AGENDA AXYS Overview Client Objectives in Per and Highly Fluorinated Compound Analysis Method Basics Method Validation, Accuracy and Handling AFFF App

Transcription

1 AXYS ANALYTICAL Services Ltd. Methods and Considerations Related to Per and Highly Fluorinated Compounds For FCSAP Management of Perfluoroalkylated Compounds at Federal Contaminated Sites Feb. 19 th and 20 th 2014

2 AGENDA AXYS Overview Client Objectives in Per and Highly Fluorinated Compound Analysis Method Basics Method Validation, Accuracy and Handling AFFF Applications and Objectives Questions

3 AXYS Analytical Services 100 employees located in Victoria B.C. (Vancouver Island) ISO Quality Platform CALA / NELAP Accreditation Focus Multi Target Ultra Trace Organic Analysis (pg or ng levels) POPs CECs HRMS, LC MS/MS, GC/MS instrumentation 3A Analytical la Areas Environmental (All matrices associated with Bioaccumulation cycle Biomonitoring Method Development (i.e. EPA 1668, 1614, 1694)

4 Markets Served 65% U.S., 30% Cdn., 5% International CECs pre-regulatory regulatory or early stages Government and Regulatory Authorities (60% of work) Federal - EPA, DOI, HC, EC, DND State, Provincial, and Municipal Clients TMDL Studies, Ambient / Baseline Levels Legal and RP issues Method Development Environmental Consultants (30% of work) Assessment and Remediation Regional and Ambient / Background Work Risk Assessment / Litigation / RP

5 Per and Highly Fluorinated Compounds AXYS Methods PFOS and PFOA (approx. 2002) Other Carboxylates (C4 to C12) and Sulfonates (C4,C6) Manufacturing and Product Precursors Telomer Alcohols, saturated and unsataurated acids Sulfonamido + acetate + acrylate compounds Intermediate compounds in metabolism process Other Products (some PFOS + PFOA precursors) Fluorotelomer Sulfonates (6:2, 8:2, 10:2) PFPA, mono and di-paps SAM PAPs Other Compound Groups Monomers in polymer manufacture (old and new) More complex molecules (ie ie. FTS +, Fl unsaturated C chains) PFOS speciation (branched / linear, isomers)

6 Client Purposes in PFAA Analysis Occurrence, Transport, and Fate Baseline Occurrence (low detection limit, low blanks) Multi-matrix (water, soil/sediment, biota, serum, air, WWTP) Transformation and Toxicology Contaminated Sites PFAA Manufacturing Sites (none in Canada) AFFF sites Plating, Cleaning, Textile Operations

7 PFAA Example Regulatory Levels Limited Development Jurisdiction Matrix PFOA PFOS Canada HC DW 700 ng/l 300 ng/l Canada HC Soil 0.7 to 5.0 mg/kg (based on direct soil contact) EPA DW 400 ng/l 200 ng/l MN DW 300 ng/l 200 ng/l MN Water Sources to 6 ng/l L. Calhoun Water Bodies with Fish Advisory 17 ng/l Miss. Pool 2 NJ DW 40 ng/l Germany DW Sum PFOA and PFOS

8 Analysis Applied to Regulatory Criteria Detection Levels relative to criteria DW matrices 1/10 to ½ MAC or IMAC Water Values vs. Fish Consumption most stringent States and Provinces may apply most stringent clause Limited Info on PFAAs PFOA and PFOS most advanced, some criteria Current Interest in PFHxS and PFHxA, PFNA Precursors Considered in Policy Not applied at sites Tools for Assessment Other PFAAs and Precursors may be valuable in assessing risk and mobility

9 AXYS Method Management Structure 13 Default PFAAs Common to All Matrices 1) Instrument programs and QA 2) Materials QA and Calibration / Spiking Standards 3) Personnel and Training 4) Analytes and Surrogates, SPE choice Specific to Matrix 1) Extraction Fluid and Concentration 2) SPE Size 3) Additional Clean-ups 4) PE programs May be Custom to a Project 1) Sample Preparation / Creation of Samples 2)Reporting and Flagging Conventions 3) Custom spiking / dilution / handling for high levels, matrix, unique samples

10 AXYS PFC Method Basics Aqueous Example Applies principles of EPA 1600 series performance based methods and EU 657 identification / quantification 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 Standard AXYS PFC In Water Method MLA 060 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) Elute: 4 ml of 0.3% NH4OH in MeoH Microvial 300uL portion Analyze by (-ESI) LC-MS/MS

11 AXYS Standard PFAA Methods Key Notes LC analysis: C18 reverse phase column, with aqueous ACN / NH 4 OAc mobile phases (Waters Quattro or API 4000) LMCL > 2-5x MDL, 10-30X IDL Reporting Limits ng/l (LMCL) from 500 ml sample 125PFCA 1.25 PFCA, PFSA 1/X calibration curve, not linear 6 point report in calibration range Matrix matched calibration MS ionization by electrospray negative ionization mode Data acquisition by MRM Multiple transitions acquired where applicable / available Secondary transition(s) used as analyst diagnostic tools Isotope dilution / recovery correction quantification PFOS 70/30 linear / branched Wellington primary source for surrogates / natives CFR 40 defined QC limits Blank Levels < 0.25 ng / sample Instrument sensitivity is not limit, ability to remove matrix is key

