GLP10-01-02: Interim Report 26 - Analysis of PFBS. PFHS. and PFOS in Surface Water 

Samples Collected at Bert Jeffries Landfill in Decatur. AL in February 2012 

Study Title 

Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and 

Perfluorobutane Sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 

Site-Related Monitoring Program 

Data Requirement 

EPA TSCA Good Laboratory Practice Standards 40 CFR Part 792 

Study Director 

Jaisimha Kesari P.E., DEE 

Weston Solutions, Inc. 

1400 Weston Way 

West Chester, PA 19380 

Phone: 610-701-3761 

Author 

Susan Wolf 

3M Environmental Laboratory 

Interim Report Completion Date 

Date of signing 

Performing Laboratory 

3M Environmental Health and Safety Operations 

Environmental Laboratory 

3M Center, BIdg 260-05-N-17 

St Paul, MN 55144 

Project Identification 

GLP10-01-02-26 

Total Number of Pages 

77 

mm 

The testing reported herein meet the requirements of ANSI/ISO/lEC 17025:2005 "General Requirements for 

, T ^ . the Competence of Testing and Calibration Laboratories", In accordance with the A2LA Testing Certificate # 

|ACCREPlf¥Dl 2052.01. Testing that compiles with this International Standard also meets principles of ISO 9001:2000. 

Testing Cert #2052.01 
This page has been reserved for specific country requirements. 

Page 2 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

GLP COMPLIANCE STATEMENT 

Report Title: Interim Report 26 - Analysis of PFBS, PFHS, and PFOS in Surface Water Samples 

Collected at Bert Jeffries Landfill in Decatur, AL in February 2012 

Study: Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and 

Perfluorobutane Sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 

Site-Related Monitoring Program. 

This analytical phase was conducted in compliance with Toxic Substances Control Act (TSCA) Good 

Laboratory Practice (GLP) Standards, 40 CFR 792, with the exceptions listed below: 

• These are environmental samples where there is no specific test substance, no speciflc test 

system and no dosing of a test system. 

• The reference substances have not been characterized under the GLPs and the stability under 

storage conditions at the test site have not been determined under GLPs. 

% / 

Gary' Hohe||^steinySponsor Representative Date 

Jaisimha Kesari, P.E., DEE, Study Director ' ' Date 

Page 3 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

QUALITY ASSURANCE STATEMENT 

Report Title: Interim Report 26 - Analysis of PFBS, PFHS, and PFOS in Surface Water Samples 

Collected at Bert Jeffries Landflll in Decatur, AL in Febaiary 2012 

Study: Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and 

Perfluorobutane Sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 

Site-Related Monitoring Program. 

This analytical phase was audited by the 3M Environmental Laboratory Quality Assurance Unit (QAU), 

as indicated in the following table. The findings were reported to the principal investigator (P.I.), 

laboratory management and study director. 

Inspection Dates Phase 

Date Re 3orted to 

Inspection Dates Phase Testing Facility 

Management 

Study Director 

4/2/12-4/3/12 Data and Report 4/9/12 4/6/12 

QAU Represeraative Date 

Page 4 of 77 
TABLE OF CONTENTS 

GLP Compliance Statement 3 

Quality Assurance Statement 4 

Table of Contents 5 

List of Tables 6 

1 Study Infomiation 7 

2 Summary 8 

3 Introduction 9 

4 Test & Control Substances 9 

5 Reference Substances 10 

6 Test System 11 

7 Method Summary 12 

7.1 Methods 12 

7.2 Sample Collection 12 

7.3 Sample Preparation 12 

7.4 /^alysis 12 

8 Analytical Results 13 

8.1 Calibration 13 

8.2 System Suitability 14 

8.3 Limit of Quantitation (LOQ) 14 

8.4 Continuing Calibration 14 

8.5 Blanks 14 

8.6 Lab Control Spikes (LCSs) 14 

8.7 Analytical Method Uncertainty 16 

8.9 Field Matrix Spikes (FMS) 16 

Page 5 of 77 
9 Data Summary and Discussion 16 

10 Conclusion 20 

11 Data/Sample Retention ' 20 

12 /attachments 20 

13 Signatures 21 

LIST OF TABLES 

Table 1. Summarized PFBS, PFHS, and PFOS Results (Jeffries Landfill Site, Feb 2012) 8 

Table 2. Sample Description Key Code 11 

Table 3. Instrument Parameters 12 

Table 4. Liquid Chromatography Conditions 13 

Table 5. Mass Transitions 13 

Table 6. Limit of Quantitation (LOQ) 14 

Table 7. Laboratory Control Spike Recovery 15 

Table 8. Analytical Uncertainty 16 

Table 9. Field Matrix Spike Levels 16 

Table 10. JPAL SW ET01 120228 17 

Table 11. JPAL SW ET02 120228 17 

Table 12. JPAL SW ET03 120228 18 

Table 13. JPAL SW ET04 120228 18 

Table 14. Trip Blank 120228 19 

Page 6 of 77 
1 study Information 

Sponsor 

3M Company 

Sponsor Representative 

Gary Hohenstein 

3M EHS Operations 

3M Building 224-5W-03 

Saint Paul, MN 55144-1000 

Phone: (651)737-3570 

Study Director 

Jaisimha Kesari, P.E., DEE 

Weston Solutions, Inc. 

Westchester, PA 19380 

Phone: (610)701-3761 

Fax: (610) 701-7401 

j.kesari(@westonsolutions.com 

Study Location 

Testing Facility 

3M EHS Operations 

3M Environmental Laboratory 

Building 260-5N-17 

St. Paul, MN 55144 

Study Personnel 

William K. Reagen, Ph.D., 3M Laboratory Manager 

Cleston Lange, Ph.D., Principal /Analytical Investigator, (clange(S).mmm.com): phone (651)-733-9860 

Susan Wolf, 3M /Analyst 

Chelsie Grochow, Analyst 

Kevin Eich, Analyst 

Kelly Ukes, Analyst 

Jonathan Steege, Analyst 

Study Dates 

Study Initiation: March 8, 2010 

Interim 26 Experimental Termination: March 14, 2012 

Interim Report Completion: Date of Interim Report Signing 

Location of Archives 

All original raw data and the analytical report have been archived at the 3M Environmental 

Laboratory according to 40 CFR Part 792. The test substance and analytical reference standard 

reserve samples are archived at the 3M Environmental Laboratory according to 40 CFR Part 792 

Page 7 of 77 
2 Summary 

The 3M Environmental Laboratory received surface water samples from four different locations located 

at Jefl'ries Landfill in Decatur, AL. A total of nineteen sample bottles were received at the 3M 

Environmental Laboratory for perfiuorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHS) 

and perfluorobutane sulfonate (PFBS), and included duplicate surface water samples and two field 

matrix spike (FMS) samples from each sampling location. A set of trip blank samples; single trip blank 

containing Milli-QTM water and two trip blank spikes, were included with the sample bottles. /All samples 

were logged into the laboratory information management system (LIMS) under project GLP10-01-02-

26. The surface water samples and trip blanks were received from Weston personnel on March 2, 

2012. /Ml of the samples were prepared and analyzed for PFBS, PFHS, PFOS, and the surrogate 

recovery standard ^^C4-PF0S, following 3M Environmental Laboratory Method ETS-8-044.1. 

The average measured PFBS, PFHS, and PFOS concentrations are summarized in Table 1. The trip 

blank sample was below the lower limit of quantitation (LLOQ) for all analytes, indicating adequate 

control of sample contamination during shipping and sample collections. The analytical method 

uncertainties associated with tiie reported results are: PFBS + 22%, PFHS + 19% and PFOS + 15%. 

Table 1. Summarized PFBS, PFHS, and PFOS Results (Jeffries Landfill Site, Feb 2012). 

3M LIMS ID Sample Description 

PFBS 

Concentration 

(ng/mL) 

PFHS 

Concentration 

(ng/mL) 

PFOS 

Concentration 

(ng/mL) 

GLP10-01-02-026-005 JPAL-SW-ET01-0-120228 0.0345 <0.0250 0.0302 

GLP10-01-02-026-006 JPAL-SW-ET01-DB-120228 0.0362 <0.0250 0.0302 

Average 0.0354 <0.0250 0.0302 

%RPD Sample/Sample Dup 4.8 NA 0.0 

GLP10-01-02-026-009 JPAL-SW-ET02-0-120228 <0.0250 <0.0250 0.0661 

GLP10-01-02-026-010 JPAL-SW-ET02-DB-120228 <0.0250 <0.0250 0.0593 

Average <0.0250 <0.0250 0.0627 

%RPD Sample/Sample Dup NA NA 11 

GLP10-01-02-026-013 JPAL-SW-ET03-0-120228 <0.0250 <0.0250 0.303 

GLP10-01-02-026-014 JPAL-SW-ET03-DB-120228 <0.0250 0.0252 0.303 

Average <0.0250 0.0252 0.303 

%RPD Sample/Sample Dup NA NA'^' 0.0 

GLP10-01-02-026-017 JPAL-SW-ET04-0-120228 <0.0250 <0.0250 0.166 

GLP10-01-02-026-018 JPAL-SW-ET04-DB-120228 <0.0250 <0.0250 0.159 

Average <0.0250 <0.0250 0.163 

%RPD Sample/Sample Dup NA NA 4.3 

GLP10-01-02-026-025 JPAL-SW-TRIP1-0-120228 <0.0250 <0.0250 <0.0232 

NA = Not Applicable 

The analytical method uncertainties associated with the reported results are: PFBS ± 22%, PFHS ± 19 %, and 

PFOS ±15%. 

(1) A sample/sample duplicate RPD could not be determined since the concentration for the primary sample was 

BLOQ for PFHS. 

Page 8 of 77 
3 Introduction 

This analytical study was conducted as part of the Phase 3 Environmental Monitoring and Assessment 

Program for the 3M facility located in Decatur, Alabama. The objective of the overall program is to gain 

infomiation regarding concenti-ations of perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate 

(PFHS) and perfluorobutane sulfonate (PFBS), in various environmental media such as groundwater, 

soils and sediments that are associated with and near the Decatur facility. This analytical study was 

conducted to analyze surface water samples collected from four locations at or near Jeffries Landfill in 

Decatur, AL for PFBS, PFHS, and PFOS in an effort to characterize surface water conditions. 

The 3M Environmental Laboratory prepared sample containers (250 mL high-density polyethylene 

botties) which were shipped to Decatur, AL Weston personnel prior to field sampling. Sample 

containers for each sampling location included a field sample, field sample duplicate, and two field 

matrix spike samples. Each empty container was mari<ed with a "fill to here" line to produce a final 

sample volume of 200 mL. Containers designated for field matiix samples were fortified with an 

appropriate matrix spike solution containing PFBS (linear isomer), PFHS (linear isomer), and PFOS 

(linear and branched isomers) prior to being sent to the field for sample collection. /Ml sample bottles 

included the addition of ^^Oz-PFBS, ''^Ca-PFHS, and ^^Cg-PFOS (intemal standard) at a nominal 

concentration of 1 ng/mL. All sample bottles also included the addition of "C4-PFOS (surtogate 

recovery standard) at a nominal concentration of 0.1 ng/mL. See section 8.8 of the report for field 

matrix spike levels. 

Samples were prepared and analyzed according to the procedure defined in 3M Environmental 

Laboratory metiiod ETS-8-044.1 "Method of /Analysis for the Detennination of Perfiuorinated 

Compounds In Water by LC/MS/MS; Direct Injection Analysis". The use of internal standards was 

used to aid in the data quality objectives. 

Table 1 summarizes the average PFBS, PFHS, and PFOS concenti-ations for the duplicate surface 

water samples collected and the trip blank sample. Tables 10-14 summarize the individual sample 

results and the associated field matrix spike recoveries. All results for the quality control samples 

prepared and analyzed with the samples are reported and discussed elsewhere in tills report 

4 Test & Control Substances 

There was not a test substance or control substances in the classic sense of a GLP study. This study 

was purely analytical in nature. 

Page 9 of 77 
5 Reference Substances 

Reference Substance 

PFBS 

(predominantly linear) 

"O2-PFBS 

Chemical Name 

Potassium 

Perfluorobutane sulfonate 

f*02]-Ammonium 

Perfluorobutanesulfonate 

Chemical Formula C4F9SO3X" C4F9S['*02]0-NH/ 

Identifier NA NA 

Use 

Target Analyte Reference 

Standard Intemal Standard 

Source 3M RTI Intemational 

Expiration Date 01/10/2017 03/09/2015 

Storage Conditions Frozen Frozen 

Chemical Lot Number 41-2600-8442-5 11546-107-2 

TCR Number TCR-121 TCR-1044,TCR-1040 

Physical Description White Powder Liquid 

Purity 96.7% >99% 

Reference Substance 

PFHS 

(Linear) 

"C3-PFHS "C3-PFHS 

Chemical Name 

Sodium Perfluorohexane 

sulfonate 

Sodium 

Perfluorohexanesulfonate 

Sodium 

Perfluorohexanesulfonate 

Chemical Formula CgFisSOs'Na^ ''Cs^'CsFiaSOs-Na' "Ca^'CaFiaSOs-Na' 

Identifier L-PFHXS MPFC-C-0511 MPFC-C-0112 

Use 

Target Analyte Reference 

Standard Intemal Standard Intemal Standanj 

Source Wellington Wellington Wellington 

Expiration Date 03/25/2018 05/25/2014 01/24/2015 

Storage Conditions Frozen Frozen Frozen 

Chemical Lot Number LPFHxSAMOS MPFC-C-0511 MPFC-C-0112 

TCR Number TCR08-0018 TCR11-0016 TCR12-0004 

Physical Description Crystalline Liquid Liquid 

Purity 100% 5|jg/mL<^' 5|jg/mL<^' 

(1) Custom mixture of seven mass-labeled ("C) perfluoroalkylcarboxyllc acids, two mass labeled ("C) 

perfluoroalkylsulfonates and one mass-labeled ("C) perfluoro-1-octanesulfonamide. 

