AXYS ANALYTICAL SERVICES Ltd AFFF Primer For DND and Transport Canada March 29, 2011

PFC AGENDA PFC Basics PFC Basics –Properties and Regulations –Analysis AFFF AFFF –Types –Applying knowledge to sites Stratification / Heterogeneity Stratification / Heterogeneity If we have time If we have time –Options to fill knowledge gaps –On some frequently asked questions

Some Perfluorinated Compounds Stockholm Treaty Monomers Perfluorinated Sulfonates: e.g. PFOS (C4, C6 and C8) Perfluorinated Sulfonates: e.g. PFOS (C4, C6 and C8) Perfluorinated Carboxylates: e.g. PFOA (C4- C12) Perfluorinated Carboxylates: e.g. PFOA (C4- C12)

Highly Fluorinated Compounds Examples Wide variety of monomers and polymers Wide variety of monomers and polymers Example Monomer Structures (telomer alcohols and sulfonates Example Monomer Structures (telomer alcohols and sulfonates –Telomer alcohol - CF3-(CF)n-CH2-CH2-OH, typically n = 3 to 15 –Telomer sulfonate – CF3-(CF)n-CH2-CH2-SO3 Nomenclature Nomenclature –X: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 FTOH E.g. 4:2 FTOH, 6:2 FTOH, …16:2 FTOH Above examples are finished products, precursors from manufacturing, polymer building blocks Above examples are finished products, precursors from manufacturing, polymer building blocks

PFOS – Early Human Concerns Sources Serum Levels (Mean ppb) Production workers 300-8,000 (2,500) Non-production employees (47) Human serum samples 7-82 (28) Blood bank pools 9-56 (30) Children (44) Olsen et al. (1999) J. Occup. Environ. Med. 41: 799. Olsen et al. (2001) 3M Epidemiology Report.

PFOS – Early Env. Concerns Sources Liver (ppb) Plasma (ppb) Marine mammals (seal/dolphin) Fresh water mammals (otter/mink) Birds Fish Turtles and Frogs Polar bears 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 measurable at trace levels Well absorbed orally (95% within 24 h) Well absorbed orally (95% within 24 h) Distributed mainly in serum and liver Distributed mainly in serum and liver Not metabolized Not metabolized Fecal and urinary excretion Fecal and urinary excretion Rat: Plasma t ½ = 7.5 days Monkey: Serum t ½ = 200 days Human: Estimated Serum t ½ = ~8.7 years

PFC Occurrence (Dioxin.org and SETAC) 50 yrs. of history (info varies by compound) 50 yrs. of history (info varies by compound) Present around globe Present around globe –Humans – Average 30 ng/mL PFOS, 5 ng/mL PFOA, 3 ng/mL PFHS in serum –Ubiquitous in surface water, ambient air –Bioaccumulation 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, Rhur Valley, NJ plumes) –Textile Industry –Airport and Fire Fighting Training Sites (AFFF) –Paper Industry –Landfills –POTW

PFC Regulatory Highlights Voluntary withdrawal of PFOS (3M in ) Voluntary withdrawal of PFOS (3M in ) Declaration of PFOS and PFOA as PTS by multiple regulators including Env. Canada and EPA ( ) Declaration of PFOS and PFOA as PTS by multiple regulators including Env. Canada and EPA ( ) 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 select C6+ PFAS product applications in Canada and U.S. SNUR – 2003 for PFAS, restrictions and phase outs of select C6+ PFAS product applications in Canada and U.S. Site Specific Action at manufacturing plants, associated landfills and groundwater in U.S. (i.e. Dupont Action – Washington Works 2005) Site Specific Action at manufacturing plants, associated landfills and groundwater in U.S. (i.e. 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 levels lack toxicity data to finalize Risk Assessments Complete by EPA 2005 – Regulatory levels lack toxicity data to finalize EPA action level for water dropped to 200 ppt PFOS, 400 ppt PFOA from 2000 ppb to 2009 EPA action level for water dropped to 200 ppt PFOS, 400 ppt PFOA from 2000 ppb to 2009

Regulatory Action (cont.) Acceptable or recommended regulatory levels rapidly declining Acceptable or recommended regulatory levels rapidly declining Minnesota (PFOS) Minnesota (PFOS) –Aug Env. Levels for protection of Aquatic Life 6-12 ng/L dependant on water class 6-12 ng/L dependant on water class –Dec Human Health PFOS 300 ng/L 300 ng/L New Jersey (PFOA) New Jersey (PFOA) –Drinking water at 40 ng/L PFOA Germany (PFOS, PFOA, PFHxS) Germany (PFOS, PFOA, PFHxS) –Current limit is 300 ng/L sum of analytes in drinking water –Call for 30-50ng/L based on bioaccumulation rate in humans Limit for human health effect level reduction is lack of controlled study data in humans Limit for human health effect level reduction is lack of controlled study data in humans

