)

• Electrochemical Fluorination (ECF)Electrochemical Fluorination (ECF)– 3M Process for Perfluoroalkyl Sulfonates (PFAS including 3M Process for Perfluoroalkyl Sulfonates (PFAS including

PFOS)PFOS)– Mixture of branched vs. linear products Mixture of branched vs. linear products

• Telomerization Process (Dupont) for FluoropolymersTelomerization Process (Dupont) for Fluoropolymers– Telomer Alcohols plus acrylates are raw materialsTelomer Alcohols plus acrylates are raw materials– Straight chain materialsStraight chain materials

• 6 primary manufacturers, many products used by 6 primary manufacturers, many products used by downstream industries and consumers downstream industries and consumers

Monomer Properties Monomer Properties

• General CharacteristicsGeneral Characteristics

– Surfactants (Polar by design but repels water)Surfactants (Polar by design but repels water)

– Unique solubility - F on chain repels water and Unique solubility - F on chain repels water and hydrocarbon, surfactant favors solid interaction as hydrocarbon, surfactant favors solid interaction as conc. rises conc. rises

– Extremely resistant to degradation, reactionExtremely resistant to degradation, reaction

– C8 chain length provides optimum “rigidity” for C8 chain length provides optimum “rigidity” for surfactantssurfactants

– C4 - 6 plus alkyl groups and highly fluorinated compounds C4 - 6 plus alkyl groups and highly fluorinated compounds are replacements for C8 PFC surfactantsare replacements for C8 PFC surfactants

– lower chain length PFCs plus sulfonamides and telomers lower chain length PFCs plus sulfonamides and telomers volatile, subject to air transportvolatile, subject to air transport

– Higher C #s more accumulative Higher C #s more accumulative

Widespread UseNon-polymer applications

• Fabric coatingsFabric coatings• Carpet coatingsCarpet coatings• Paper coatingsPaper coatings• Floor polishFloor polish• Alkaline cleanersAlkaline cleaners• Denture cleanersDenture cleaners• ShampoosShampoos• Ant/roach Ant/roach

insecticidesinsecticides

• AFFF (Aqueous AFFF (Aqueous Film Forming Film Forming Foams)Foams)

• Aviation hydraulic Aviation hydraulic fluid (e.g. Skydrol)fluid (e.g. Skydrol)

• Mining/oil well Mining/oil well surfactantsurfactant

• Acid rust Acid rust suppressantsuppressant

• Metal plating mist Metal plating mist suppressant suppressant

• Electronic etching Electronic etching bathbath

Ubiquitous PFC OccurrenceUbiquitous PFC Occurrence8 months POTW Influent / Effluent 8 months POTW Influent / Effluent

levelslevels

Analytes UnitsNo. of

SamplesNo. of

Detects

Percent of

Detects

Observed Concentration

Avg Conc. Found

Min Conc. Found

Max Conc. Found

PFBA ng/L 339 234 69 65.5 1.15 8540

PFBS 339 84 24.8 568 2.19 21000

PFDA 339 109 32.2 3.79 1.1 29.1

PFDoA 339 2 0.6 1.45 1.23 1.66

PFHpA 339 233 68.7 52.9 1.03 9610

PFHxA 339 253 74.6 328 1.03 76200

PFHxS 339 117 34.5 1650 2.03 190000

PFNA 339 210 61.9 5.62 1.03 28.1

PFOA 339 276 81.4 74.2 1.38 15600

PFOS 339 175 51.6 445 2.02 25200

PFOSA 339 25 7.4 15.3 1.04 61.7

PFPeA 340 216 63.5 174 1.04 29200

PFUnA 339 5 1.5 2.57 1.18 4.73

PFC Occurrence in POTW BiosolidsPFC Occurrence in POTW Biosolids

Analytes UnitsNo. of

SamplesNo. of

Detects

Percent of

Detects

Observed Concentration

Avg Conc. Found

Min Conc. Found

Max Conc. Found

PFBA ng/g 123 11 8.9 7.26 1.14 16.2

PFBS 123 14 11.4 9.12 2.45 32.4

PFDA 123 91 74 14.6 0.712 57.5

PFDoA 123 56 45.5 8.08 0.292 58.9

PFHpA 123 12 9.8 6.54 2.01 28.1

PFHxA 123 22 17.9 14 0.727 105

PFHxS 123 25 20.3 32.3 1.82 147

PFNA 123 60 48.8 9.37 0.139 39.2

PFOA 123 55 44.7 17 0.585 256

PFOS 123 85 69.1 476 0.901 7480

PFOSA 123 39 31.7 40.8 0.194 343

PFPeA 123 21 17.1 12.4 0.567 69.6

PFUnA 123 52 42.3 6.44 1.12 35.2

Ultra-Trace Analysis PrinciplesUltra-Trace Analysis Principles

• Performance of ions monitored and reported to meet Performance of ions monitored and reported to meet response, ratio, and retention criteriaresponse, ratio, and retention criteria