Page 10 of 77 
Reference 

Substance 

PFOS 

(Linear + Branched) 

"C4-PFOS "Ca-PFOS "Ca-PFOS 

Chemical Name 

Potassium 

Perfluorooctane 

sulfonate 

Sodium 

Perfluorooctane 

sulfonate 

Sodium 

Perfluorooctane 

sulfonate 

Sodium 

Perfluorooctane 

sulfonate 

Chemical Formula CsF-iySOs K ^^C4^^C4Fi7S03'Na^ ^^C8Fi7S03"Na" 

Identifier Br-PFOSK MPFOS MPFC-C-0511 MPFC-C-0112 

Use 

Target Analyte 

Reference Standard Surrogate Intemal Standard Intemal Standard 

Source Wellington Wellington Wellington Wellington 

Expiration Date 

03/17/2014; 

12/01/2014 09/08/2013 05/25/2014 01/24/2015 

Storage Conditions Frozen Frozen Frozen Frozen 

Chemical Lot Number 

brPFOSK0708; 

brPFOSKim 

MPFOS0910 MPFC-C-0511 MPFC-C-0112 

TCR Number 

TCR11-0010; 

TCR11-0041 TCR10-0044-7/9 TCR11-0016 TCR12-0004 

Physical Description Liquid Liquid Liquid Liquid 

Purity 99.9% >98% 5|jg/mL'^' Spg/mL'^' 

(1) Custom mixture of seven mass-labeled ("C) perfluoroalkylcarboxylic acids, two mass labeled ( C) 

perfluoroalkylsulfonates and one mass-labeled ("C) perfluoro-1-octanesulfonamide. 

6 Test System 

The test systems for this study are surface water samples collected from wells located in Decatur, AL 

by Weston Solutions, Inc. personnel. Samples for this study are "real world" samples, not dosed with a 

specific lot of test substance. 

Table 2. Sample Description Key Code. 

string Number String Descriptor Example 

Example JPAL-SW-ET01-0-120228 

1 Sample Location JPAL= Jeffries Property, Alabama 

2 Sample Type SW = Surface Water 

3 Well ID Example: ET01 

ET=Eastern tributary to Mallard Creek 

4 Sampling Date 120228- February 28, 2012 

5 Sample Type 0 = primary sample 

DB = duplicate sample 

LS" low spike 

HS = high spike 

Page 11 of 77 
7 Method Summary 

7.1 Method 

Analysis for all analytes was completed following 3M Environmental Laboratory method ETS-8-044.1 

"Method of Analysis for the Determination of Perfiuorinated Compounds In Water by High Perfomnance 

Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". 

7.2 Sample Collection 

Samples were collected in 250 mL NalgeneTM (high-density polyethylene) bottles prepared at the 3M 

Environmental Laboratory. Sample bottles associated with GLP10-01-02-26 were retumed to tiie 

laboratory at ambient conditions on March 2, 2012. Samples were stored refrigerated at the laboratory 

after receipt. A set of laboratory prepared Trip Blank and Trip Blank field matrix spikes were sent with 

the sample collection bottles. 

7.3 Sample Preparation 

Samples were prepared by removing an aliquot of the well mixed sample and placing it in an autovial for 

analysis. 

During tiie preparation of the laboratory control samples, an aliquot of a separate intemal standard 

spiking solution was added to the laboratory control samples (nominal concentration of 1 ng/mL). The 

samples bottles were spiked witii an intemal standard mix at a nominal concentration of 1 ng/mL prior to 

being sent to the field for sample collection 

7.4 Analysis 

All study samples and quality control samples were analyzed for PFBS, PFHS, and PFOS using high 

perfomiance liquid chromatography/ tandem mass spedrometiy (HPLC/MS/MS). Detailed instnjment 

parameters, the liquid chromatography gradient program, and tiie specific mass ti-ansitions analyzed are 

described in the raw data hard copies placed in the final data packet, and are briefiy described below. 

Table 3. Instrument Parameters. 

Instrument Name ETS Ginger ETS McCoy 

Analytical Method Followed ETS-8-044.1 ETS-8-044.1 

Analysis Date 3/7/12-PFBS and PFHS 3/13/12-PFOS 

Liquid Chromatograph Agilent 1100 Agilent 1290 

Guard column Betasil CI 8 (4.6 mm X100 mm), 5n Betasil CI 8 (4.6 mm X100 mm), 5n 

Analytical column Betasil C18 (4.6 mm X100 mm), 5n Betasil C18 (4.6 mm X100 mm), 5|x 

Injection Volume 25 nL 50 nL 

Mass Spectrometer Applied Biosystems API 5000 Applied Biosystems API 5500 

Ion Source Turbo Spray Turbo Spray 

Electrode Turbo ion electrode Turbo ion electrode 

Polarity Negative Negative 

Software Analyst 1.4.2 Analyst 1.5.2 

Page 12 of 77 
Table 4. Liquid Chromatography Conditions. 

step Total Time Flow Rate Percent A PercentB 

Number (min) (juUmin) (2 mM ammonium acetate) (methanoO 

ETS-8-044.1 Analyzed 3/7/12 

0 0.0 750 97.0 3.0 

1 2.0 750 97.0 3.0 

2 14.5 750 5.0 95.0 

3 15.5 750 5.0 95.0 

4 16.5 750 97.0 3.0 

5 20.0 750 97.0 3.0 

Step Total Time Flow Rate Percent A Percent S 

Number (mIn) (fdJmin) (5 mM ammonium acetate: (acetonitrile) 

0.01% acetic acid) 

ETS-8-044.1 Analyzed 3/13/12 

0 0.0 750 97.0 3.0 

1 2.0 750 97.0 3.0 

2 14.5 750 5.0 95.0 

3 15.5 750 5.0 95.0 

4 16.5 750 97.0 3.0 

5 20.0 750 97.0 3.0 

Table 5. Mass Transitions. 

Analyte 

Mass Transition 

Q1/Q3 

Reference 

Material 

Structure 

intemal Standard Mass Transition 

Q1/Q3 

PFBS 299/80 

299/99 

Linear t'OJ-PFBS 303/84 

PFHS 

399/80 

399/99 Linear rcj-PFHS 402/80 

PFOS 

499/80 

499/99 

499/130 

Linear + 

Branched t'CsI-PFOS 507/80 

C'CJ-PFOS 503/80 Linear rcJ-PFOS 507/80 

Dwell time was 50 msec for each transition. The individual transitions were summed to produce a "total ion 

chromatogram" (TIC), which was used for quantitation. 

8 Analytical Results 

8.1 Calibration 

Samples were analyzed using a stable isotope intemal standard calibration curve. Calibration standards 

were prepared by spiking known amounts of the stock solution containing the target analytes into a 

laboratory-prepared synthetic groundwater containing calcium and magnesium. A separate intemal 

standard spiking solution was prepared and an aliquot was added at tiie same level to all calibration 

standards and laboratory conti"ol samples at a nominal concentration of 1 ng/mL. A calibration curve 

ranging from approximately 0.025 ng/mL to 100 ng/mL (0.025 ng/mL to 10 ng/mL for ^^C4-PF0S 

sun-ogate) was prepared. The reference standard used for the calibration standards for PFOS 

contained both linear and branched isomers. 

Page 13 of 77 
A quadratic, 1/x weighted, calibration curve of tiie standard peak area/peak area ratios was used to fit 

the data for each analyte. The data were not forced through zero during the fitting process. Calculating 

the standard concentrations using tiie peak area/peak area ratios and tiie resultant calibration curve 

confimied accuracy of each curve point. 

Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method 

calibration accuracy requirements of 100±25% (100±30% for the lowest curve point) were met for all 

analytes. The comelation coefficient (r) was greater than 0.995 for PFBS, PFHS, PFOS, and ^^C4-PF0S. 

8.2 System Suitability 

A calibration standard was analyzed four times at the beginning of each analytical sequence to 

demonstrate overall system suitability. The acceptance criteria of less than or equal to 5% relative 

standard deviation (RSD) for peak area and retention time criteria of less than or equal to 2% RSD was 

met for PFBS, PFHS, PFOS, and ^^C4-PF0S. 

8.3 Limit of Quantitation (LOQ) 

The LOQ for this analysis is the lowest non-zero calibration standard in the curve that meets linearity 

and accuracy requirements and for which the area counts or area ratio are at least twice those of the 

appropriate blanks. The LOQ for all analytes can be found in Table 6. 

Table 6. Limit of Quantitation (LOQ). 

PFBS 

LOQ, ng/mL 

PFHS 

LOQ, ng/mL 

PFOS 

LOQ, ng/mL 

0.0250 0.0250 0.0232 

8.4 Continuing Calibration 

During the course of each analytical sequence, continuing calibration verification samples (CCVs) were 

analyzed to confimn that the instiument response and the initial calibration curve were still in control. All 

CCVs met method criteria of 100% ± 25% for PFBS, PFHS, PFOS, and ^^C4-PF0S. 

8.5 Blanks 

Two types of blanks were prepared and analyzed with tiie samples: procedural blanks and tiip blanks. 

Procedural blank results were reviewed and used to evaluate metiiod perfomiance to determine tiie 

LOQ. Trip blanks reflect the shipping and sample collection conditons the sample bottles and samples 

experience. 

8.6 Lab Control Spikes (LCSs) 

Low, mid, and high lab control spikes were prepared for the target analytes and analyzed in triplicate, 

while only low and high lab control spikes were prepared for the ^^C4-PF0S sun-ogate. LCSs were 

prepared by spiking known amounts of the analyte into syntiietic groundwater to produce the desired 

concentration. The spiked water samples were then prepared and analyzed in the same manner as the 

samples. The method acceptance criteria, average of LCS at each level should be within 100% ± 20% 

with an RSD <20%, was met for all analytes. 

The following calculations were used to generate data in Table 7 for laboratory conti"ol spikes. 

1 r> »r> Calculated Concentration , . .„„, 

LCS Percent Recovery = * 100% 

Spike Concentration 

LCS%RSD = standard deviationlCSreplicates .^^^y^ 

average LCS recovery 

Page 14 of 77 
Table 7. Laboratory Control Spike Recovery. 

ETS-8-044.1 

Analyzed 3/7/12 PFBS PFHS 

Spiked 

Concentration 

Calculated 

Concentration 

Spiked 

Concentration 

Calculated 

Concentration 

Lab ID (ng/mL) (ng/mL) 'ARecovery (ng/mL) (ng/mL) VoRecovery 

LCS-120306-1 0.198 0.209 105 0.198 0.191 96.3 

LCS-120306-2 0.198 0.209 106 0.198 0.182 91.8 

LCS-120306-3 0.198 0.207 104 0.198 0.185 93.3 

Average ± %RSD 105% ±0.95% 93.8% ±2.4% 

LCS-120306-4 1.98 2.17 110 1.98 2.08 105 

LCS-120306-5 1.98 2.19 111 1.98 1.92 97.1 

LCS-120306-6 1.98 2.09 106 1.98 1.94 98.0 

Average ± %RSD 109% ±2.4% 100% ±4.3% 

LCS-120306-7 19.9 18.9 95.1 19.8 18.5 93.5 

LCS-120306-8 19.9 18.1 91.1 19.8 18.1 91.3 

LCS-120306-9 19.9 19.8 99.6 19.8 19.2 96.9 

Average ± %RSD 95.3% ±4.5% 93.9% ±3.0% 

ETS-8-044.1 

Analyzed 3/13/12 PFOS (Linear + Branclied) C4-PFOS surrogab 

Spiked 

Concentration 

Calculated 

Concentration 

Spiked 

Concentration 

Calculated 

Concentration 

Lab ID (ng/mL) (ng/mL) VoRecovery (ng/mL) (ng/mL) "ARecovery 

LCS-120306-1 0.184 0.178 97.0 0.189 0.221 117 

LCS-120306-2 0.184 0.170 92.6 0.189 0.215 114 

LCS-120306-3 0.184 0.170 92.6 0.189 0.225 119 

Average ± %RSD 94.1% ±2.7% 117% ±2.2% 

LCS-120306-4 1.84 1.76 95.6 1.89 2.21 117 

LCS-120306-5 1.84 1.72 93.6 1.89 2.14 113 

LCS-120306-6 1.84 1.71 92.9 1.89 2.14 113 

Average ± %RSD 94.0% ±1.5% 114% ±2.0% 

LCS-120306-7 18.4 17.1 92.8 NA NA NA 

LCS-120306-8 18.4 16.6 90.4 NA NA NA 

LCS-120306-9 18.4 17.4 94.3 NA NA NA 

Average ± %RSD 92.5% ±2.1 % NA 

NA = Not Applicable 

Page 15 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

8.7 Analytical Method Uncertainty 

Analytical uncertainty is based on historical QC data that is control charted and used to evaluate 

method accuracy and precision. The method uncertainty is calculated following ETS-12-012.2. The 

standard deviation is calculated for the set of accuracy results (in %) obtained for the QC samples. The 

expanded uncertainty is calculated by multiplying the standard deviation by a factor of 2, which 

con-esponds to a confidence level of 95%. 

Table 8. Analytical Uncertainty. 