PFC Basics Wide variety of monomer types Wide variety of monomer types –Carboxylates and Sulfonates –Telomer alcohols, telomer sulfonates, telomer iodides, Telomer carbons, acrylates –Monomer may be intermediate in polymer production, monomer may be a product salt (PFOS + K) –Analysis typically as anion (CAS may not match analysis) Electrochemical Fluorination (ECF) Electrochemical Fluorination (ECF) –3M Process for Perfluoroalkyl Sulfonates (PFAS including PFOS) –Mixture of branched vs. linear products Telomerization Process (Dupont) for Fluoropolymers Telomerization Process (Dupont) for Fluoropolymers –Telomer Alcohols plus acrylates are raw materials –Straight chain materials 6 primary manufacturers, many products used by downstream industries and consumers 6 primary manufacturers, many products used by downstream industries and consumers

Monomer Properties General Characteristics General Characteristics – Surfactants (Polar by design but repels water) – Unique solubility - F on chain repels water and hydrocarbon, surfactant favors solid interaction as conc. rises –Extremely resistant to degradation, reaction – C8 chain length provides optimum “rigidity” for surfactants –C4 - 6 plus alkyl groups and highly fluorinated compounds are replacements for C8 PFC surfactants –lower chain length PFCs plus sulfonamides and telomers volatile, subject to air transport –Higher C #s more accumulative

Widespread Use Non-polymer applications Fabric coatings Fabric coatings Carpet coatings Carpet coatings Paper coatings Paper coatings Floor polish Floor polish Alkaline cleaners Alkaline cleaners Denture cleaners Denture cleaners Shampoos Shampoos Ant/roach insecticides Ant/roach insecticides AFFF (Aqueous Film Forming Foams) AFFF (Aqueous Film Forming Foams) Aviation hydraulic fluid (e.g. Skydrol) Aviation hydraulic fluid (e.g. Skydrol) Mining/oil well surfactant Mining/oil well surfactant Acid rust suppressant Acid rust suppressant Metal plating mist suppressant Metal plating mist suppressant Electronic etching bath Electronic etching bath

Ubiquitous PFC Occurrence 8 months POTW Influent / Effluent levels AnalytesUnits No. of Samples No. of Detects Percent of Detects Observed Concentration Avg Conc. Found Min Conc. Found Max Conc. Found PFBAng/L PFBS PFDA PFDoA PFHpA PFHxA PFHxS PFNA PFOA PFOS PFOSA PFPeA PFUnA

PFC Occurrence in POTW Biosolids AnalytesUnits No. of Samples No. of Detects Percent of Detects Observed Concentration Avg Conc. Found Min Conc. Found Max Conc. Found PFBAng/g PFBS PFDA PFDoA PFHpA PFHxA PFHxS PFNA PFOA PFOS PFOSA PFPeA PFUnA

Ultra-Trace Analysis Principles Performance of ions monitored and reported to meet response, ratio, and retention criteria Performance of ions monitored and reported to meet response, ratio, and retention criteria Use of recovery correction means that surrogate recovery specs. can be wider allowing greater severity, types and numbers of clean-up without biasing results Use of recovery correction means that surrogate recovery specs. can be wider allowing greater severity, types and numbers of clean-up without biasing results Maximizing chromatographic separation and selectivity achieved through cleanup, columns, instrument type Maximizing chromatographic separation and selectivity achieved through cleanup, columns, instrument type Selectivity achieves low detection limits, ruggedness Selectivity achieves low detection limits, ruggedness Basis for 96/23/EC standard for positive identification and quantification of targets with no specified reference method Basis for 96/23/EC standard for positive identification and quantification of targets with no specified reference method Many NA reference methods would be considered a non-positive screen by this standard Many NA reference methods would be considered a non-positive screen by this standard