• Use of recovery correction means that surrogate recovery Use of recovery correction means that surrogate recovery specs. can be wider allowing greater severity, types and specs. can be wider allowing greater severity, types and numbers of clean-up without biasing resultsnumbers of clean-up without biasing results

• Maximizing chromatographic separation and selectivity Maximizing chromatographic separation and selectivity achieved through cleanup, columns, instrument typeachieved through cleanup, columns, instrument type

• Selectivity achieves low detection limits, ruggednessSelectivity achieves low detection limits, ruggedness

• Basis for 96/23/EC standard for positive identification and Basis for 96/23/EC standard for positive identification and quantification of targets with no specified reference methodquantification of targets with no specified reference method

• Many NA reference methods would be considered a non-Many NA reference methods would be considered a non-positive screen by this standard positive screen by this standard

AXYS PFC Method BasicsAXYS PFC Method Basics

• For water, soils, sediments, tissues, For water, soils, sediments, tissues, serum, airserum, air

• Applies principles of EPA 1600 Applies principles of EPA 1600 series performance based methodsseries performance based methods

• Key AXYS PFC Method AttributesKey AXYS PFC Method Attributes– Recovery CorrectedRecovery Corrected– Matrix Matched Calibration Matrix Matched Calibration – Pre-Concentration by SPE Pre-Concentration by SPE

CartridgeCartridge– Low detection limits and blank Low detection limits and blank

levelslevels– Big “D”, small “R”Big “D”, small “R”– Benchmarked, multiple method Benchmarked, multiple method

validations to insure accuracyvalidations to insure accuracy– LOQ is LMCL point above MDL or LOQ is LMCL point above MDL or

client specific levelclient specific level

Adjust pH to 5.5 ±0.5 With HCOOHSpike labeled surrogates

SPE extraction with WAXCondition: 5 mL 0.3% NH4OH in MeOH

and 5mL0.1 M HCOOH

Wash: with 5 mL of H2O 5 mL & With 1:1 (0.1 M HCOOH: MeOH)

Analyze by (-ESI) LC-MS/MS

Elute: 4 mL of 0.3% NH4OH in MeOHMicrovial 300uL portion

Standard AXYS PFC In Water MethodMLA 060

Time0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00

%

1

17.65

16.91

16.39

21.17 m in13.00 14.00 15.00 16.00 17.00

%

0

100

PP7J_222S16

Dehydronefidipine

LC / MS vs. LC MS/MSLC / MS vs. LC MS/MSTIC (Total Ion Chromatogram) vs. MRM TIC (Total Ion Chromatogram) vs. MRM

MonitoringMonitoring

TechniqueTechnique # of Ions (native plus # of Ions (native plus labeled surrogate)labeled surrogate)

# of Points# of Points

GC/MS (EI or CI)GC/MS (EI or CI) NN NN

LC/MSLC/MS NN NN

GC MS/MSGC MS/MS 1 precursor, 2 daughter1 precursor, 2 daughter 44

LC MS/MSLC MS/MS 1 precursor, 2 daughter1 precursor, 2 daughter 44

LC MS/MSLC MS/MS 2 precursor, each with one 2 precursor, each with one daughterdaughter

55

HRMSHRMS NN 2N2N

96 / 23 / EC Point Criteria for 96 / 23 / EC Point Criteria for Positive Identification if Using Positive Identification if Using

Isotope DilutionIsotope Dilution(4 Points Required for a Positive)(4 Points Required for a Positive)

PFC MRM Transitions and SurrogatesPFC MRM Transitions and SurrogatesTarget AnalyteTarget Analyte MRM TransitionMRM Transition ISIS MRMMRM SurrogateSurrogate