Analyte Standard Deviation Method Uncertainty 

PFBS 10.8 ±22% 

PFHS 9.42 ±19% ' 

PFOS 7.60 ±15% 

8.8 Field Matrix Spikes (FMS) 

Low, mid, and high field matrix spikes (FMS) were collected at each sampling point to verify that the 

analytical method is applicable to the collected matrix. Field matrix spikes were generated by adding a 

measured volume of field sample to a container spiked by the laboratory with PFBS (linear), PFHS 

(linear), and PFOS (linear+branched) prior to shipping sample containers for sample collection. Field 

matrix spike recoveries within method acceptance criteria of 100±30% confirm that "unknown" 

components in the sample matrix do not significantly interfere with the extraction and analysis of the 

analytes of interest. Field matrix spike concentrations must be 50% of the sample concentration to be 

considered an appropriate field spike. Field matrix spikes are presented in section 9 of this report. 

Table 9. Field Matrix Spike Levels. 

Sampling Location Spike Level PFBS, 

ng/mL 

PFHS, 

ng/mL 

PFOS, 

ng/mL 

All locations and Trip Blank Low 1.00 0.998 0.928 All locations and Trip Blank 

High 10.0 9.98 9.28 

FMS Recovery J Sample Concentration of FMS - Average Concentration: Field Sample & Field Sample Dup.) • .,QQO/ 

Spike Concentraton 

d Data Summary and Discussion 

The tables below summarize the sample results and field matrix spike recoveries for the sampling 

locations as well as the Trip Blank. Results and average values are rounded to three significant figures 

according to EPA rounding rules. Because of rounding, values may vary slightly from those listed in the 

raw data. Field matrix spike recoveries meeting the method acceptance criteria of ± 30%, demonstrate 

that the method was appropriate for the given matrix and their respective quantitative ranges. 

Page 16 of 77 
Table 10. JPAL SW ET01 120228 

PFBS PFHS PFOS "C4PFOS 

Concentration Concentration Concentration 

3M LIMS ID Description (ng/mL) "ARecovery (ng/mL) 'ARecovery (ng/mL) "ARecovery "ARecovery 

GLP10-01-02-26-005 JPAL-SW-ET01-0-120228 0.0345 NA <0.0250 NA 0.0302 NA 109 

GLP10-01-02-26-006 JPAL-SW-ET01-DB-120228 0.0362 NA <0.0250 NA 0.0302 NA 102 

GLP10-01-02-26-007 JPAL-SW-ET01-LS-120228 1.08 104 0.946 94.8 0.863 89.7 110 

GLP10-01-02-26-008 JPAL-SW-ET01-HS-120228 10.4 104 8.62 86.4 8.38 90.0 110 

Average Concentration (ng/mL) ± %RPD 0.0354 ng/mL ±4.8% <0.0250 ng/mL 0.0302 ng/mL ±0.0% 10S"A±3.3"A 

NA = Not Applicable 

Table 11. JPAL SW ET02 120228 

PFBS PFHS PFOS "C4PFOS 

Concentration Concentration Concentration 

3M LIMS ID Description (ng/mL) "ARecovery (ng/mL) VoRecovery (ng/mL) "ARecovery "ARecovery 

GLP10-01-02-26-009 JPAL-SW-ET02-0-120228 <0.0250 NA <0.0250 NA 0.0661 NA 107 

GLP10-01-02-26-010 JPAL-SW-ET02-DB-120228 <0.0250 NA <0.0250 NA 0.0593 NA 106 

GLP10-01-02-26-011 JPAL-SW-ET02-LS-120228 1.08 108 1.030 103 0.924 92.8 109 

GLP10-01-02-26-012 JPAL-SW-ET02-HS-120228 9.63 96.3 8.640 86.6 8.45 90.4 107 

Average Concentration (ng/mL) ± "ARPD <0.0250 ng/mL <0.0250 ng/mL 0.0627 ng/mL ±11"A 107% ± 1.2"A 

NA = Not Applicable 

Page 17 of 77 
Table 12. JPAL SW ET03 120228 

PFBS PFHS PFOS "C4PFOS 

Concentration Concentration Concentration 

3MLiMSiD Description (ng/mL) "ARecovery (ng/mL) VoRecovery (ng/mL) "ARecovery "ARecovery 

GLP10-01-02-26-013 JPAL-SW-ET03-0-120228 <0.0250 NA <0.0250 NA 0.303 NA 109 

GLP10-01-02-26-014 JPAL-SW-ET03-DB-120228 <0.0250 NA 0.0252 NA 0.303 NA 109 

GLP10-01-02-26-015 JPAL-SW-ET03-LS-120228 1.05 105 0.992 96.9 1.13 89.1 103 

GLP10-01-02-26-016 JPAL-SW-ET03-HS-120228 9.14 91.4 8.820 88.1 8.72 90.7 106 

Average Concentration (ng/mL) ± "ARPD <0.0250 ng/mL 0.0252 ng/mU^' 0.303 ng/mL ± 0.0% 707% ±2.7% 

NA = Not Applicable 

(1) A sample/sample duplicate RPD could not t>e determined since the concentration of the primary sample was BLOQ for PFHS. 

Table 13. JPAL SW ET04 120228 

PFBS PFHS PFOS "C4PFOS 

Concentration Concentration Concentration 

3M LIMS ID Description (ng/mL) "ARecovery (ng/mL) %Recovery (ng/mL) "ARecovery "ARecovery 

GLP10-01-02-26-017 JPAL-SW-ET04-0-120228 <0.0250 NA <0.0250 NA 0.166 NA 113 

GLP10-01-02-26-018 JPAL-SW-ET04-DB-120228 <0.0250 NA <0.0250 NA 0.159 NA 109 

GLP10-01-02-26-019 JPAL-SW-ET04-LS-120228 1.14 114 0.931 93.3 1.03 93.5 110 

GLP10-01-02-26-020 JPAL-SW-ET04-HS-120228 10.6 106 8.45 84.7 8.47 89.5 105 

Average Concentration (ng/mL) ± "ARPD <0.0250 ng/mL <0.0250 ng/mL 0.163 ng/mL ±4.3"A 109'A±3.2"A 

NA = Not Applicable 

Page 18 of 77 
Table 14. Trip Blank 120228 

PFBS PFHS PFOS "C4PFOS 

3M LIMS ID Description 

Concentration 

(ng/mL) %Recovery 

Concentration 

(ng/mL) "ARecovery 

Concentration 

(ng/mL) "ARecovery "ARecovery 

GLP10-01-02-26-025 JPAL-SW-TRIP1 -0-120228 <0.0250 NA <0.0250 NA <0.0232 NA 108 

GLP10-01-02-26-026 JPAL-SW-TRIP1 -LS-120228 1.06 106 0.947 94.9 0.809 87.2 109 

GLP10-01-02-26-027 JPAL-SW-TRIP1 -HS-120228 9.32 93.2 9.21 92.3 8.07 87.0 107 

NA = Not /Applicable 

Page 19 of 77 
10 Conclusion 

Laboratory conti-ol spikes and field mati-ix spikes were used to determine the analytical metiiod 

accuracy and precision for PFBS, PFHS, and PFOS. Analysis was successfully completed following 

3M Environmental Laboratory method ETS-8-044.1 described herein. 

11 Data/Sample Retention 

All remaining samples and associated project data (hardcopy and electi-onic) will be archived according 

to 3M Environmental Laboratory standard operating procedures. 

12 Attachments 

Attachment A: Protocol Amendment 26 (General Project Outiine) 

Attachment B: Representative Chromatograms and Calibration Curves 

Attachment C: Analytical Method-ETS-8-044.1 

Page 20 of 77 
13 Signatures 

GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

Cleston Lange, Ph.D., 3M Principal Analytical Investigator Date 

William K. Reagen, Ph.D., 3M Environmental Laboratory Department Manager Date 

t Gary Hbhenatein, Siponsor Representative Date 

Jk/rti 

' Date 

Jaisimha Kesari, Study Director 

Page 21 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

ATTACHMENT A: PROTOCOL AMENDMENT 

Page 22 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

Analytical Protocol: GLP10-01-02 

Amendment 26 

Study Title 

Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and 

Perfluorobutane sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M 

Decatur Phase 3 Site-Related Monitoring Program 

PROTOCOL AMENDMENT NO. 26 

Amendment Date: 

February 21, 2012 

Performing Laboratory 

3M Environmental, Health, and Safety Operations 

3M Environmental Laboratory 

Building 260-5N-17 

Maplewood. MN 55144-1000 

Laboratory Project Identification 

GLP10-01-02-26 

Sampling Event 

Bert Jeffries Landfill -Surface Water Sampling 

Page 1 of 6 

Page 23 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

Analytical Protocol: GLP10-01-02 

Amendment 26 

This amendment modifies tiie following portion of protocol: 

"Analysis of PFOS, PFHS and PFBS in Groundwater, Soil and Sediment for the 3M 

Decatur Phase 3 Site-Related Monitoring Program" 

PROTOCOL FISADS: 

No changes to the wording of the protocol are required. 

AMEND TO READ: 

No changes to the wording of the protocol are required. This amendment only addresses and documents 

the addition of the General Project Outline (GPO) for the collection and analysis of groundwater samples 

from Decatur, AL, and conducted as part of the 3M Decatur Phase 3 Prograin for PFOS, PFHS and PFBS 

(GLP10-01-02). Sampling activities at and near the Bert Jeffries landfill are scheduled for the week of 

February 27, 2012 and will consist of 6 paired surface water and sediment samples. This protocol. 

amendment addresses the sampling and analysis of the surface water samples. Surface water samples 

collected under this sampling event will be entered into the 3M Environmental Laboratory LIMS as project 

GLP10-01-02-26 and reported as interim report GLP10-01-02-26 (reflecting study GLP10-01-02 and 

amendment -26). 

Reason: 

The reason for this amendment is to document the General Project Outline (GPO) which describes the 

anticipated surface water sample collection event to be conducted at and near the Bert Jeffries landfill in 

Lawrence County, AL. 

The GPO Is three pages in length and included as attached to tills amendment form. 

Page 2 of 6 

Page 24 of 77 
Amendment Approval 

GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

Analytical Protocol: GLP10-01-02 

Amendment 26 

'71 

Gary Hohenstein, Sponsor Representative Date 

Cleston C. Lange, Principal Analytical Investigator Date 

William Reagen, EMS Opns Environmental Lab Management Date 

Date 

Page 3 of 6 

Page 25 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

Analytical Protocol: GLP10-01-02 

Amendment 26 

Environmental Health & Safety Operations, Environmental Laboratory 

General Project Outline 

To: Gary Hohenstein, 3M EHS&Opns 

From: Susan Wolf, 3M EHS&Opns; Environmental Lab 

cc: William Reagen, 3M EHS&Opns; Environmental Lab 

Jai Kesari, Weston Solutions 

Charles Young, Weston Solutions 

Date: February 21,2012 

Subject: Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and 

Perfluorobutane sulfonate (PFBS) in Groundwater, Soil and Sediment for tiie 3M Decatur 

Phase 3 Site-Related Monitoring Program; GLP Interim Report 26 - Bert Jeffries Landfill; 

Surface Water sampling the week of February 27, 2012. 

1 General Project Information 

3M Sponsor Representative 

Gary Hohenstein 

3M EHS Operations 

3M Building 224-5W-03 

Saint Paul, MN 55144^1000 

Phone: (651)737-3570 

aahohensteinffimmmicom 

3M Environmental Laboratory n/lanagenient 

William K. Reagen 

3M EHS Opns, Environmental Latioratory 

260-5N-17 

Contacts 651 733-9739 

wkreaaen@mmm.com 

Principal Analytical Investigator 

Cleston Lange 

3M EHS Opns, Environmeiital Laboratoiy 

260-5N-17 

651 733-9860 

cclanae@mmm.com 

Sampling Coortllnator 

Timothy Frinak 

Weston Solutions 

Timothv.frinakffiwestonsoluiion8,cQm 

Phone: (334).332-9123 

Lab Request Number qLP10-01-02-26 

Six Digit Department Number Oept #530711, Project #0022674449 

Project Schedule/Test Dates Tentatively scheduled for the weeK of Febaiary 27,2Q12. 

AH verbal end written correspondence will be directed to Gary Hohenstein. 

Page 4 of 6 

Page 26 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

Analytical Protocol: GLP10-Q1-02 

Amendment 26 

2 Background Information and Project Objective(s) 

The 3M EHS Operations Laboratory (3M Environmental Lab) will receive and analyze surface water 

samples collected from six (6) locations at and near the Bert Jeffries landfill. Surtace water samples will 

be collected by Weston. The 3M Environmental Laboratory will prepare the sample bottles; Samples will 

be analyzed for Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and 

Perfluorobutane Sulfonate (PFBS). Analyses will be conducted under the GLP requirements of EPA 

TSCA Good Laboratory Practice Standards 40 CFR 792. 

The final report will be submitted to Gary Hohenstein and Jai Kesari upon completion under interim report 

GLP10-01-02-26. 

3 Project Schedule 

Sample collection bottles will be prepared by the 3M Environmental Laboratory. Sample bottles will be shipped 

in coolers overnight to 3M Decatur for anival by Friday, Febmary 24,2012. Sample bottles should be stored 

refrigerated on-site until sample collection. 

Martin Smith \ Weston Trailer 

3M Decatur Plant 

1400 State Docks Road 

Decatur, Alabama 35601 

4 Test Parameters 

The targeted limit of quantitation will be 0.025 ng/mL (ppb) for PFBS, PFHS, and PFOS. 

A total of six sampling locations have been specified. For each sampling location, a total of four sample bottles 

will be collected (sample, sample duplicate, low-level field matrix spike, and high-level field matrix spike). The lill 

to here" line on each 250 mL Nalgene bottle will be 200 mL. One set of trip blanks consisting of reagent-grade 

water, a low-level trip blank spike, and a high-level trip blank spike will be prepared at the 3M Environmental 

Laboratory and sent to the sampling location with the other bottles. No previous data on fluorochemicals in 

groundwater, surface water or sediment media exist for the site. The low field matrix spike will be prepared at 1 

ng/mL and the high field matrix spike at 10 ng/mL. 