AXYS PFC Method Basics For water, soils, sediments, tissues, serum, air For water, soils, sediments, tissues, serum, air Applies principles of EPA 1600 series performance based methods Applies principles of EPA 1600 series performance based methods Key AXYS PFC Method Attributes Key AXYS PFC Method Attributes – Recovery Corrected – Matrix Matched Calibration – Pre-Concentration by SPE Cartridge – Low detection limits and blank levels – Big “D”, small “R” – Benchmarked, multiple method validations to insure accuracy – LOQ is LMCL point above MDL or client specific level Adjust pH to 5.5 ±0.5 With HCOOH Spike labeled surrogates SPE extraction with WAX Condition: 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 MeOH Microvial 300uL portion Standard AXYS PFC In Water Method MLA 060

Dehydronefidipine LC / MS vs. LC MS/MS TIC (Total Ion Chromatogram) vs. MRM Monitoring

Technique # of Ions (native plus labeled surrogate) # of Points GC/MS (EI or CI) NN LC/MSNN GC MS/MS 1 precursor, 2 daughter 4 LC MS/MS 1 precursor, 2 daughter 4 LC MS/MS 2 precursor, each with one daughter 5 HRMSN2N 96 / 23 / EC Point Criteria for Positive Identification if Using Isotope Dilution (4 Points Required for a Positive)

PFC MRM Transitions and Surrogates Target Analyte MRM Transition ISMRMSurrogate PFBA (C4 Acid) 213>169 13C 4 PFBA 217>172 13C2 PFOA 417>372 PFPeA (C5 Acid) 263>219217>172 PFHxA (C6 Acid) 313>269, 313>119 13C 2 PFHxA 315>270 PFHpA (C7 Acid) 363>319, 363> >372 PFOA (C8 Acid) 413>369, 413>219, 413>169 13C2 PFOA 415>370 PFNA (C9 Acid) 463>419, 463>219, 463>169 13C 5 PFNA 468>423 PFDA (C10 Acid) 513>469, 513>269, 513>219 13C 2 PFDA 515>470 PFUnA (C11 Acid) 563>519, 563>269, 563>219 13C 2 PFUnA 565>520 PFDoA (C12 Acid) 613>569, 613>319, 613>169 13C 2 PFDoA 615>570 PFBS (C4 Sulfonate) 299>80, 299>99 303>84 13 C2 FOUEA 18 O2 PFOS PFHS (C6 Sulfonate) 399>80, 399>99 18O 2 PFHS 403>84 PFOS (C8 Sulfonate) 499>80, 499>99, 499>130 13C2 PFOS 503>80 FOSA (C8 Sulfonamide) 498>70 503>80

PFC ANALYSIS – KEY POINTS Carboxylates and Sulfonates Suppression Monitoring / Control Suppression Monitoring / Control –Rough Definition – Analytes present in sample are incompletely ionized due to competing compounds in droplets, targets measured low or missed (creating false positives and negatives) –If occurs with instrument standard alone (non-recovery corrected) false positives or negatives may occur –Referred to as suppression or enhancement –Monitored with C labeled instrument standard (low level) vs. labelled surrogates –Multiple transitions provide confirmation of positives –Confirmed by dilution, may require smaller sample size / extra SPE clean-up steps to resolve

Typical AXYS PFC Batch Sequence Max. Batch Size (excluding QC) is 20 samples (8 to 14 is more common) Max. Batch Size (excluding QC) is 20 samples (8 to 14 is more common) –1-2 instrument blanks –6 initial calibration standards (matrix matched) –Batch and Batch QC –1-2 instrument blanks Batch QC samples adjusted in size to match samples Batch QC samples adjusted in size to match samples –Spiked Reference Material (SPM or OPR) –Instrument Blank –Method Blank –Field QC MS/MSD (precision and accuracy) MS/MSD (precision and accuracy) Duplicate (precision) Duplicate (precision)

PFC Method QC data for water. PFC Method QC data for water. Analyte Analyte Blank Acceptance (ng/L) IPR, n=5 %rec. (%RSD) MDL (ng/L), n=7 PFBA (9.5)0.72 PFPeA (2.7)0.48 PFHxA (2.5)0.37 PFHpA (1.5)0.59 PFOA (7.6)0.50 PFNA (8.1)0.66 PFDA (5.5)0.48 PFUnA (3.0)0.28 PFDoA (9.6)0.29 PFBS (5.2)1.64 PFHxS (3.7)1.14 PFOS (2.4)1.18 PFOSA (9.5)0.43 Example EPA Tier 1 Validation AXYS MLA 060 – PFCs in Water