PFBA (C4 Acid)PFBA (C4 Acid) 213>169213>169 13C13C4 4 PFBAPFBA 217>17217>1722

13C2 PFOA13C2 PFOA

417>372417>372

PFPeA (C5 Acid)PFPeA (C5 Acid) 263>219263>219 217>17217>1722

PFHxA (C6 Acid)PFHxA (C6 Acid) 313>269,313>269, 313>119 313>119 13C13C2 2 PFHxAPFHxA 315>27315>2700

PFHpA (C7 Acid)PFHpA (C7 Acid) 363>319363>319, 363>169, 363>169 417>37417>3722

PFOA (C8 Acid)PFOA (C8 Acid) 413>369, 413>219,413>369, 413>219, 413>169413>169 13C2 PFOA13C2 PFOA 415>37415>37

00

PFNA (C9 Acid)PFNA (C9 Acid) 463>419463>419, 463>219, , 463>219, 463>169463>169

13C13C5 5 PFNAPFNA 468>42468>4233

PFDA (C10 Acid)PFDA (C10 Acid) 513>469513>469, 513>269, , 513>269, 513>219513>219

13C13C2 2 PFDAPFDA 515>47515>4700

PFUnA (C11 Acid)PFUnA (C11 Acid) 563>519563>519, 563>269, , 563>269, 563>219563>219

13C13C2 2 PFUnAPFUnA 565>52565>5200

PFDoA (C12 Acid)PFDoA (C12 Acid) 613>569613>569, 613>319, , 613>319, 613>169613>169

13C13C2 2 PFDoAPFDoA 615>57615>5700

PFBS (C4 Sulfonate)PFBS (C4 Sulfonate) 299>80, 299>99299>80, 299>99 303>84303>84 13 C2 FOUEA 13 C2 FOUEA 18 O2 PFOS18 O2 PFOS

PFHS (C6 Sulfonate)PFHS (C6 Sulfonate) 399>80, 399>99399>80, 399>99 18O18O2 2 PFHSPFHS 403>84403>84

PFOS (C8 Sulfonate)PFOS (C8 Sulfonate) 499>80, 499>99,499>80, 499>99, 499>130499>130 13C2 PFOS13C2 PFOS 503>80503>80

FOSA (C8 FOSA (C8 Sulfonamide)Sulfonamide) 498>70498>70 503>80503>80

PFC ANALYSIS – KEY POINTSPFC ANALYSIS – KEY POINTSCarboxylates and SulfonatesCarboxylates and Sulfonates

• Suppression Monitoring / ControlSuppression Monitoring / Control

– Rough Definition – Analytes present in sample are incompletely Rough Definition – Analytes present in sample are incompletely ionized due to competing compounds in droplets, targets ionized due to competing compounds in droplets, targets measured low or missed (creating false positives and measured low or missed (creating false positives and negatives)negatives)

– If occurs with instrument standard alone (non-recovery If occurs with instrument standard alone (non-recovery corrected) false positives or negatives may occurcorrected) false positives or negatives may occur

– Referred to as suppression or enhancementReferred to as suppression or enhancement

– Monitored with C labeled instrument standard (low level) vs. Monitored with C labeled instrument standard (low level) vs. labelled surrogateslabelled surrogates

– Multiple transitions provide confirmation of positivesMultiple transitions provide confirmation of positives

– Confirmed by dilution, may require smaller sample size / extra Confirmed by dilution, may require smaller sample size / extra SPE clean-up steps to resolve SPE clean-up steps to resolve

Typical AXYS PFC Batch SequenceTypical AXYS PFC Batch Sequence

• Max. Batch Size (excluding QC) is 20 samples (8 to 14 is Max. Batch Size (excluding QC) is 20 samples (8 to 14 is more common)more common)– 1-2 instrument blanks1-2 instrument blanks– 6 initial calibration standards (matrix matched)6 initial calibration standards (matrix matched)– Batch and Batch QCBatch and Batch QC– 1-2 instrument blanks1-2 instrument blanks

• Batch QC samples adjusted in size to match samplesBatch QC samples adjusted in size to match samples

– Spiked Reference Material (SPM or OPR)Spiked Reference Material (SPM or OPR)– Instrument BlankInstrument Blank– Method BlankMethod Blank– Field QC Field QC

• MS/MSD (precision and accuracy)MS/MSD (precision and accuracy)• Duplicate (precision)Duplicate (precision)

PFCPFC Method QC data for waterMethod QC data for water. .