All sample bottles will Include the addition of ^*OrPFBS, "CrPFHS, and "Cs-PFOS. nntemal standards) at a 

nominal concentration of 1 ng/mL. M sample bottles will also Include the additbn of ^ C4-PFOS (sun-ogate 

recovery standard) at a nominal concentration of 0.1 ng/mL, 

To aid in sample collection, a non-spiked 1-L sample bottle will be provided for each sampling location. 

Sample collection will consist of direct immersion. Aliquots will be decanted from the collection bottle to 

the primary, duplicate and matrix spike bottles. No rinseate blank will be collected. 

Page 5 of 6 

Page 27 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

Analytical Protocol: GLP10-01-02 

Amendment 26 

S Test Methods 

Samples will be prepared and analyzed by LC/MS/MS following ETS-8-044.1 "Method of Analysis for the 

Detennination of Perfiuorinated Compounds In Water by High Perfomnance Liquid ChnDmatography/Mass 

Spectrometry Direct Injection Analysis". Altemately, samples may be analyzed by ETS 8-154.3 "Detemiination 

of Perfiuorinated Acids, Alcohols, Amides, and Sulfonates In Water By Solid Phase Extraction and High 

Perfomiance Liquid Chromatography/Mass Spectrometry" 

Where applicable, samples will be analyzed against an intemal standard calibration cun/e. Each cun/e point will 

contain isotopically-labeled PFBS, PFHS, and PFOS at a nominal cxjncentration of 1 ng/mL. The calibration 

cun/e will be generated by taking the ratio of the standard peak area counts over the intemal standard peak 

area counts to fit the data for each analyte. 

Laboratory control samples prepared with the samples must have an average recovery within 100±20% and a 

RSD S20%. The data quality objective for this study Is quantitative results for the target analytes with an 

analytical accuracy of 100+30%. Field matrix spikes not yielding recoveries within 100+30% will be addressed 

in the report and the final accuracy statement may be adjusted accordingly. 

6 Reporting Requirements 

For each sampling location, the report will contain the results for the sample, sample duplicate, and the two field 

matrix spikes. Trip blank and trip blank spikes will be reported for the sampling event. Laboratory control spikes 

of reagent water prepared at the time of sample extraction will also be reported and used to evaluate the overall 

method accuracy and precision. Method blanks of reagent water prepared at the time of sample extraction will 

be used to determine the method detection limit For those sampling locations where the field matrix spike level 

vras not appropriate due to higher than expected analyte concentrations, a target analyte laboratory matrix spike 

may be prepared and will be included in the final report. 

Page.e of 6 

Page 28 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

ATTACHMENT B : REPRESENTATIVE SAMPLE CHROMATOGRAMS AND 

CALIBRATION CURVE(S) 

Page 29 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

*ETS-McCoy Results Name: mcl20313a.rdb 

4.0 4.5 5.0 5.5 6.0 

Analyte Cone. / IS Cone. 

Data printe d by STW 

Printin g Time: 11:30:32 AM 

Printin g Date: Wednesday, Apri l 11, 2012 

Page 1 o f 1 

Page 30 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

*ETS-McCoy Result s Name: mcl20313a.rdb 

0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0 17.0 18.0 19.0 20.0 21.0 22.0 23.0 24.0 

Analyte Cone. / IS Cone. 

Data printe d by STW 

Printin g Time: 11:31:55 AM 

Printin g Date: Wednesday, Apri l 11, 2012 

Page 1 o f 1 

Page 31 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

Ginger AG01330509 Result s Name: gl20307a.rdb 

45 50 55 60 

Analyte Cone. / IS Cone. 

Data printe d by STW 

Printin g Time: 12:26:08 PM 

Printin g Date: Wednesday, Apri l 11, 2012 

Page 1 of 1 

Page 32 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

Ginger AG01330509 Result s Name: gl20307a.rdb 

Data printe d by STW 

Printin g Time: 12:24:26 PM 

Printin g Date: Wednesday, Apri l 11 , 2012 

Page 1 o f 1 

Page 33 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

*ETS-McCoy Result s Name: mcl20313a.rdb 

Data printe d by STW 

Printin g Time: 11:34:46 AM 

Printin g Date: Wednesday, Apri l 11, 2012 

Page 1 o f 

Page 34 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

*ETS-McCoy Result s Name: mcl20313a.rdb 

II Sample Name' -n:ic120313a033' Sample ID: -LC&-12O306-r Fie' 

PeakName'-13C4PFOS-Surr* Mats(es)'-503.000/80.000 Da' 

II Comnwit •20ppb LCS' Annotetten' -

Smoothing Kldth ; 

I

Sample Name' 'mc12O313a040" Sample ID; 'GLP11V01-02-27-025' File' •mc120313a.wtfr 

Peak Name' -13C4PFOS-Sun- Mass(M}: '503.000/80.000 Da' 

Comment; "JPAL-SW-TRIPI-O" Anrwtatoo;" 

Sample Index: 40 

Sample Type: Unknown 

Concentration . It/A 1 10B4 ' 

Calculated Cone: 0.103 ng/mL 

Acq. Date: 3/14/2012 1.05e4-

Acq. Time: 3:31:34 AM 

1.0064-

Hodlf led: tie 

- HQ II I 9500.00-

9000.00-

8500.00-

8000.00-

7500.00-

7000.00 

6500.00-

Retentlon Time: 13.3 nl n g 6000.00-

Height: 1.12e-f004 cps ^5500.00-

Statt Time: 13.2 nl n g 

End Time- 13.< min c 5000.00-

4500.00-

4000.00: 

3500.00-

3000.00-

2600.00-

2000.00-

1500.00-

1000.00-

500.00-i 

0.00-

Ittim; Specify I 

Base To Bos 

I

Sample Name •mc120313aO41" Sample ID; •GLP10-01-02-27-026- Fie 'mcl2031Sa.wifT 

Peak Name. -13C4PF0S-SurT- MaM(ea)- '503.000/80.000 Da' 

CommenI 'JPAL-SW-TRIPI-LS- Annolallon'** 

Sample Type: Unknown 

Concentration: H/A 

Calcuiaterf Cone: 0.104 ng/mL 1.1064-

Acq. Date: 3/14/2012 iftfj j 

Acq. Time- 3:52-4B AM I.K>»4-

1.00e4 

- MQ Ti l 9500.00 

9000.00 

8500.00' 

8000.00-

" 7500.00' 

7000.00-

6500.00' 

& 6000.00-

KLii. Pea 

. Window: 1.00 

1. Factor: 2 

rgeat Peak; Yea 

iight : 0.00 

Peak Width: 

RT V 

Use Felativ i 

Int . Type: 

Retention T: 

Area: 

Height: 

13.3 

Yes 

'alle y 

I 5500.00' 

1 5000.00-

4500.00-

4000.00-

3500.00-

3000.00-

2500.00-

2000.00-

1500.00-

1000.00-

500.00-

I

Sample Name: 'mcl 20313a044' Sample ID. "GLP10-01-02-27-005' 

pMkNama •13C4PFOS-Sufi' Mass(es).'503.000/80.000Da' 

CkHnmant; "JPAL-SW-ETOI-O" Annotation. ~ 

Sample Index: 44 

Sample Type: Unknown 

Concentration: II/A 

Calculated Cone: 0.104 ng/mL 

Acq. Date: 3/14/2012 

Acq. Time: 4:56:32 AM 

Pioc. Algorithm : Specify Parameter: 

Peak Width: 

Base To Base 

13.3 min 

237E0 counts 

6.31e'0O3 cps 

Data printe d by STW 

Printin g Time: 11:34:46 AM 

Printin g Date: Wednesday, Apri l 11, 

Page 2 o f 9 

Page 35 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

*ETS-McCoy Results Name: mcl20313a.rdb 

r

Sample Name; 'mcl 20313a052' Sample ID. •GLP1O-O1-O2-2T-O09' 

Peak Name; '13C4PFOS-Sun' Mass(©s)- -503.000/80.000 Da' 

Conrirrwnl' 'JPAL-SW-ET02-0' Annotation: ~ 

Smoothing Kid 

Expected RT: 

Height: 

Start Tif 

End Time5.98et003 cps 

4.5 15.0 15.5 

I SampleNarr* •mc120313a054- SamptelD:'GLP1CH)1-02-27-011" RIo"•mcl20313a.wir 

Peal;Nan» '13C4PFOS-Sun* Massfes) '503.000/80.000 Da' 

I Comment •JPAL-SW-ET02-LS" Annotation." 

nthra: Specify Pari 

Area: 

Height: 

13. 

21957 

11.0 11.5 12.0 12.5 130 13.5 14.0 14.5 15.0 15.5 

I

Sample Name •mc120313a057- Sample ID. •GLP1D-01-02-27-013- Fie; •n>c120313a.wffr 

Peak Name; •13C4PFOS-SurT- Mass(es): -503.000/80.000 Da" 

Comrrkenl •JPAL-SW-ET03-O' /Vinotation: "" 

sample Index: 57 

Sample Type: Unknown 

Concentration: ll/A t 

Calculated Cone- 0.104 ng/mL 

Acq. Date: 3/14/2012 

Acq. Tine- 9-32:37 AM i 

Proc. Algorithm; Spi 

Noise Percentage: 

Base. Sub Window 

I

SampteName -mcl20313a065" Sample ID;•GLP1O-01-02-27.O17' Rte'•mc120313a. 

Peak Name. -13C4PFOS-Sun- Mass(es). "503,000/80.000 Da' 

CommenI •JPAL-SW-ET04-0" Annotation- ~ 

Sample Index: 65 

Sample Type: Unknoian 

Concentration: ll/A 

Calculated Conct 0.108 nq/raL 

Specify Parj 

)w: 1.00 

Peak-Split. Factor: 

Report Largest Peak; 

Hln . Peak Height: 

Hin . Peak Width: 

SmoQthing Width: 

RT Window: 

14.5 15.0 15.5 

Data printe d by STW 

Printin g Time: 11:34:46 AM 

Printin g Date: Wednesday, Apri l 11, 

Page 3 o f 9 

Page 36 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

*ETS-McCoy Results Name: mcl20313a.rdb 

Data printed by STW 

Printin g Time; 11:34:46 AM 

Printin g Date: Wednesday, Apri l 11, 2012 

Page 

Page 37 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS. PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

*ETS-McCoy Result s Name: mcl20313a.rdb 

J

Sample Name' •mc120313a033- Sample ID;'LCS-120306-r Fie: -mcl 203130.wifT 

Peak Mama; "ISCaPFOS-ISpS)- MaM(es); -507.000/80.000 Da' 

CortWTwnt; *20ppb LCS- AnrmtaUon, ~ 

I Sample Name;'mc120313a040" Sample 10: •GLP10-01-02-27-025" File, "mcl2031aa.wiT 

PeakNamo'-13C8PFOS-IS(IS)- M8w(es), •507.00(V80.000DaI Comment "JPAL-SW-TRIPI-O- Annotalxwi.-

Proc. Algorithm : IntelliOua n -

Min. Peak Height: 0.00 cps 

Hin. Peak Width: 0.00 sec 

ng Width: 3 pol l 

RT Window: 30.0 set 

Expected RT: 

• RT: 

13.3 

321692 c< 

e. B2e*004 

I

Sample Name -mcl20313o04r Sample ID; "GL PI 0-01-02-27-026" 

Peak Nan>e' •13C8PFOS-IS{IS)' MaM(es); '507.000/BO.OOO Da' 

Commenl -JPAL-SW-TRIPI-LS- AnnolaUon- " 

Sample Type: Unknown 

lodified : 

Ptoc. Algorithm: Intel1lOi 

Min. Peak Height: 0.00 

Min. Peak Width: 0.00 

Smoothing Width: 3 

RT Windov: 30.0 

Expected RT: 13.^ 

! Relal • RT: 1(0 

13.5 tain 

(

Sample Name. •mc120313a044" Sample ID: -GLPl 0.01-02-27-005- RIe; -mc120313a. 

Peak Name. -13C8PFO&JS(IS)- Mass(es): -507.000^80.000 DaComment. -JPAL-SW-ETOI-O- Annotation; -

Sample Index: 14 

Height: 

Start Til 

End Tine 

Data printe d by STW 

Printin g Time: 11:34:46 AM 

Printin g Date: Wednesday, Apri l 11, 2012 

Page 5 of 

Page 38 of 77 
GLPl 0-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

*ETS-McCoy Result s Name: mcl20313a.rdb 

Data printe d by STW 

Printin g Time: 11:34:46 AM 

Printin g Date: Wednesday, Apri l 11 , 

Page 6 o f 9 

Page 39 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

*ETS-McCoy Results Name; incl20313a . rdb 

I

Sample Name' 'mcl 20313a015* Sample ID, -11012-W Flo' -mc120313a. 