Percent recovery (Accuracy) and precision (%RSD) for aqueous matrices at three spiking levels. Percent recovery (Accuracy) and precision (%RSD) for aqueous matrices at three spiking levels. Reagent water Groundwater Surface water LowMidHighLowMidHighLowMidHigh PFBA102(12)110(2.6)109(9.9)106(10)96.7(6.8)105(11)97.6(3.7)98.8(5.6)103(14) PFPeA99.6(7.3)90.3(4.1)98.8(6.0)101(5.7)87.8(8.0)99.8(9.1)98.2(5.6)85.6(3.1)81.2(3.9) PFHxA103(3.4)93.4(5.1)101(6.8)100(7.7)94.9(3.3)102(4.9)99.4(4.4)102(4.0)101(4.0) PFHpA95.3(9.2)94.8(3.4)103(6.2)104(11)95.3(9.2)106(11)100(3.6)108(4.7) 116(6. 6) PFOA99.7(5.3)95.2(4.5)104(5.9)106(10)98.8(5.3)102(4.5)103(6.8)102(5.1)101(7.4) PFNA95.0(8.4)92.8(5.4)100(3.1)102(5.2)96.0(5.3)101(5.3)101(9.6)96.6(2.5)100(9.2) PFDA89.2(9.7)94.3(6.4)104(6.5)108(5.9)101(4.9)103(4.2)93.1(7.5)108(3.3)108(3.1) PFUnA95.3(5.4)89.9(5.8)100.0(8.3)86.8(7.3)89.5(7.8)95.1(5.2)97.6(6.4)105(8.1)105(5.0) PFDoA105(6.8)108(3.9)111(2.7)102(9.6)103(7.0)109(4.9)98.6(11)103(6.5)105(7.5) PFBS116(5.0)118(5.1)104(3.8)109(17)114(10)106(15)92.9(8.2)84.9(5.1)83.2(9.3) PFHxS111(6.5)120(5.8)103(2.7)115(13)107(7.4)106(5.9)101(6.8)103(4.46)96.9(8.2) PFOS107(7.8)107(5.7)100.0(3.6)105(6.7)98.5(3.5)97.2(5.2)100(7.0)109(5.1)100(5.0) PFOSA108(7.4)95.9(5.5)104(4.6)103(7.1)99.6(8.5)93.6(6.0)108(7.7)113(2.8)100(5.6) 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. 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 Study 90 Day Hold Time and Container Study 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. Analyte Spiked Amount (ng) Polypropylene container Amber Glass container HDPE Container Day 28 Day 60 Day 90 Day 28 Day 60 Day 90 Day 28 Day 60 Day 90 PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnA PFDoA PFBS PFHxS PFOS PFOSA 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%.

AFFF Foams Aqueous Film Forming Foams used in fire suppression may contain PFOS and other fluorinated compounds Aqueous Film Forming Foams used in fire suppression may contain PFOS and other fluorinated compounds Also contain non fluorinated hydrocarbon surfactants that enhance surfactant activity Also contain non fluorinated hydrocarbon surfactants that enhance surfactant activity % w/w PFOS + other fluorinated compounds. Replacements are lower “C” number PFCs plus fluorotelomer compounds % w/w PFOS + other fluorinated compounds. Replacements are lower “C” number PFCs plus fluorotelomer compounds

Typical AFFF Formulation (FC-203CF) Component Composition (%) Water69.0−71.0 Diethyleneglycolbutylether (Butyl Carbitol) 20 Amphoteric fluoroalkylamide derivative 1−5 Alkyl sulfate salts 1.0−5.0 Perfluoroalkylsulfonate salts 0.5−1.5 Triethanolamine0.5−1.5 Tolyltriazole (Corrosion inhibitor) 0.05

AFFF Composition Surfactant + water + mixing produces “stable” foam Surfactant + water + mixing produces “stable” foam Target Perfluorinated and Fluorinated compounds as a layer on top of water / hydrocarbon column, enhanced by foam Target Perfluorinated and Fluorinated compounds as a layer on top of water / hydrocarbon column, enhanced by foam Surfactants Surfactants –Perfluorinated Compounds PFOS PFOS C4 – C8 carboxylates C4 – C8 carboxylates 6:2 and 8:2 fluorotelomer sulfonates 6:2 and 8:2 fluorotelomer sulfonates –Hydrocarbon surfactants –Other perfluorinated compounds Other Components Other Components –Targeted at product handling / stability, cold weather stability, corrosion control