AnalyteAnalyte

Blank Blank AcceptanceAcceptance

(ng/L)(ng/L)IPR, n=5IPR, n=5

%rec. (%RSD)%rec. (%RSD)MDLMDL

(ng/L), n=7(ng/L), n=7

PFBAPFBA 0.250.25 93.1(9.5)93.1(9.5) 0.720.72

PFPeAPFPeA 0.250.25 84.6(2.7)84.6(2.7) 0.480.48

PFHxAPFHxA 0.250.25 89.8(2.5)89.8(2.5) 0.370.37

PFHpAPFHpA 0.250.25 85.0(1.5)85.0(1.5) 0.590.59

PFOAPFOA 0.250.25 106(7.6)106(7.6) 0.500.50

PFNAPFNA 0.250.25 88.8(8.1)88.8(8.1) 0.660.66

PFDAPFDA 0.250.25 94.8(5.5)94.8(5.5) 0.480.48

PFUnAPFUnA 0.250.25 95.6(3.0)95.6(3.0) 0.280.28

PFDoAPFDoA 0.250.25 105(9.6)105(9.6) 0.290.29

PFBSPFBS 0.250.25 110(5.2)110(5.2) 1.641.64

PFHxSPFHxS 0.250.25 105(3.7)105(3.7) 1.141.14

PFOSPFOS 0.250.25 107(2.4)107(2.4) 1.181.18

PFOSAPFOSA 0.250.25 108(9.5)108(9.5) 0.430.43

Example EPA Tier 1 ValidationAXYS MLA 060 – PFCs in Water

Percent recovery (Accuracy) and precision (%RSD) for aqueous matrices Percent recovery (Accuracy) and precision (%RSD) for aqueous matrices at three spiking levelsat three spiking levels. .

Reagent waterReagent water GroundwaterGroundwater Surface waterSurface water

LowLow MidMid HighHigh LowLow MidMid HighHigh LowLow MidMid HighHigh

PFBAPFBA 102(12)102(12) 110(2.6)110(2.6) 109(9.9)109(9.9) 106(10)106(10)96.7(6.896.7(6.8

)) 105(11)105(11) 97.6(3.7)97.6(3.7)98.8(5.698.8(5.6

)) 103(14)103(14)

PFPePFPeAA

99.6(7.399.6(7.3))

90.3(4.190.3(4.1)) 98.8(6.0)98.8(6.0) 101(5.7)101(5.7)

87.8(8.087.8(8.0))

99.8(9.199.8(9.1)) 98.2(5.6)98.2(5.6)

85.6(3.185.6(3.1))

81.2(3.981.2(3.9))

PFHxPFHxAA 103(3.4)103(3.4)

93.4(5.193.4(5.1)) 101(6.8)101(6.8) 100(7.7)100(7.7)

94.9(3.394.9(3.3)) 102(4.9)102(4.9) 99.4(4.4)99.4(4.4) 102(4.0)102(4.0) 101(4.0)101(4.0)

PFHpPFHpAA

95.3(9.295.3(9.2))

94.8(3.494.8(3.4)) 103(6.2)103(6.2) 104(11)104(11)

95.3(9.295.3(9.2)) 106(11)106(11) 100(3.6)100(3.6) 108(4.7)108(4.7)

116(6. 116(6. 6)6)

PFOAPFOA99.7(5.399.7(5.3

))95.2(4.595.2(4.5

)) 104(5.9)104(5.9) 106(10)106(10)98.8(5.398.8(5.3

)) 102(4.5)102(4.5) 103(6.8)103(6.8) 102(5.1)102(5.1) 101(7.4)101(7.4)

PFNAPFNA95.0(8.495.0(8.4

))92.8(5.492.8(5.4

)) 100(3.1)100(3.1) 102(5.2)102(5.2)96.0(5.396.0(5.3

)) 101(5.3)101(5.3) 101(9.6)101(9.6)96.6(2.596.6(2.5

)) 100(9.2)100(9.2)

PFDAPFDA89.2(9.789.2(9.7

))94.3(6.494.3(6.4

)) 104(6.5)104(6.5) 108(5.9)108(5.9) 101(4.9)101(4.9) 103(4.2)103(4.2) 93.1(7.5)93.1(7.5) 108(3.3)108(3.3) 108(3.1)108(3.1)

PFUnPFUnAA

95.3(5.495.3(5.4))