Peak Name; "Pf OS" Mass{es): MgS.OOOraO.OOO Da.499.000/99.000 Da,499.000/130.000 Da* 

Commeni -0.25 n^ml FC std n Sjnth. Water* Arewtatton; ~ 

Sample Inden: 15 

Sanple Type: Standard 

Concentration: 0.232 ng/mL 

Calculate ng/mL 

roc. AlgotiChni: Specify Pari 

ise. Sub. Window- 1.00 

lak-Spllt . Factor; S 

•port Largest Peak: Yea 

In. Peak Kelgtit: 0.00 

i n. Peak Kldth : 0.00 

:ioothlng Width: 3 

Retention Tine : 13.3 

Area: 72071 coi 

Height: 1.42e*004 

Start Time; 12.8 

End Time: 13.S 

I

SampteName "mcl 20313a026" Sample ID. •12001-150- File "mcl 20313a .wtT 

Peak Name "PFOS- Mass(es)' M99.0O0/80.0O0 Da,499.000/99.000 Da,499.000/130.000 DaComment 'MeitMyl Blank: Annotation. ~ 

Sanple Index: 26 

Sample Type: Unkno-n 

[

Sample Name; -rT>c120313a02r Sample ID- TCS-120306-1- Fie: 'mc120313a. wifT 

Peak Name' 'PFOS* Mass(es): '499.000/BO.OOO Da.499.000/99.000 Da.499.000/130.000 Da' 

Conmeol' '0.2ppb LCS- AnmUIton: ~ 

Modified : 

Proc. Mgorlthm: Sy 

Noise Percentage: 

Base. Sub, Hindow: 

Peak-Split. Factor. 

Repoct Largest Peal 

Min. Peak Height: 

Min. Peak Width: 

RT V 

Ftne. mtn 

Data printe d by STW 

Printin g Time: 11:34:46 AM 

Printin g Date: Wednesday, Apri l 11, 

Page 

Page 40 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS. PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

*ETS-McCoy Result s Name: mcl20313a.rdb 

B

Ssmpt e Name . -mcl20313a033 ' Sampl e ID; -LCS-120306- r Fi e -mc l 20313a.wi r 

Peak Name . 'PFOS ' Mass(es): -499.0DO/B0.0O0 Da,499.000/99.000 Da,499.000/130.000 Da ' 

Commerit. -20ppb LCS- Annotation. ~ 

Sainple Index: 33 

Sample Type. QC 

Concentration: 19.4 ng/mL 

Calculated Cone: 17.1 ng/raL 

Acq. Date: 3/14/2012 

Acq Time: 1:02:57 AM 

Modified: Yes 

Smoothing Width; 

Expected RT: 

I

Sampte Name, -mcl 20313a040- Samp4e ID; -GLPl 0<H-02-27-025- FOe' "mcl 20313a.wtT 

Peak Name' 'PFOS* Massfes)' '499.000/BO.OOO Da,499.000/99.000 Da,499.000/130.000 Da' 

Comment'JPAL-SW-TRlPl-0- Annotattofi"-

Algorithni : Spe f 

le Sub. Windox: 

ik-Split. Factor: 

>ort Largest Pea) 

1. Peak Height: 

1. Peak Width: 

lOthlng Width: 

Window: 

lected RT: 

) Rela l 

Type: 

• RT: 

14 5 15.0 

I

Sampl e Name . *nr)Cl20313aO41' Sample ID- 'GLP l 001-02-27-026 ' Fi e 

Pea k Name . 'PFOS ' Mass{es); -499.000/80.000 Da,499.00Q/99.000 Da,4! 

CommenI , 'JPAL-SW-TRIPI-LS- Annotalion; ~ 

Saaipl e Index : 41 

Sampl e Type : Unknow n 

Date : 3/14 / 

Time : 3:52 : 

09 ng/mL 

:hir: Specify Paramete 

Peak Height: 

Peak Width: 

ithin g Width: 

9.5e4 

9.0e4 

e.5o4 

e.0e4 

7.5e4 

7.0»4-

e.5e4 

e.0e4-

5.5wJ 

5.0»4 

4.5»4-

4.0e4-

3.5e4 

3.0e4-

2.5e4 

20e4 

1.5e4-

i 

I Sampl e Name;'mc120313a044 ' Sampl e ID-'GLPHW>1-02-27-005 ' Rl e "mc l 20313a.w W 

Peak Name ; 'PFOS * Mass{es)' •499.000/80.000 Da,499.000/99.000 Da,499.000/130.000 Da ' 

I Comment"JPAL-SW-ETOl-O - Annotation: " 

Window : 

:se Relatii 

n t Type : 

.etentio n 1 

eight: 

Data printe d by STW 

Printin g Time: 11:34:46 AM 

Printin g Date: Wednesday, Apri l 11, 

Page 

Page 41 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

*ETS-McCoy Results Name: incl20313a . rdb 

II Sample Name •mc120313a052' Sampte ID. •GLI'10-01-02-27-009* Flo:'mclZOSlSa.wtfT 

Peak Name 'PFOS' Mass(es):'499.000/80.000 Da,499.000/99.000 Da,499.000/130.000 Da* 

II Comment •JPAL-SWCT02-0' AnnotaUon " 

: Type: 

.ated Cone 

Algorithm: Spec 

Peak-Split. Factor 

Report Largest Peal 

Hin . Peak Height: 

Hin . Peak WidthRT Window: 

Expected RT: 

RetentK 

Area. 

Height: 

f y Par£ 

50 

1.00 

(

SampleName "mcl20313a054' SampteID;"GLPl(Ml-02-27011' Rle''mc1203l3a. 

Peak Name: 'PFOS' Massfos); '499.000/80.000 Da,499.000^9.000 •a.499.000/130.000 

Comnnent: 'JPAL-SW-HT02-I-S" Annotation." 

Sample Index: 54 

Sample Type: Unknown 

Concentration; ll/A 

Calculated Cone: 0.924 ng/mL 

Acq. Date: 3/14/2012 

Acq. Time: Bi2B:55 AM , 

Ptoc. Algorithm: Spec 

Noise Percentage: 

Base. Sub. Window: 

Peak-Split. Factor: 

Min. Peak Height: 

Int . Type: 

Retention 1 

Area: 

Height: 

13.2 

27ei«B cc 

5.49e-t004 

12.7 

15.0 15.5 

Sample Name •mc120313a057' Sample ID:'GLP10-01-02-27-013' Fie •mc120313a.wifr 

Peak Name 'PFOS' Mass(e*): '499.000/60.000 Da,499.000/99.000 Da,499.000/130.000 Da' 

CommenI 'JPAL-SW-ETOa-C Annotatton -

Sample Index; 57 

Calculate d Cone: 0.303 

Acq. Date: 3/14/2012 

Acq. Time: 9:32:37 AM 

(

Sample Name 'mc120313aO65' Sample ID: 'GLPl 0-01-02-27-017' Rle. 'mcl20313a vtifT 

Peak Name 'PFOS' Mass(es) '499.000/80.000 Da,499.000/99.000 Da,499.000/130.000 DaComment "JPAL-SW-ET04-0' Annotation, ~ 

Sample Type; tjnknown 

Concentration: ll/A 

Calculated Cone: 0,l£ e ng/nL 

Acq. Date: 3/14/2012 8500-

Acq. Time- 12:22:32 PH 

8000-

7SM. 

7000-

Proc. Algorithm: Specify Pan 

Hoise Percentage: 50 

Base. Sub. Window: 1.00 

Min. Peak Height: 

Min. Peak Width: 

Smoothing Width: 

5500' 

5000' 

4SO0 

4000-

11.0 11.5 12.0 12.5 13.0 13.5 

Time, mm 

Data printe d by STW 

Printin g Time: 11:34:46 AM 

Printin g Date: Wednesday, Apri l 11, 2012 

Page 9 of 9 

Page 42 of 77 
GLPl 0-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

Ginger AG01330509 Result s Name: gl20307a.rdb 

•

Sample Name: 'o120307o014' Sample ID.'11012-6-6' Fie; 'a120307a. 

Peak Name 'ISCSPFHS-ISOSr Mass<es). '402.0^0.0 ami " 

Comment "0.25 n^'mL FC std m Synth. Watei- Annoialion 

Sample Index: 14 

ilated Cone. 

9;35:19 PM 

Led: 

Hin. Peak Height: 

Min. Peak width: 

Smoothing Width: 

RT Window: 

Expected RT: 

Use Relative RT; 

0.00 

J 

30 0 

I

SampteName •gl20307a02r Sample ID,'12001. 

Peak Name: '13C3PFHS-IS{IS)' M3M(es): '402," 

Commant 'Method Blank" Annotation:" 

Sacaple Index: 27 

Sample Type; Unknown 

Concentration; 0.945 ng/mL 

Calculated Cone: ll/A 

Acq. Date; 3/8/2012 

Acq. Tine; 2:00:24 AM 

Hin. Peak Height; 

Hln. Peak width. 

Smoothing width' 

I

Sampte Name' '91203073028' Sampte ID: •LCS-120306-r Fite' •g120307a.wir 

Peak Name-'13C3PFHS-IS{IS)' Mass(es):'402.0/80.0 

Comment; •0.2ppb LCS' Annotatkin." 

Sample Index: 26 

Saople Type: QC 

Concentration; 0.937 ng/mL 

Calculated Cone- N/A 

Acq. Date; 3/B/2012 

Acq. Tine; 2.21:34 AH 

Modified; 

Proc. Algorithm: 

Min. Peak Height: 

Hin. Peak Width; 

Smoothing Width: 

RT WindowExpect 

Use Rt ! RT: 

2.56etO05 cps 

I

Sample Name: *g12O307aO31' Sampte ID: 'LCS-120306-4' Fie. 'a120307a.wtr 

PeakName, '13C3PFHS-IS(tS)' Mass(ai)' "402.0/80.0 

CommenI •2ppb LCS' Annotalian:" 

Sample Index: 31 

ic. Algorithm: ] 

I. Peak Height: 

I. Peak Width: 

lOthing Width; 

Window: 

lected RT: 

It. Type. 

866432 cc 

2.47e»O05 

14.7 

Data printe d by STW 

Printin g Time: 12:30:11 PM 

Printin g Date: Wednesday, Apri l 11, 2012 

Page 1 o f 12 

1438 1488 

T1n>e, min 

Page 43 of 77 
GLPl 0-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

Ginger AG01330509 Result s Name: gl20307a.rdb 

r

Samf*, Name, •g120307a034- Sampte ID' TCS-120306-r fU - •g120307a.wr 

Paak Name: •13C3PFHS.1S(IS)- Mass{8S)'•402.r 

Commam. "20ppb LCS' Annolation -

Data printe d by STW 

Printin g Time: 12:30:11 PM 

Printin g Date: Wednesday, Apri l 11, 

Page 2 o f 12 

Page 44 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS. PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

Ginger AG01330509 Result s Name: gl20307a.rdb 

I

Sample Name '9l20307a046' Sample ID 'GLP1041-02-

Peak Name '13C3PFHS4S(IS)' Mass(es), '402.0/60.0 

Comment; 'JPAL-SW-ET01-D8' Annotation." 

Sample Type: Unknown 

H m. Peak Height: 

Min. Peak Width: 

Snoothing width : 

Expected RT: 

!-. 14.9 

884201 cc 

2.66e+005 

14.7 

15.2 

I

Sampte Name: 'g120307a053' Sampte ID 'GLPl 0-01-02-27-009' F.le, •gl20307a.wir 

Peak Name, '13C3PFHS-IS(IS)- MaM(es) '402.0/80.0 ai ~ 

Comment •JPAL-SW-eT02.0- Annotation: " 

Sample Index: 53 

Sample Type: Unknown 

Concentration: 0.94 5 ng/mL 

Calculated Cone: ll/A 

Acq. Date: 3/8/2012 

Acq. Time: 11:11:10 AM 

2.6e5 

Height; 

Start Ti l 

End Tine 

1240 12S9 

I

Sampte Name:'a120307a05e' Sampta 10: •GLP1lW)1-02-27-013' F*e 'g120307a.wtfr 

Peak Name MSCSPFHS-IStiS)' Mass{es): '402.0/80.0 

Comment: 'JPAL-SW-ETOS-O" Annotation. " 

sanple lnde«; SS 

Saople Type: Unknown 

Acq. Time; 12:57:11 PH 

Modified: Yes 

Proc Algorithm : IntelliQua n - ] 

Min. Peak Height; 0.00 cps 

Hln. Peak Width; 0.00 sec 

SnoQthing width : 3 point ; 

RT K 30.0 

Expected l 

Use Relativ e BT. Ho 

Int . Type: Valle y 

Retention Time; 14.S roin 

Atea: 96287B counts 

Height; 2.89e»005 cps 

I

Sampte Nartw •g120307a066' Sample ID: 'GLP10-01-02-27-0ir Fito: '81203073. 

Peak Name- -13C3PFHS-B{IS)' Mas»(es), -402.0/80.0 

Cocranenl: 'JPAL-SW-ET04-0' Annotation." 