12 AXYS Standard Method PFAA MRM Transitions and Surrogates (Red = default) Target Analyte Anion MRM Transition IS IS MRM Recovery Surrogate PFBA (C4 Acid) 213>169 13C 4 PFBA 217>172 PFPeA (C5 Acid) 263>219 13C PFHxA 2 217>172 PFHxA (C6 Acid) 313>269, 313>119 13C 2 PFHxA 315>270 PFHpA (C7 Acid) 363>319, 363>169 13C PFHxA 2 417>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 13C4 PFOA 417>372 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 18O PFHS 2 303>84 PFHS (C6 Sulfonate) 399>80, 399>99 18O 2 PFHS 403>84 13 C2 FOUEA PFOS (C8 Sulfonate) 499>80, 499>99, 499>130 13C2 PFOS 503>80 FOSA (C8 Sulfonamide) 498>70 13C8PFOSA 503>80

13 PFC ANALYSIS - Key Points Solubilities and Losses All QC and unknown samples go through entire analytical process after sample created Indicates / reduces bias, enhancement, or suppression 2 nd injection (diluted) used when suspected Higher C chain analytes sticky, detail in processing to avoid Lower C chain analytes volatile control with base / avoid blow down to dryness SPE Extraction / Clean-Up WAX used, HLB fine for higher chain lengths Optional incremental clean-ups (Envirocarb Envirocarb) Default is dissolved portion measurement Whole water or 2 separate analysis may be required where solids levels high (SPE and direct injection method limitation) project specific discussion Definition of sample and objectives key

14 Example EPA Tier 1 Validation PFC Method QC data for water. Analyte Blank (ng/l) IPR, n=5 %rec. (%RSD) MDL (ng/l), n=9 PFBA (9.5) 0.72 PFPeA (2.7) 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

15 Aqueous Sam[ple Handling AXYS / DuPont PFC and FTOH Study Experimental design Perfluorinated acids (PFAs) Method validation: Validated in three matrices, at three concentrations, in triplicate, and at three different days. Hold time study: Matrix = reagent water Container types = polypropylene, amber glass, and High Density Polyethylene (HDPE). Hold time intervals = 0, 2, 7, 14, 28, 60 and 90 Days. # of samples analyzed = 3 samples per hold time interval. Storage temperature = 4oC Experimental design FTOHs Experimental Design - FTOHs Method Validation; Validated in two matrices, at three concentrations, in triplicate, and at three different days. Hold time study Matrix = Methanol and filter Container types = Amber glass jar with polypropylene caps. Hold time intervals = 0, 2, 7, 14, 28, 60 and 90 Days. # of samples analyzed = 3 samples per hold time interval. Storage temperature = -20oC

16 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 25% under all the variables investigated. Percent recovery and precision (%RSD) for aqueous matrices at three spiking levels. Low Reagent water Mid High Low Groundwater Mid High Low Surface water PFBA 102(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) PFPeA 99.6(7.3) 90.3(4.1) 98.8(6.0) 8(6 101(5.7) 87.8(8.0) 8(8 99.8(9.1) 98.2(5.6) 85.6(3.1) 81.2(3.9) PFHxA 103(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) PFHpA 95.3(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) PFOA 99.7(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) PFNA 95.0(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) PFDA 89.2(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) PFUnA 95.3(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) PFDoA 105(6.8) 108(3.9) 111(2.7) 102(9.6) 103(7.0) 0) 109(4.9) 9) 98.6(11) 103(6.5) 105(7.5) 5) PFBS 116(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) PFHxS 111(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) PFOS 107(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) PFOSA 108(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. Mid High

17 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. 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. * % recovery for all compounds except PFUnA and PFDoA were above 80% prior to Day 28%.

18 PFOA in PP container PFOS in PP container Amount (ng) PFOA Spiked Amount (ng) PFOS Spiked Storage (Days) Storage (Days) PFOA in AG container PFOS in AG container Amount (ng) PFOA Spiked Amount (ng) PFOS Spiked Storage (Days) Storage (Days) PFOA in HDPE container PFOS in HDPE container Amount (ng) PFOA Spiked Amount (ng) PFOS Spiked Storage (Days) Storage (Days)

19 PFC Adsorption to Polypropylene Containers Recovery by Methanol Rinse Percent recovery of analytes from aqueous sample and associated polypropylene container. Analyte Spike in ng % rec. on aqueous matrix % rec. on PP container DAY 0 DAY 7 DAY 14 DAY 28 DAY 0 DAY 7 DAY 14 DAY 28 % Rec. % Rec. % Rec. % Rec. % Rec. % Rec. % Rec. % Rec. PFBA nd PFPeA nd nd nd PFHxA nd PFHpA nd PFOA nd PFNA PFDA PFUnA PFDoA PFBS nd PFHxS PFOS PFOSA nd = Analyte not detected. Each data point represents an average of at least duplicate measurements. nd nd nd nd nd nd nd nd nd nd nd