89.9(5.889.9(5.8))

100.0(8.3100.0(8.3))

86.8(7.386.8(7.3))

89.5(7.889.5(7.8))

95.1(5.295.1(5.2)) 97.6(6.4)97.6(6.4) 105(8.1)105(8.1) 105(5.0)105(5.0)

PFDoPFDoAA 105(6.8)105(6.8) 108(3.9)108(3.9) 111(2.7)111(2.7) 102(9.6)102(9.6) 103(7.0)103(7.0) 109(4.9)109(4.9) 98.6(11)98.6(11) 103(6.5)103(6.5) 105(7.5)105(7.5)

PFBSPFBS 116(5.0)116(5.0) 118(5.1)118(5.1) 104(3.8)104(3.8) 109(17)109(17) 114(10)114(10) 106(15)106(15) 92.9(8.2)92.9(8.2)84.9(5.184.9(5.1

))83.2(9.383.2(9.3

))

PFHxPFHxSS 111(6.5)111(6.5) 120(5.8)120(5.8) 103(2.7)103(2.7) 115(13)115(13) 107(7.4)107(7.4) 106(5.9)106(5.9) 101(6.8)101(6.8)

103(4.46103(4.46))

96.9(8.296.9(8.2))

PFOSPFOS 107(7.8)107(7.8) 107(5.7)107(5.7)100.0(3.6100.0(3.6

)) 105(6.7)105(6.7)98.5(3.598.5(3.5

))97.2(5.297.2(5.2

)) 100(7.0)100(7.0) 109(5.1)109(5.1) 100(5.0)100(5.0)

PFOSPFOSAA 108(7.4)108(7.4)

95.9(5.595.9(5.5)) 104(4.6)104(4.6) 103(7.1)103(7.1)

99.6(8.599.6(8.5))

93.6(6.093.6(6.0)) 108(7.7)108(7.7) 113(2.8)113(2.8) 100(5.6)100(5.6)

Spiking levels for carboxylates = 2.5, 50 and 250 ng for Low, Mid and High respectively.Spiking levels for carboxylates = 2.5, 50 and 250 ng for Low, Mid and High respectively.Spiking levels for sulfonates = 5, 100, and 500 ng for Low, Mid and High respectively.Spiking levels for sulfonates = 5, 100, and 500 ng for Low, Mid and High respectively.

EPA Tier 3 Validation – AXYS PFC Water Method (MLA 060)Variables: Three concentrations, three matrices and time (three different days). Accuracy: Mean recovery values ranged between 85 and 120% for all test variables.Precision: Inter-day variance was below 15% under all the variables investigated.

Intra- day variance was below 26% under all the variables investigated.

AXYS / DuPont StudyAXYS / DuPont Study 90 Day Hold Time and Container Study 90 Day Hold Time and Container Study

Urban Myth – Polypropylene Best Urban Myth – Polypropylene Best

Percent recovery of analytes after storage in reagent water for 28, 60 and 90 days. Percent recovery of analytes after storage in reagent water for 28, 60 and 90 days.

AnalytAnalytee

SpikedSpikedAmount Amount

(ng) (ng)

Polypropylene containerPolypropylene container Amber Glass containerAmber Glass container HDPE ContainerHDPE Container

Day 28Day 28 Day 60Day 60 Day 90Day 90 Day 28Day 28 Day 60Day 60 Day 90Day 90 Day 28Day 28 Day 60Day 60 Day 90Day 90

PFBAPFBA 249249 110110 82.282.2 85.685.6 96.896.8 108108 92.692.6 112112 98.498.4 90.490.4

PFPeAPFPeA 250250 81.581.5 80.380.3 81.781.7 86.486.4 105105 88.688.6 93.293.2 86.286.2 91.691.6

PFHxAPFHxA 249249 88.088.0 73.373.3 75.775.7 90.490.4 99.699.6 85.485.4 93.493.4 79.379.3 83.883.8

PFHpAPFHpA 251251 79.079.0 74.674.6 81.681.6 86.486.4 99.099.0 80.680.6 87.887.8 80.080.0 87.487.4