Sample Index; 66 

imple Type: 

Cone 

Calculai 

0.945 

11/A 

Acq. Time' 3:46:46 I 

Modified: Yes 

Ptoc. Algorithm; IntelliQ i 

Min. Peak Height; 0.00 

Min. Peak width : 0.00 

Smoothing Width: 3 

BT Window: 30.0 

Expected RT: 14.9 

! RT: Wo 

Valle y 

:: 14.8 mm 

942729 counts 

2.896*005 cps 

14.7 min 

15.2 min 

Data printe d by STW 

Printin g Time: 12:30:11 PM 

Printin g Date: Wednesday, Apri l 11 , 2012 

Page 3 o f 12 

Page 45 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

Ginger AG01330509 Results Name: gl20307a.rd b 

Sampte Name: •gl20307a014' SamplelD.'11012-6-6' Fie:'g120307a.wir 

PeakName '13CBPFOS-tSpS)' M3ss(as) '507.0/80.0amiT 

Comment: "0.25 n^'mL FC std m Synth. Water Annotation: ~ 

sample Index. 14 

Sample Type: Scandacd 

Concentration: 0.960 ng/mL 

Calculate d Cone: N/A 

Acq. Date: 3/7/2012 

Acq. Time: 9:25:19 PM 

Modified: Yes 

Proc. Algorithm: IntelliQua n - IQfi 

Min. Peak Height; 0.00 cps 

Min. Peak width: O.OO sec 

Snoothing Width; 3 point s 

RT Window: 30.0 sec 

Expected RT; 15.9 min 

Use Relative RT; Ho 

Int . Type: Valle y 

5. Gle->004 

Sampte Name' •g120307a027' Sample ID: '12001-160' fie- •g120307a.wifr 

I

Peak Name: '13C8PFOS-lS(ISr M3ss(es). '507.0/80.0 ar 

Comment'MattMxlBlank" Annotation,' 

Sample Index: 27 

Sample Type: Unknown 

Concentration; 0.960 ng/mL 

Calculated Cone: N/A e.0o4-

7.5o4 

7.0o4-

6.5o4-

6.0e4 

5.5e4 

5.0e4 

I 

^ 4.0e4 

S 

S 3.5M 

3.0e4' 

2.5e4 

2.0e4 

1.5e4-

1.0e4-

5000.0-

Modified ; Yes 

Proc. Algorithm; IntelliQu ; 

Min. Peak Height: 0.00 

Min. Peak Width; 0.00 

Snoothing width; 3 f 

RT Window: 30.0 

Expected RT; 

Use Relativ e BT: 

Heiglit ; 

Star t 1 

End Tin 

1339 1388 

I

Sampte Name: •gl20307aO28" Sample ID' •LCS-120306-r Fie: -a120307a.iMr 

Peak Name' '13C8PFOS-IS{IS)- Mass(»s)' •507.0/00.0 amiT 

Comment* '0.2ppb LCS" Annotation: ~ 

Modified ; 

28 

QC 

0. 951 

N/ft 

3/B/2012 

2:21:34 ftM 

Yes 

IntelliQua r 

Min. Peak Height: 0.00 

Min. Peak Width: 0.00 

Snoothing width : 3 

RT Mindow; 30.0 

I

Sampte Name: •Bl20307a031' Sampte ID' •LCS-12030S-4' Fie- 'g120307a.wirr 

Peak Name 'ISCePFOS-ISflS)' Mass(es)''507.0/60.0 

Comment '2ppb LCS" Annotation ~ 

Sample Index: 31 

Sample Type' QC 

Concentiatlon; 0.9S1 ng/mL 

Calculated Cone: H/fi 

Acq. Date: 3/S/2012 

Acq. Time: 3:25:11 AM 

Use Belativ t 

Int . Type; Valley 

252437 CI 

1537 1587 

Time, min 

Data printe d by STW 

Printin g Time: 12:30:11 PM 

Printin g Date: Wednesday, Apri l 11, 2012 

Page 4 of 12 

Page 46 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

Ginger AG01330509 Result s Name: gl20307a.rdb 

Peak Height: 

Peak Width; 

Jthing Width: 

0.00 

0.00 

3 

30.0 

H Sampte Name;'g120307a034' SaniplelD •LCS-120306-r Fie* •g120307a.wir 

PeakName •13C8PFOS-tS{lS)' Mass(es) '507.0^0.0 amu' 

II CommenL'20ppbLCS* Annotation." 

g.0e4' 

8.5e4 

8.0e4 

7.5o4-

7.0e4-

6.5e4 

6.0e4 

5.5e4' 

5.0e4' 

4.5o4 

4.0e4 

3.5*4-

3.0e4-

2.5«>4' 

2.0e4' 

1.0e4 

5000.0-

1339 1388 1438 

I

Sampte Name' 'g1203D7a041' 

Peak Name' 'nCBPFOS-ISdSr 

Comnfient 'JPAL-SW-TRIPI-O" 

Sample Index: 41 

Sample Type: Unknown 

Concentration; 0.960 

Sampte ID 'GLP10-01-02-

Mass(es): '507.0/80.0 

Annotation." 

0.0 0 

3 

30. 0 

Smoothing Wic 

RT Window: 

Expected RT: 

Use Relative 

Int . Type; Valley 

Retention Time: 15.8 

Atea: 739264 ci 

I

Sampte Name •a120307aO42- Sampte ID: 'GLPl ^01-02-27-026' Fie' 'g12O307a.wifr 

Peak Nam* 'ISCSPFOS-ISOS)' Mass{os), '507.0/80.0 amu" 

Comment:'JPAL-SW-TRIPI-LS' Annotation:" 

Sample Index; 42 

Sample Type: Unknown 

Concentration; 0.960 ng/mL 

calculated Cone- N/A 

Acq. Date: 3/8/2012 

Acq. Time. 7:18:11 AM 

Proc. Algorithm; IntelliQua n - I 

Min. Peak Height; 0.00 cps 

Hin . Peak Width; 0.00 sec 

Smoothing width; 3 points 

Height. 

Start 1 

End TiD 

I

Sampte Name' 'g120307a045' Sampte ID, "GLP10-01-02-27-005' Fite' •g120307a.wrfr 

P«akNam*''13C8PFOS-IS(IS)' Mass(*a),'507.f 

Comment "JPAL-SW-ETOI-O' /Annotation.' 

Modified: 

Min. Peak Height; 

Min. Peak Width; 

Data printe d by STW 

Printin g Time: 12:30:11 PM 

Printin g Date: Wednesday, Apri l 11, 

Page 5 o f 12 

Page 47 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

Ginger AG01330509 Result s Name: gl20307a.rdb 

I Sampte Name 'g12O307BO46" Sampte ID,'GLP1CM)l-02-27-006' FN'"g120307B.wir 

Peak Name: "ISCePFOS-ISOS)' Massfes). '507.0/80.0 amiT 

J Comment 'JPAL-SW-ETOI-OB' AnnoUlion: -

Proc. Algorithm: 

Kin . Peak Height: 

Win, Peak Width; 

Smoothing Width; 

RT Mindow: 

Height: 

Star t T: 

End Tim. 

Valley 

•: 15.8 min 

324S10 counts 

1.04e«OOS cps 

I

SampteName. 'g120307B053' 

Peak Name. '13C8PFOS-IS(IS)' 

CommenL 'JPAL-SW/-ET02-0' 

Sample Index: 53 

Sample Type; Unknown 

Con< 

Call 

Sampte ID- "GLPl 04)1-02-27-009- Fite 'g1203078.w 

Mass<as)' '507.0/30.0 amu' 

Annotation; — 

1.960 

Proc. Algorithm ; : 

Min. Peak width : 

Smoothing Width; 

BT Window: 

ed RT; 

Relal 

Height; 

End Tine; 

i BT; 

itelliOu a 

O.OO 

J F 

30.0 

15.9 

llo 

Valle ' 

15.i 

372046 

l.lOeS1.05e5-

LOOeS9.50e4-

9.00e4' 

a.50e4-

8.00e4' 

7.50*4-

7.00e4 

6.50»4 

6.00*4-

E S.50»4' 

i 

I 5.00*4' 

4.50*4-

4.00*4-

3.50*4-

3.00*4-

2.50e4-

2.00*4-

1.50*4-

1.00*4-

5000.00-

0.00 

I

Sampte Name 'a120307a058" Sampte ID' 'GLP 10-01-02-27-013' Fte' 'g120307a. wlfT 

Peak Name: "laCSPFOS-ISOS)' Masa(*s) '507.0/80.0 

Comment 'JPAL-SW-ET03-0' Annolallon -

Sample Index: 5S 

Sample Type; Unknown 

Concentration: 0.960 ng/mL 

Calculated Cone; K/A 

Acq. Date; 3/S/2012 

Acq. Time: 12:57:11 PM 

Modified ; Yes 

Proc. Algorithm; IntelliCua n - IQA 

Min. Peak Height: 0.00 cps 

Hin . Peak Width; 0.00 sec 

Height: 

Start Til 

End Tine 

I

Sampte Name' 'gl20307a066' Sampte ID "GLPl 0-01-02-27-0ir Fito' •g120307a.wifr 

PeakName.'13CePF0S-IS(IS)' Mass(es) '507.0/80.0 

Comment *JPAL-SW-ET04-0' Annotation. ~ 

Modified : ^es 

Proc. Algorithm : IntelliQua n -

Min. Peak Height; 0.00 cp: 

Min, Peak Width; 0.00 set 

Smoothing Width 3 polr 

RT Window; 30.0 sec 

( BT. 

15.9 

llo 

Data printe d by STW 

Printin g Time: 12:30:12 PM 

Printin g Date: Wednesday, Apri l 11, 

Page 6 of 12 

Page 48 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

Ginger AG01330509 Result s Name: gl20307a.rdb 

I

Sampte Nam*: •9l20307a014* Sampte ID.'11012-&6' Fie.'g120307a.wifr 

Peak Name: *PFBS' Masses) '299.0/99.0 amu,299.0/80.0ar ~ 

ComoMnt: "Oas ng/mL FC std In Synth. WateT Annotation: ~ 

Sample Index; 14 

.250 

Sample Type; 

Calculated Cone: 1.285 

3/7/ 

Peak-Split. Factor' 

Report Largest Pea) 

Min. Peak Height: 

Mm. Peak width; 

1.15e5 

1.10*5 

1.05e5 

1.00e5 

9.50*4 

9.00*4 

8.50e4 

s 8.00*4 

7.50*4 

7.00*4 

6.50*4 

^ 6.00*4 

I 5.60e4-

^ 5.00*4 

4.50*4' 

4.00e4-

3.50*4-

3.0De4 

2.S0e4 

2.00*4' 

1.50e4-

1.00s4' 

5000.00' 

0.00-

1091 1141 

I

Sampte Nsme, 'gl20307a027' Sampte ID: '12001-160' Fla' -g120307a.wifr 

Peak Name. 'PFBS' Mass(es): "299.0/99.0 amu,299.CV80.0 amu* 

Comment: -Method BlanW Annotation: -

Sample Index: 27 

I

Sampte Name- •gl2O307aO28' Sampte ID' -105-120306-1' Fie: 'gl20307a.wtr 

Peak Nam*'-PFBS- Maaa(es):'299.0/99.0 amu.299.0iW.O ' 

Comment: *0.2ppb LCS- Annotation: ~ 

Sample Type: QC 

Calculated Coi 

: Height: 

: Width. 

[ Width: 

Height: 

Start 1 

End Tin 

Valley 

13.4 

325226 cc 

9.25et004 

13.3 

13.6 

I

Sampte Name: 'g12O307aO31' Sampte ID' 'LCS-120306-4' 

Peak Name. -PFBS" Mass(es): -299.0/99.0 amu,299. 

Comment -2ppb LCS* Annotation' ~ 

Sample Index: 31 

Sanple Type; QC 

Concentration: 1.98 ng/mL 

Calculated Cone: 2.17 ng/mL 

Acq. Date; 3/B/2012 

Acq. Time: 3.25:11 AM 

Nois< Pen 

Und o 

Peak-Spilt. 

Report Larg< 

Hin. Peak H< 

Min. Peak widt h 

Smoothing width: 

RT Hindow; 

Expected RT: 

Use Relativ e RT. 

Int . Type: 

:elli(;uar 

50 

1.00 

320336B col 

8.72e-'005 

13.3 

Data printe d by STW 

Printin g Time: 12:30:12 PM 

Printin g Date: Wednesday, Apri l 11 , 2012 

Page 7 of 12 

Page 49 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

Ginger AG01330509 Result s Name: gl20307a.rd b 

II SampteName'*g120307B034' Sampte ID, •LCS-120306-r 

I Peak Nam*''PFBS' Mass(es) '299.0/99.0 amu,299.0«(0.0 

II Comment'"20ppbLCS' Annotation:" 

Saople Type 

Concenttatl 

Calculated 

Acq. Date; 

Noise Percentage: 

Base. Sub. Hindow 

Peak-Split. FactO] 

Peak Height; 

I

Sampte Name- 'gl20307o041' Sampte ID. 'GLPl0-01-02-27-025' FOe, •gl20307a.w«r 

Peak Name: -PFBS' Mass{BS)' '299.0/99.0 amu,299.0/B0.O amu' 

Comment: 'JPAL-SW-TRIPl-C Annotatton:" 

Sample Index: 41 

Smoothing width: 

RT Window: 

Expected RT; 

Height: 

Start Tin 

End Time: 

I

Sampte Name' •gl20307a042' Sampte ID' 'GLP 10^1-02-27-026" Fie: -9l203Q7a.wifr 

Peak Name: TFBS' MaM(es): •299.0ra9.0 amu,299.)V80.0 

Comment: 'JPAL-SW-TRIPI-LS' Annotation:" 

ict Largest F( 

Peak Height; 

Peak Width: 

I

Sampte Name: •gt20307a045' Sampte ID: 'GLP10-01-02-27-005' Fite' •3l20307a.wtr 

Peak Nam*' TFBS' Masa(as}' "299.0/99.0 amu,299.0/30.~ 

Comment'JPAL-SW-ETOI-C Annotation: " 

Sample Index; 45 

Sample Type- Unknown 

tion; ll/A 

d Cone: 0.0345 2.0*4 

Acq. Time: S 

Modified; 

Proc, Algorithm: ] 

Base. Sub. window: 

-Split. Factoi 

Repo. 

n. Peak I 

Height: 

Start Tir 

End Time. 

•ight: 

^»' 

Data printe d by STW 

Printin g Time: 12:30:12 PM 

Printin g Date: Wednesday, Apri l 11 , 

Page 

Page 50 of 77 
GLPl 0-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

Ginger AG01330509 Results Name: gl20307a.rdb 

Data printed by STW 

Printin g Time: 12:30:12 PM 

Printin g Date: Wednesday, Apri l 11, 2012 

Page 9 of 12 

Page 51 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

Ginger AG01330509 Result s Name: gl20307a.rdb 

I

Sampte Name, '9l20307a014' Sampte ID- '11012-6-6' Fie. •g120307a.w(r 

Peak Name: 'PFHS" Mass(es)' -399.0/99.0 amu,399.0/80.0 amu' 

Comment. "0.25 nglml FC std In Synth. Water* Annotation 

Valley 

•: 14.9 

386284 cc 

Height: 

Start Ti l 

End Time 

1240 

Sampte Name "9l20307aO27" Sampte ID''12001-160- Fla •9l20307a.wifr 

Peak Name 'PFHS' Mass(es): '399.0/99.0 amu,399.0/80." 