20 AXYS / DuPONT Hold Time and Container Conclusions Hold time and container selection Perfluorinated carboxylic and sulfonic acids Up to 28% PFUnA and 34% PFDoA were recovered from polypropylene containers that were used for storing water samples contaminated with Perfluorinated acids. Polypropylene containers are therefore not suitable for sample collection for these analytes. Mean percent recovery e values of all PFA analytes were e above 90% after 60 days of storage in Amber glass containers. Mean percent recovery values of all PFA analytes were above 70% after 60 days of storage in HDPE containers. Fluorotelomer alcohols Volatile components of FTOHs (e.g 4:2 FTOH and 6:2 FTOH) were lost significantly as soon as they were spiked on filter samples. Quantitative recovery values were observed for 8:2, to 16:2 FTOHs spiked and stored in closed amber glass jars. Analyte stability Perfluorinated carboxylic and sulfonic acids were observed to be stable in reagent water samples through the study period. Any observed losses were explained by adsorption onto the container. Fluorotelomer alcohols were observed to be stable on filter samples through the study period. Any observed losses were explained by volatility of the compounds.

21 AFFF Site Aqueous Analysis Active since 2007 for 13 default PFAAs aqueous and solid matrices High Level Aqueous Sample Protocol ( ) 11) High level of matrix creates suppression and enhancement Matrix includes non-target fluorinated compounds Default sample size reduction to place result in calibration range Pre-Screen for range finding (direct injection) from 500 ml sample container 2 sample containers (500mL and 50 ml), entire sample used. Surrogate overspike /extract split based on pre-screen to maintain result in calibration range High Level Samples Potential to create multi-phase liquids (i.e. foam or heterogenous samples) Multi-Phase Samples (Solid / Liquid) Analysis is dissolved phase only for water unless otherwise defined Multi-phase samples may need phase separation and separate treatment

22 Aqueous Sample from Hell

23 AFFF Samples Effect of Full Sample Utilization (Sub-sampling of Heterogenous Sample Avoided Analyte MW 1286D MW 1286D Dup C MW 1286D Dup C Sample Size 500 mls of 26 mls of 1L 26 mls of 1L 50 mls of 50 mls of 1L Sample Sample Sample 50 ml 50 ml (May (October (October Sample sampling) Sampling) Sample Sampling) (October (October Sampling) Sampling) PFBA 2, ,700 2,800 2,671 2,732 PFPeA 8,000 11,000 11,000 10,533 10,289 PFHxA 9,400 12,000 11,000 11,297 10,667 PFHpA 1,800 2,600 2,500 2,319 2,045 PFOA 2,900 3,000 2, , ,819 PFNA <93 PFDA PFUnA <1 <19 <19 <94 <93 PFDoA <1 <19 <19 <94 <93 PFBS 3,600 1, ,951 1,672 PFHxS 14,000 5,500 3,900 13,788 12,225 PFOS 50, ,602 13, PFOSA 910 <19 <

24 Effect of Filter Types on AFFF Aqueous Samples Filtration Used to Eliminate High Solids in Aqueous Samples Nylon filters used Discovered in 2012 that high level, complex AFFF samples has significant analyte loss (30 90%) for some targets Situation Investigated by Matrix (DW, non-afff site ground and surface waters, POTW waters, high h level l AFFF groundwaters with 4 filter types Losses applicable to AFFF high level samples (PFSA C6+, PFCA 9+) Glass Fiber filtration validated as compatible filter

25 AFFF Site Sample Heterogeneity at AFFF Sites PFOS (Left) PFBS (Left) PFBA (Right) PFHXA (Right) PFHXS (Right) 60 Concentra ation (ng/l L) Concentra ation (ng/l L) Layer (Top to Bottom) 0

26 AFFF Foams 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, plus product handling additives /solvents (cold weather and corrosion protection) Historically % w/w PFOS or FTS compounds. New PFOS replacements are lower C number PFAA + FTS as a backbone with other groups added

27 Typical AFFF Formulation Information (FC-203CF) Component Composition (%) Water Diethyleneglycolbutylether (Butyl Carbitol) 20 Amphoteric fluoroalkylamide derivative Alkyl sulfate salts Perfluoroalkylsulfonate salts Triethanolamine Tolyltriazole (Corrosion inhibitor) 0.05

28 FTS Typical Occurrence at AFFF Sites

29 AFFF High Level Samples Future Analysis Processes for accurate measurement, handling of high level / high solids samples exists Current Procurement Process May be direct to sampler / end user sampling protocols and data objectives considered May be through 3 rd party, short term bid - $. TAT, detection limits only discussed Latter may limit data quality Multiple levels of analysis? Targeted levels Analyte list (PFOS / PFOA or more comprehensive lists) Whole Water / High solids guidance from users

30 Open Forum Questions Follow-Ups