PFOAPFOA 250250 86.086.0 73.773.7 77.077.0 89.689.6 98.898.8 84.284.2 96.296.2 79.479.4 84.684.6

PFNAPFNA 251251 84.284.2 75.075.0 67.867.8 89.489.4 98.898.8 83.483.4 91.691.6 78.078.0 77.077.0

PFDAPFDA 250250 81.981.9 69.369.3 70.170.1 88.188.1 95.895.8 87.987.9 90.790.7 75.375.3 84.984.9

PFUnAPFUnA 252252 63.063.0 40.740.7 47.647.6 99.799.7 105105 85.085.0 101101 84.384.3 81.381.3

PFDoAPFDoA 249249 60.660.6 42.542.5 34.034.0 82.282.2 94.394.3 90.590.5 81.681.6 78.878.8 88.188.1

PFBSPFBS 501501 86.786.7 95.395.3 79.679.6 77.577.5 96.496.4 83.383.3 76.876.8 82.682.6 82.982.9

PFHxSPFHxS 500500 87.987.9 94.294.2 84.984.9 75.775.7 95.995.9 88.688.6 82.382.3 81.681.6 84.884.8

PFOSPFOS 498498 86.786.7 83.683.6 74.174.1 83.083.0 99.199.1 88.788.7 86.986.9 85.185.1 87.887.8

PFOSAPFOSA 250250 91.291.2 75.875.8 69.869.8 93.693.6 96.096.0 86.086.0 84.484.4 70.270.2 68.268.2

•Each data points represent an average of at least duplicate measurements. Each data points represent an average of at least duplicate measurements. * % recovery for all compounds except PFUnA and PFDoA were above 80% prior to Day 28%.* % recovery for all compounds except PFUnA and PFDoA were above 80% prior to Day 28%.

AFFF FoamsAFFF Foams

• Aqueous Film Forming Foams Aqueous Film Forming Foams used in fire suppression may used in fire suppression may contain PFOS and other contain PFOS and other fluorinated compoundsfluorinated compounds

• Also contain non fluorinated Also contain non fluorinated

hydrocarbon surfactants that hydrocarbon surfactants that enhance surfactant activityenhance surfactant activity

• 0.5-1.5% w/w PFOS + other 0.5-1.5% w/w PFOS + other fluorinated compounds. fluorinated compounds. Replacements are lower “C” Replacements are lower “C” number PFCs plus number PFCs plus fluorotelomer compoundsfluorotelomer compounds

Typical AFFF Formulation (FC-203CF)Typical AFFF Formulation (FC-203CF)

ComponentComponent Composition (%)Composition (%)

WaterWater 69.0−71.069.0−71.0

Diethyleneglycolbutylether (Butyl Carbitol)Diethyleneglycolbutylether (Butyl Carbitol) 2020

Amphoteric fluoroalkylamide derivativeAmphoteric fluoroalkylamide derivative 1−51−5

Alkyl sulfate saltsAlkyl sulfate salts 1.0−5.01.0−5.0

Perfluoroalkylsulfonate saltsPerfluoroalkylsulfonate salts 0.5−1.50.5−1.5

TriethanolamineTriethanolamine 0.5−1.50.5−1.5

Tolyltriazole (Corrosion inhibitor)Tolyltriazole (Corrosion inhibitor) 0.050.05

AFFF Composition AFFF Composition • Surfactant + water + mixing produces Surfactant + water + mixing produces

“stable” foam“stable” foam• Target Perfluorinated and Fluorinated Target Perfluorinated and Fluorinated

compounds as a layer on top of water / compounds as a layer on top of water / hydrocarbon column, enhanced by foam hydrocarbon column, enhanced by foam

• SurfactantsSurfactants– Perfluorinated CompoundsPerfluorinated Compounds

• PFOSPFOS• C4 – C8 carboxylatesC4 – C8 carboxylates• 6:2 and 8:2 fluorotelomer sulfonates6:2 and 8:2 fluorotelomer sulfonates

– Hydrocarbon surfactantsHydrocarbon surfactants– Other perfluorinated compoundsOther perfluorinated compounds

• Other ComponentsOther Components– Targeted at product handling / stability, cold Targeted at product handling / stability, cold

weather stability, corrosion controlweather stability, corrosion control

Jan. to May 2010 - AFFF and Chrome Plating Jan. to May 2010 - AFFF and Chrome Plating SitesSites

Reproducibility Issues Noted Reproducibility Issues Noted (20% RPD Spec.)(20% RPD Spec.)