I Commam: 'Mettwd Blank' AnnotatKm " 

Sampl e Index . 

Sampl e Type : 

ll/ A 

Acq . Tine : 

3/8/2012 

2;0l):24 f LK 

9000 

Mod i fled : l l o 

mtelli O a n - 13A eooo 

Hln . Pea k Width : 

Smoothin g Width ; 

0.0 0 

3 point s 

7500 

Us e Relativ e RT : 

14. 9 m i n 7000 

Retentio n Time : 

Valle y 

14. 9 m i n 6000 

Height . 1.06et00 3 

14. 8 roin 5500 

E n d Time : 14. 9 rain 

§ 5000 Intensity. 

3500 

3000 

2500 

2000 

1500 

1000 

500 

0 

I

Sampte Namo:'g120307a028' Sampte ID: •LCS-120306-1' Fite:'g 120307a. 

Peak Name. -PFHS" Mass(as) '399.0/99.0 ' 

Comment.'0.2ppbLCS* Annotation:" 

sample Index: 2B 

Sampl e Type ' QC 

1.191 

Acq. Dal 

I . Peak Height' 

I . Peak Width: 

lOthing Width. 

Valle y 

:: 14.9 

27655S cc 

I

Sampte Name-'91203073031' Sampte ID''LCS-120306-4' File:'gl20307a.wi(r 

Peak Name-•PFHS' Mas5{es), •399.0/99.0 an 

Comment •2ppti LCS' Annotation' " 

Sample Type; 

Concentration: 1.98 ng/mL 

Calculated Cone; 2.06 ng/nL 

Acq, Date: 3/8/ZOlZ 

Acq. Tine: 3:25:11 AM 

liCuan - IQA 

Valle y 

:: 14-9 

3008319 C( 

Data printe d by STW 

Printin g Time: 12:30:13 PM 

Printin g Date: Wednesday, Apri l 11, 

Page 10 o f 12 

Page 52 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS. PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

Ginger AG01330509 Result s Name: gl20307a.rdb 

Sampte Name. 'gl20307aO4r Sampte ID- 'GLPlCH)l-02-

Peak Name •PFHS" Mass(es)' '399.0/99.0 amu 

Comment •JPAL-SW-TRIP1-0' Armoiatioo'~ 

Sample Index: 41 

Sample Type: Unknown 

Concentration: H/A 

Valley 

14.9 

2545 C( 

1240 

I

Sampte Name: 'g1203D7a042' 

Peak Name "PFHS" Massfes) 

Comment 'JPAL-SW-TRIPI-LS' 

S.imple Index; 42 

Sarople Type: Unknown 

Concentration: N/A 

Calculated Cone 

Sampte ID: 'GLP10-01-02-

•399.0/99.0 amu 

Anr>otation, 

Acq. Tlm( 

Proc AlgorithmMln. Peak Height: 

1/2012 

8:11 M 

ling Width: 3 

itelliQua 

0.00 

0.00 

Expected RT; 

Use Relative 

Int. Type: 

Retention Tm 

Height: 

I

Sampte Name: 'g120307aa45" Sampte ID: 'GLPl 0-01-02-27-005' 

Peak Name, 'PFHS' Massfes)- '399.0/99.0 amu,399.0/80.0 

CommenL 'JPAL-SW.fTOI-O' Annotation:' 

Sample Index' 45 

Sampl e Type -

Caloi Led Cone: 0.00965 

:e; 3/8/Z012 

l e : 8:21:42! 

ng/mL 

Modified: 

Expected RTUse Relativ e 

Int . Type: 

Retention Tin 

Height: 

Data printe d by STW 

Printin g Time: 12:30:13 PM 

Printin g Date: Wednesday, Apri l 11, 

Page 11 o f 12 

Page 53 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

Ginger AG01330509 Result s Name: gl20307a.rdb 

I

Sampte Name: •g120307aO46' Sampte ID. 'GLP10-01-02-27-006' Flo: 'g120307a.wrfr 

Peak Name' "PFHS" Ma*s(es)- -399.0^99.0 amu.399.0/80.0 amu* 

Comment' •JPW.-SW-ETOI-OB" Annoialion:" 

Sample Type: Unknown 

Concentration: N/A 

Calculated Cone; 0.0110 ng, 

Acq. Date: 3/8/2012 

Acq. TimeModiiied. 

RT WindowExpected RT. 

9500 

9000 

8500 

8000 

7500 

7000 

5500 

5000 

4500 

4000 

3500 

3000 

2500 

2000 

1500 

1000 

17.30s^ 

I

Sampte Name: 'g120307o053" Sampte ID* "GLPl 0-01-02-27-009' Fite, 'g120307a.wir 

Peak Name' TFHS' Mas5(as): *399.0/99.0 amu ,399.0/80.0 amu' 

Cotrenem. 'JPAL-SW-eT02-0- AnnotaUon " 

Sample Index: 53 

sample Type; 

Cone ll/A 

i Cone: 0.00708 ng/mL 

Height: 

Start T; 

End Tim 

9000 

7500 

7000 

5500 

5000 

^ 45O0 

1 4000 

3500 

3000 

2500 

2D00 

1500 

1000 

I

Sampte Name; 'gl2O307aOS8' Sampte ID: 'GLPKMl 1-02-27-013' Fie' 'Bl20307a.wifr 

Peak Name.'PFHS- Mass(es):'399.0/99.0 amu,399.0/80.0 

Comment. 'JPAL-SW-ETOS-O' Annotatton " 

I t. Type: 

ttention 1 

1.23e-«004 

14.6 

14.9 

Sampte Name: •g120307a066" Sampte ID- 'GLPlO-01-02-27-017' Fite: •g120307a wir 

Peak Name' 'PFHS' Mass(es): -399.0/99.0 amu ,399.0/80.0 amu' 

Commefit 'JPAL-SW-ET04-0" AnnotaUon. ~ 

sample Index; 66 

Sample Type; 

Calculated Cone: 

Height; 

Start T: 

End Tim 

1.00e4 

9500.00 

9000.00 

8500.00 

8000.00 

7500.00 

7000.00 

6500.00 

6000.00 

g 5500.00 

^ 5000.00 

i 

E 4500.00 

4000.00 

M00.00-

3000.00 

2500.00 

2000.00 

1500.00 

1000.00 

500.00 

0.00 

Data printe d by STW 

Printin g Time: 12:30:13 PM 

Printin g Date: Wednesday, Apri l 11, 2012 

Page 12 o f 12 

1438 1466 

Page 54 of 77 
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Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

ATTACHMENT C: ANALYTICAL METHOD(S) 

Page 55 of 77 
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Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

3M Environmental Laboratory 

Metiiod 

Method of Analysis for the Determination of Perfiuorinated Compounds in Water 

by LC/MS/MS; Direct Injection Analysis 

Method Number: ETS-8-044.1 

Adoption Date: 4/12/07 

Effective Date: / l/f/// 

Approved By: 

William K. Reagen, Technical Director, Environmental Laboratory Date 

ETS-8-044.1 Page 1 of 22 

Method of Analysis for the Determination of Perfiuorinated Compounds in Water by LC/MS/MS; Direct 

Injection Analysis 

Page 56 of 77 
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Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

1 Scope and Application 

This method describes the direct injection analysis of perfiuorinated compounds (PFCs) from 

water matrices using high-perfomiance liquid chromatography tandem mass spectrometry 

(HPLC/MS/MS). The method is generally applicable but not limited to the measurement of 

perfluoroalkyi sulfonamides and perfiuorinated alkyi acids (PFAAs) such as perfluorosulfonic 

acids (PFSAs) and perfluorocarboxylic acids (PFCAs) (Table 1). Water samples containing 

heavy particulate may require preparation by an alternate method such as ETS-8-154 

"Deteimination of Perfiuorinated Acids, Alcohols, Amides, and Sulfonates In Water By Solid 

Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry". The 

method is applicable to both external standard and internal standard calibration V 

Table 1. Representative Target Analytes 

Acronym Analyte 

Chemical Abstract Services 

Registry Number (CASRN) 

PFBA (04 Acid) Perfluorobutanoic acid 375-22-4 

PFPeA (05 Acid) Perfluoropentanoic acid 2706-90-3 

PFHxA (06 Acid) Perfluorohexanoic acid 307-24-4 

PFHpA (07 Acid) Perfluoroheptanoic acid 375-85-9 

PFOA (08 Acid) Perfluorooctanoic acid 335-67-1 

PFNA (09 Acid) Perfluorononanoic acid 375-95-1 

PFDA(OIOAcid) Perfluorodecanoic acid 335-76-2 

PFUnA(011 Acid) Periluoroundecanoic acid 2058-94-8 

PFDoA (012 Acid) Perfluorododecanoic acid 307-55-1 

PFTrDA (013 Acid) Perfluorotridecanoic acid 72629-94-8 

PFBS (04 Sulfonate) Perfluorobutanesulfonic acid 375-73-5 

PFHS (06 Sulfonate) Perfluorohexanesulfonic acid 355-46-4 

PFOS (08 Sulfonate) Perfluorooctanesulfonic acid 1763-23-1 

FBSA (04 Sulfonamide Perfluorobutanesulfonamide 30334-69-1 

FOSA (08 Sulfonamide) Pefluorooctanesulfonamide 754-91-6 

The Minimum Reporting Level (MRL) is the Limit of Quantitation (LOQ) that meets Data 

Quality Objectives (DQOs) that are developed based on the intended use of this method. 

Method Flexibility - This is a perfomnance-based method and may be generally applied to the 

detennination of perfiuorinated compounds in water matrices when analysis batch quality 

control (QC) criteria are met^. Each set of samples are prepared in an analysis batch with 

calibration standards, LCSs, blanks, and continuing calibration check standards analyzed on 

the same instmment during a time period that begins and ends with the analysis of the 

appropriate continuing calibration check standards. The laboratory is permitted to modify the 

LC column, mobile phase composition, LC conditions, and MS/MS conditions. Method 

modifications should be considered to improve method perfomiance or to meet data quality 

objectives for the study. In all cases where method modifications are implemented, the batch 

' The method is supported by validation with intemal standard calibration for C4-C13 PFCAs, C4, C6, and C8 PFSAs, 

and C8 perfluoroalkane sulfonamide in laboratory control samples under 3M method validation El 1-0667. 

^ Guidance for establishing method QC Criteria based on a.) FDA May 2001, "Guidance for Industry, Bioanalytical 

Method Validation", b.) EPA Method 537, and c.) European Commission: Guidance for Generating and Reporting 

Methods of Analysis in Support of Pre-registration Data Requirements for Annex II (Part A, section 4) and Annex III 

(Part A,section 5) of Directive 91/414, SANCO/3029/99 rev. 4 (11/07/00). 

ETS-8-044.1 Page 2 of 22 

Method of Analysis for the Determination of Perfiuorinated Compounds in Water by LC/MS/MS; 

Direct Injection Analysis 

Page 57 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

analytical QCs (section 9) must be completed and pass QC acceptance criteria (section 13) if 

the data from the analytical batch are to be reported. 

2 Method Summary 

Water samples are analyzed as neat aqueous sample or as solvent diluted aqueous samples 

by direct injection using LC/MS/MS. Samples containing heavy particulate may not be 

suitable for analysis by this method. Samples containing suspended particulate should be 

centrifuged or filtered prior to removing a sample aliquot or diluting with solvent. The water 

sample is mixed well prior to removing an aliquot or diluting, if necessary, with ASTM Type I 

water, HPLC water, other suitable water, or solvent (methanol). 

Quantitation is by stable isotope intemal standard calibration in laboratory reagent water. All 

perfiuorinated compounds (PFCs) target analyte concentrations of perfluorosulfonic acids 

(PFSAs) and perfluorocarboxylic acids (PFCAs) are reported as anions and corrected for 

their salt or free acid fomns. Aiternatively, quantitation may be perfonned by external 

standard calibration. 

This is a peri'omiance-based method. Method uncertainty for each target analyte is 

detennined for each analytical batch using multiple laboratory control spikes at multiple 

concentrations. This method also requires that the precision and accuracy for each sample 

be detennined using field matrix spikes to verify that the method is applicable to each sample 

matrix. 

Calibration standards for PFUnA, PFDoA, PFTrDA, and FOSA have been found to be 

unstable for more than 2 days in 100% water. Samples requiring analysis for these 

compounds by this method should be diluted 1:1 with methanol and analyzed against a 

calibration curve prepared in 1:1 synthetic groundwaterMeOH. 

3 Definitions 

3.1 Analysis Batch 

A set of study samples that are prepared with calibration standards, laboratory control 

samples, and procedural blanks, and analyzed on the same instrument during a time period 

that begins and ends with the analysis of the appropriate continuing calibration check 

standards. 

3.2 Analytical Sample 

A portion of a laboratory sample prepared for analysis. 

3.3 Calibration Standard 

A solution prepared by spiking a known volume of the Working Standard (WS) into a 

predetennined amount of ASTM Type I, HPLC grade water, or other suitable water (i.e. 

matrix water), and analyzed according to this method. Calibration standards are used to 

calibrate the instrument response with respect to analyte concentration. 