Jan. to May AFFF and Chrome Plating Sites Reproducibility Issues Noted (20% RPD Spec.) Analyte Original (ng/L) 0.25 L Repeat (ng/L) 0.01 L PFBA2,8002,750 PFHXA11,6009,120 PFOA2,5903,510 PFBS3,3201,190 PFHXS13,0003,840 PFOS22,0004,000AnalyteOriginal(ng/L) 0.25 L 0.25 LRepeat(ng/L) 0.01 L PFBA23.3 ND 125 PFHXA55.4 PFOA ND 4.92 ND 125 PFBS>200002,670 PFHXS ND 9.84 ND 250 PFOS19,600

Pre- May 2010 – Procedure for Handling Suspected High Level Samples (OLR = Outside Linear Range of Method Calibration) Pre-Screening Pre-Screening –Small aliquot with direct injection to prevent OLR result and matrix effects. –Taken from mid - sample after shake to homogenize –Results help to select sample size Pre-Screening Limits Pre-Screening Limits –Analyst guidance only, not a valid result –Pre-screen aliquot must be representative Dilution Dilution –Instrument extract diluted (3-10X common) to bring result in calibration range or control matrix effects Dilution Limits Dilution Limits –Limited amount of dilution possible before surrogate value too low –Sample must be representative

Duplication Issues Noted Differences between pre-screening, original and repeat results in multiple samples from 2 sites Differences between pre-screening, original and repeat results in multiple samples from 2 sites –London Transport Canada site (but confounded by high solids content) –Chrome Plating - in effluent stream and roof top snow melt Only occurred where less than entire sample analyzed and sample OLR. Only occurred where less than entire sample analyzed and sample OLR. Not all analytes affected equally, PFC sulfonates most affected Not all analytes affected equally, PFC sulfonates most affected Samples showing foam formation on homogenization show discrepancies but - Samples showing foam formation on homogenization show discrepancies but - –Not all samples showing foam formation show this effect –Samples that did not foam sometimes showed effects

A Groundwater Sample from Hell

May 2010 Upon Review – Are samples stratifying? Can this be controlled with smaller sample sizes? Confirming Experiment MPCA supplied samples from chrome plating site MPCA supplied samples from chrome plating site 1L samples 1L samples –5 200 mL sub-samples by layer for each 1L sample –Performed in triplicate 10 mL samples 10 mL samples –Entire sample 3x 1L spiked clean samples 3x 1L spiked clean samples

Results from 1L Samples Stratification Present

1L Spiked Sample No Stratification

1L Sample vs. 10 mL Sample Duplication Achieved Analyte 1 L Total (ng) 10 mL (ng) (Extrapolated to 1L) PFBA PFHxA PFBS PFHxS29.1ND PFOS

Protocol for Handling Suspected High level Samples Collect 1L and 50 mL samples Collect 1L and 50 mL samples Evidence of high level field samples? Evidence of high level field samples? Pre-Screen from top of 1L sample (suspected highest level) Pre-Screen from top of 1L sample (suspected highest level) If OLR, use entire 50 mL sample If OLR, use entire 50 mL sample Add enough surrogate to allow 1/10 or 9/10 injection of instrument (final) extract Add enough surrogate to allow 1/10 or 9/10 injection of instrument (final) extract

Protocol Applied at Greenwood (through Dillon Consulting Oct. – Dec. 2010) Analyte MW 1286D Dup C MW 1286D Dup C Sample Size 500 mLs of 1L Sample (May sampling) 26 mLs of 1L Sample (October Sampling) 26 mLs of 1L Sample (October Sampling) 50 mLs of 50 mL Sample (October Sampling) 50 mLs of 50 mL Sample (October Sampling) PFBA2,2002,7002,8002,6712,732 PFPeA8,00011,00011,00010,53310,289 PFHxA9,40012,00011,00011,29710,667 PFHpA1,8002,6002,5002,3192,045 PFOA2,9003,0002,8002,9532,819 PFNA <93 PFDA PFUnA<1<19<19<94<93 PFDoA<1<19<19<94<93 PFBS3,6001, ,9511,672 PFHxS14,0005,5003,90013,78812,225 PFOS50, ,60213,123 PFOSA910<19<

Topical / Future AFFF Issues High Level / Stratified Samples High Level / Stratified Samples – Adequate protocol? – Is the sample stratifying in the field? Detection Limits Required Detection Limits Required – Drinking Water – 1/10 to ½ of MAC / IMAC – Current target? – Env. Levels – 1/10 to ½ of MAC / IMAC – Current Target Value of Other AFFF species analyzed Value of Other AFFF species analyzed – Defining Plumes, Removal % – Fluorotelomer Sulfonates Value of AFFF Composition Knowledge Value of AFFF Composition Knowledge

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