AnalytAnalytee

Original Original (ng/L) (ng/L) 0.25 L 0.25 L

Repeat Repeat (ng/L)(ng/L)

0.01 L 0.01 L

PFBAPFBA 2,8002,800 2,7502,750

PFHXAPFHXA 11,60011,600 9,1209,120

PFOAPFOA 2,5902,590 3,5103,510

PFBSPFBS 3,3203,320 1,1901,190

PFHXSPFHXS 13,00013,000 3,8403,840

PFOSPFOS 22,00022,000 4,0004,000

AnalyteAnalyte

Original Original (ng/L)(ng/L)

0.25 L0.25 L

Repeat Repeat (ng/L) (ng/L) 0.01 L0.01 L

PFBAPFBA 23.323.3 ND 125ND 125

PFHXAPFHXA 55.455.4 ND 125ND 125

PFOAPFOA ND 4.92ND 4.92 ND 125ND 125

PFBSPFBS >20000>20000 2,6702,670

PFHXSPFHXS ND 9.84ND 9.84 ND 250ND 250

PFOSPFOS 19,60019,600 ND 250ND 250

Pre- May 2010 – Procedure for Handling Pre- May 2010 – Procedure for Handling Suspected High Level SamplesSuspected High Level Samples

(OLR = Outside Linear Range of Method Calibration)(OLR = Outside Linear Range of Method Calibration)

• Pre-ScreeningPre-Screening– Small aliquot with direct injection to prevent OLR result Small aliquot with direct injection to prevent OLR result

and matrix effects. and matrix effects. – Taken from mid - sample after shake to homogenizeTaken from mid - sample after shake to homogenize– Results help to select sample size Results help to select sample size

• Pre-Screening LimitsPre-Screening Limits– Analyst guidance only, not a valid resultAnalyst guidance only, not a valid result– Pre-screen aliquot must be representativePre-screen aliquot must be representative

• DilutionDilution– Instrument extract diluted (3-10X common) to bring Instrument extract diluted (3-10X common) to bring

result in calibration range or control matrix effectsresult in calibration range or control matrix effects

• Dilution LimitsDilution Limits– Limited amount of dilution possible before surrogate Limited amount of dilution possible before surrogate

value too lowvalue too low– Sample must be representativeSample must be representative

Duplication Issues Noted Duplication Issues Noted

• Differences between pre-screening, original and Differences between pre-screening, original and repeat results in multiple samples from 2 sitesrepeat results in multiple samples from 2 sites– London Transport Canada site (but confounded by high London Transport Canada site (but confounded by high

solids content) solids content) – Chrome Plating - in effluent stream and roof top snow Chrome Plating - in effluent stream and roof top snow

meltmelt

• Only occurred where less than entire sample Only occurred where less than entire sample analyzed and sample OLR.analyzed and sample OLR.

• Not all analytes affected equally, PFC sulfonates Not all analytes affected equally, PFC sulfonates most affectedmost affected

• Samples showing foam formation on Samples showing foam formation on homogenization show discrepancies but - homogenization show discrepancies but - – Not all samples showing foam formation show this effectNot all samples showing foam formation show this effect– Samples that did not foam sometimes showed effectsSamples that did not foam sometimes showed effects

A Groundwater Sample from HellA Groundwater Sample from Hell

May 2010 Upon Review – Are samples May 2010 Upon Review – Are samples stratifying? Can this be controlled with stratifying? Can this be controlled with

smaller sample sizes?smaller sample sizes?Confirming ExperimentConfirming Experiment

• MPCA supplied samples from chrome MPCA supplied samples from chrome plating siteplating site

• 1L samples1L samples– 5 200 mL sub-samples by layer for each 1L sample5 200 mL sub-samples by layer for each 1L sample– Performed in triplicatePerformed in triplicate

• 10 mL samples10 mL samples– Entire sampleEntire sample

• 3x 1L spiked clean samples 3x 1L spiked clean samples

Results from 1L SamplesResults from 1L SamplesStratification Present Stratification Present

0

30000

60000

0 1 2 3 4 5 6

Layer (Top to Bottom)

Conce

ntr

ati

on (

ng/L)

0

30

60

Conce

ntr

ati

on (

ng/L)

PFOS (Left) PFBS (Left) PFBA (Right)PFHXA (Right) PFHXS (Right)

1L Spiked Sample1L Spiked SampleNo StratificationNo Stratification

0

50

100

150

1 2 3 4 5

Layer (Top to Bottom)

Reco

very

(%

)

PFOA PFDOA PFBS PFHXS PFOS

1L Sample vs. 10 mL Sample1L Sample vs. 10 mL SampleDuplication AchievedDuplication Achieved

AnalyteAnalyte 1 L Total (ng)1 L Total (ng) 10 mL (ng) 10 mL (ng) (Extrapolated to 1L)(Extrapolated to 1L)

PFBAPFBA 51.351.3 64.864.8

PFHxAPFHxA 29.229.2 21.821.8

PFBS PFBS 1260012600 81608160

PFHxSPFHxS 29.129.1 NDND

PFOSPFOS 2540025400 3070030700

Protocol for Handling Suspected High Protocol for Handling Suspected High level Sampleslevel Samples

• Collect 1L and 50 mL samplesCollect 1L and 50 mL samples

• Evidence of high level field samples?Evidence of high level field samples?

• Pre-Screen from top of 1L sample Pre-Screen from top of 1L sample (suspected highest level)(suspected highest level)

• If OLR, use entire 50 mL sampleIf OLR, use entire 50 mL sample

• Add enough surrogate to allow 1/10 Add enough surrogate to allow 1/10 or 9/10 injection of instrument (final) or 9/10 injection of instrument (final) extract extract

Protocol Applied at Greenwood Protocol Applied at Greenwood (through Dillon Consulting Oct. – Dec. 2010)(through Dillon Consulting Oct. – Dec. 2010)

AnalyteAnalyte MW MW 1286D 1286D

MW MW 1286D1286D

Dup CDup C MW MW 1286D1286D

Dup CDup C

Sample Sample SizeSize

500 mLs of 500 mLs of 1L Sample1L Sample(May (May sampling)sampling)

26 mLs of 26 mLs of 1L Sample 1L Sample (October (October Sampling)Sampling)

26 mLs of 26 mLs of 1L Sample1L Sample(October (October Sampling)Sampling)

50 mLs of50 mLs of50 mL 50 mL SampleSample(October (October Sampling)Sampling)

50 mLs of 50 mLs of 50 mL 50 mL SampleSample(October (October Sampling) Sampling)

PFBAPFBA 2,2002,200 2,7002,700 2,8002,800 2,6712,671 2,7322,732PFPeAPFPeA 8,0008,000 11,00011,000 11,00011,000 10,53310,533 10,28910,289PFHxAPFHxA 9,4009,400 12,00012,000 11,00011,000 11,29711,297 10,66710,667PFHpAPFHpA 1,8001,800 2,6002,600 2,5002,500 2,3192,319 2,0452,045PFOAPFOA 2,9002,900 3,0003,000 2,8002,800 2,9532,953 2,8192,819PFNAPFNA 8787 4949 5454 113113 <93<93PFDAPFDA 1212 1919 1919 9494 9393PFUnAPFUnA <1<1 <19<19 <19<19 <94<94 <93<93PFDoAPFDoA <1<1 <19<19 <19<19 <94<94 <93<93PFBSPFBS 3,6003,600 1,5001,500 1.3001.300 1,9511,951 1,6721,672PFHxSPFHxS 14,00014,000 5,5005,500 3,9003,900 13,78813,788 12,22512,225PFOSPFOS 50,00050,000 150150 3838 17,60217,602 13,12313,123PFOSAPFOSA 910910 <19<19 <19<19 120120 104104

Topical / Future AFFF IssuesTopical / Future AFFF Issues

• High Level / Stratified SamplesHigh Level / Stratified Samples– Adequate protocol?Adequate protocol?– Is the sample stratifying in the field?Is the sample stratifying in the field?

• Detection Limits RequiredDetection Limits Required– Drinking Water – 1/10 to ½ of MAC / IMACDrinking Water – 1/10 to ½ of MAC / IMAC– Current target?Current target?– Env. Levels – 1/10 to ½ of MAC / IMACEnv. Levels – 1/10 to ½ of MAC / IMAC– Current TargetCurrent Target

• Value of Other AFFF species analyzedValue of Other AFFF species analyzed– Defining Plumes, Removal %Defining Plumes, Removal %– Fluorotelomer SulfonatesFluorotelomer Sulfonates

• Value of AFFF Composition KnowledgeValue of AFFF Composition Knowledge

Open ForumOpen Forum

• QuestionsQuestions

• Follow-UpsFollow-Ups