3.4 Laboratory Duplicate Sample (LDS, or Lab Dup) 

A laboratory duplicate sample is a separate aliquot of a sample taken in the analytical 

laboratory that is analyzed separately with identical procedures. Analysis of LDSs compared 

to that of the first aliquot give a measure of the precision associated with laboratory 

procedures, but not with sample collection, preservation, or storage procedures. 

ETS-8-044.1 Page 3 of 22 

Method of Analysis for the Determination of Perfiuorinated Compounds in Water by LC/MS/MS; 

Direct Injection Analysis 

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GLPl 0-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

3.5 Field Blank (FB)/Trip Blank (TB) 

ASTM Type I, HPLC grade water, or other suitable water, placed in a sample container in the 

laboratory and treated as a sample in all respects, including exposure to sampling site 

conditions, storage, preservation and all analytical procedures. The purpose of the TB is to 

detennine if test substances or other interferences are present in the field environment. This 

sample is also refen-ed to as a Trip Blank. 

3.6 Field Duplicate Sample (FDS, Field Dup) 

A sample collected in duplicate at the same time from the same location as the sample. The 

FDS is handled under identical circumstances and treated exactly the same throughout field 

and laboratory procedures. Analysis of the FDS compared to that of the first sample gives a 

measure of the precision associated with sample collection, preservation and storage, as well 

as with laboratory procedures. 

3.7 Field Matrix Spike (FMS) 

A sample to which known quantities of the target analytes, ISs and SRSs are added to the 

sample bottle in the laboratory before the bottles are sent to the field for collection of aqueous 

sarhples. A known, specific volume of sample must be added to the sample container 

without rinsing. This may be accomplished by making a "fill to this level" line on the outside of 

the sample container. The FMS is analyzed to ascertain if any matrix effects, interferences, 

or stability issues may complicate the interpretation of the sample analysis. 

3.8 Trip Blank Matrix Spike (TBMS) 

An aliquot of ASTM Type I, HPLC grade water, or other suitable water, to which known 

quantities of the target analytes, ISs and SRSs are added in the laboratory prior to the 

shipment of the collection bottles. The TBMS is analyzed exactly like a study sample to help 

detennine if the method is in control and whether a loss of analyte or analytical bias could be 

attributed to sample holding time, sample storage and/or shipment issues. A low and high 

TBMS are appropriate when expected sample concentrations are not known or may vary. 

3.9 Internal Standard (IS) 

A compound added to each study sample, calibration standard, laboratory control samples, 

and procedural blanks at a consistent level (typically around 1 ng/mL). The intemal 

standard(s) are stable isotope labeled versions of the target analytes. The area count ratio of 

the target analyte to the internal standard is used for calibration. Surrogate ISs are applied 

when stable isotope ISs of target analytes are unavailable. A sun-ogate IS is not necessarily 

a stable isotope labeled version of the target analyte, but is treated as an internal standard for 

quantitation. 

3.10 Laboratory Control Sample (LCS) 

An aliquot of control matrix to which known quantities of the target analytes, ISs and SRSs 

(when applicable) are added in the laboratory at the time when samples are aliquotted. At 

least three levels (two levels for SRSs) in triplicate are included, one generally at the low end 

of the calibration curve and one near the mid range and the upper end of the curve. The 

LCSs are analyzed exactly like a laboratory sample to detennine whether the stability of the 

standards. LCSs should be prepared each day samples are aliquoted. 

3.11 Laboratory Matrix Spike (LMS) 

A laboratory matrix spike is an aliquot of a sample to which known quantities of target 

analytes, ISs and SRSs (when applicable) are added in the laboratory. The LMS is analyzed 

exactly like a laboratory sample to determine whether the sample matrix contributes bias to 

the analytical results. The endogenous concentrations of the analytes in the sample matrix 

must be detennined in a separate aliquot and the measured values in the LMS con^ected for 

these concentrations. LMSs are optional for analysis of aqueous samples. 

ETS-8-044.1 Page 4 of 22 

Method of Analysis for the Determination of Perfiuorinated Compounds in Water by LC/MS/MS; 

Direct Injection Analysis 

Page 59 of 77 
GLPl 0-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

3.12 Laboratory Sample 

A portion or aliquot of a sample received from the field for testing. 

3.13 Limit of Quantitation (LOQ) 

The lower limit of quantitation (LLOQ) for an analytical batch is the lowest concentration that 

can be reliably quantitated within the specified limits of precision and accuracy. The LLOQ is 

generally selected as the lowest non-zero standard in the calibration curve that meets method 

acceptance criteria. The LLOQ for each target analyte is established for each analysis batch 

as the lowest calibration standard with area counts at least twice that of the average area 

counts of the procedural blanks. 

The upper limit of quantitation (ULOQ) for an analytical batch is the highest concentration that 

can be reliably quantitated within the specified limits of precision and accuracy. The highest 

standard in the calibration curve that meets method acceptance criteria is defined as the 

ULOQ. 

3.14 Method/Procedural Blank 

An aliquot of control matrix that is treated exactly like a laboratory sample including exposure 

to all glassware, equipment, solvents, and reagents that are used with other laboratory 

samples. The method blank is used to detemnine if test substances or other interferences are 

present in the laboratory environment, the reagents, or the apparatus. 

3.15 Sample 

A sample is an aliquot removed from a larger quantity of material intended to represent the 

original source material. 

3.16 Stock Standard Solution (SSS) 

A concentrated solution of a single-analyte prepared in the laboratory with an assayed 

reference compound. 

3.17 Surrogate Internal Standard 

An IS that is not necessarily a stable isotopically labeled target analyte, but is treated as an 

internal standard for quantitation. Sun-ogate ISs are used when isotopically labeled 

counterparts of the target analyte are not commercially or readily available. 

3.18 Surrogate Recovery Standard (SRS) 

An isotopically labeled standard, not used as an internal standard, that is added to each 

sample and appropriate QC sample as a means to evaluate the method peri'onnance for a 

chemical class of compounds (e.g., PFSAs, PFCAs). 

3.19 Working Standard (WS) 

A solution of several analytes prepared in the laboratory from SSSs and diluted as needed to 

prepare calibration standards and other required analyte solutions. 

4 Warnings and Cautions 

4.1 Health and Safety 

The acute and chronic toxicity of the standards for this method have not been precisely 

detennined; however, each should be treated as a potential health hazard. The analyst 

should wear gloves, a lab coat, and safety glasses to prevent exposure to chemicals that 

might be present. 

ETS-8-044.1 Page 5 of 22 

Method of Analysis for the Determination of Perfiuorinated Compounds in Water by LC/MS/MS; 

Direct Injection Analysis 

Page 60 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

The laboratory is responsible for maintaining a safe wori< environment and a current 

awareness of local regulations regarding the handling of the chemicals used in this method. 

A reference file of material safety data sheets (MSDS) should be available to all personnel 

involved in these analyses. 

4.2 Cautions 

The analyst must be familiar with the laboratory equipment and potential hazards including, 

but not limited to, the use of solvents, pressurized gas and solvent lines, high voltage, and 

vacuum systems. Refer to the appropriate equipment procedure or operator manual for 

additional information and cautions. 

5 Interferences 

During sample preparation and analysis, major potenfial contaminant sources are reagents 

and glassware. All materials used in the analyses shall be demonstrated to be free from 

interferences under conditions of analysis by running method blanks. 

Parts and supplies that contain Teflon® should be avoided or minimized due to the possibility 

of interference and/or contamination. These may include, but are not limited to: wash bottles, 

Teflon® lined caps, autovial caps, HPLC parts, etc. 

The use of disposable micropipettes or pipettes to aliquot standard solutions is recommended 

to make calibration standards and matrix spikes. 

6 Instrumentation, Supplies, and Materials 

6.1 Instrumentation 

Analytical balance capable of reading to 0.0001 g 

HPLC/MS/MS or HPLC/MS system, as described in Section 10. 

6.2 Supplies and Materials 

Sample collection bottles—HOPE (e.g., NalgeneTM) wide-mouth bottles with screw cap. 

Note: Do not use fluorinated or Teflon® bottles or lined caps. 

Coolers or boxes for sample shipment. 

15-mL and 50-mL disposable polypropylene centrifuge tubes. 

Class A pipettes and volumetric flasks, various. 

2 mL HPLC autovials 

Disposable pipettes, polypropylene or glass as appropriate 

Centrifuge capable of spinning 15-mL and 50-mL polypropylene tubes at 3000 rpm. 

7 Reagents and Standards 

Note: Suppliers and catalog numbers are for illustrative purposes only. Equivalent 

perfomiance may be achieved using chemicals obtained from other suppliers. Do not use a 

lesser grade of chemical than those listed. 

7.1 Chemicals 

Water - Milli-Q, HPLC grade, or other suitably appropriate sources 

Calcium Acetate - A.C.S. Reagent Grade 

ETS-8-044.1 Page 6 of 22 

Method of Analysis for the Determination of Perfiuorinated Compounds in Water by LC/MS/MS; 

Direct Injection Analysis 

Page 61 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

Magnesium Acetate - A.C.S. Reagent Grade 

Methanol - HPLC grade 

Ammonium Acetate -A.C.S. Reagent Grade 

7.2 Representative Target Analytes, ISs, and SRSs 

PFBA, Heptafluorobutyric Acid, (C4 Perfiuorinated Acid) 

PFPeA, Nonafluoropentanoic Acid (C5 Perfluorinated Acid) 

PFHxA, Perfluorohexanoic Acid (Ce Perfluorinated Acid) 

PFHpA, Tridecafluoroheptanoic Acid, (C7 Perfluorinated Acid) 

PFOA, Ammonium perfluorooctanoate, (Cs Perfluorinated Acid) 

PFNA, Heptadecafluorononanoic Acid, (C9 Perfluorinated Acid) 

PFDA, Nonadecafluorodecanoic Acid (C10 Perfluorinated Acid) 

PFUnA, Perfluoroundecanoic Acid, (Cn Perfluorinated Acid) 

PFDoA, Perfluorododecanoic Acid, (C12 Perfluorinated Acid) 

PFTriDA, Perfluorotridecanoic Acid, (C13 Perfluorinated Acid) 

FBSA, Perfluorobutanesulfonamide 

FOSA, Perfluorooctanesulfonylamide 

PFBS, Potassium Perfluorobutanesulfonate 

PFHS, Perfluorohexanesulfonate 

PFOS, Potassium perfluorooctanesulfonate 

PFOA [1,2, 3,4-"C], "C4-isotopically labeled perfluorooctanoic acid (SRS) 

PFOS [1,2, 3,4-"C], "C4-isotopically labeled Perfluorooctanesulfonate (SRS) 

PFUnA [1,2-"C], "Cz-isotopically labeled Perfluoroundecanoic acid (SRS) 

A custom mix of ISs in a methanolic solution containing ([1,2,3,4-"C4]PFBA, [1,2 -

"CzjPFHxA, [1,2,3,4,5,6,7,8-"C8lPFOA, [1,2,3,4,5,6,7 8,9-"C9]PFNA, [1,2 -^^CJPFDA, 

[1,2,3,4,5,6,7-"C7]PFUnA, [1,2-XJPFDoA, [1,2,3 -''^CsjPFHS, [1,2,3,4,5,6,7,8-"C8]PFOS, 

and [1,2,3,4,5,6,7,8-"C8]PFOSA (Wellinqton Laboratories, Guelph, ON) in combinafion with 

added ([1,2,3,4,5-^CdPFPeA, ([1,2,3,4-X4]PFHpA, and [^^OJPFBS can be used to prepare 

a stock IS solution. Alternatively, individual stable isotope ISs can be used to prepare a stock 

IS mixture. 

Other ISs can be applied. 

7.3 Reagent Preparation 

2 mM Ammonium acetate solution (Analysis)—Weigh 0.3 g of Ammonium acetate and 

dissolve in 2.0 L of reagent water. 

Synthetic Groundwater (containing 25 ppm Ca and Mg) - Weigh 0.61 g of Calcium Acetate 

and 0.92 g of Magnesium Acetate and dissolve in 6.0 L of reagent water. 

Note: Altemative volumes may be prepared as long as the ratios of the solvent to solute ratios 

are maintained. 

ETS-8-044.1 Page 7 of 22 

Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; 

Direct Injection Analysis 

Page 62 of 77 
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Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

7.4 Stock Standard Solution (SSS) and Working Standard Solution 

Preparation 

The following standard preparation procedure serves as an example. Weighed amounts and 

flnal volumes may be changed to suit the needs of a particular study. For example, |JL 

volumes may be spiked into volumetric flasks when diluting stock solutions to appropriate 

levels. 

100 (jg/mL target analyte SSSs—Weigh out 10 mg of analytical standard (corrected for 

percent salt, acid[ETS-4-031] and purity) and dilute to 100 mL with methanol or other 

suitable solvent, in a 100 mL volumetric flask. Transfer to a 125 mL LDPE bottle or other 

suitable container. Prepare a separate solution for each analyte. Expiration dates and 

storage conditions of stock solutions should be assigned in accordance with laboratory 

standard operating procedure. An example of purity and salt correction is given below for 

PFOS. 

, , molecular weight of anion 

salt correction factor = 

moclecular weight of salt 

499 PFOS (K-^ )salt correction factor = — = 0.9275 

538 

10 mg C8F17SO3K* with purity 90% = 8.35 mg C8F17SO3"(10 mg*0.90*0.9275=8.35 mg) 

10 \jglmL (10,000 ng/mL) mixed working standard—Add 5.0 mL each of the 100 |jg/mL 

SSSs to a 50 mL volumetric flask and bring up to volume with solvent. 

1 |jg/mL (1,000 ng/mL) mixed working standard—Add 0.5 mL of the 100 \jglmL SSSs to a 

50 mL volumetric flask and bring up to volume with solvent. 

0.1 |jg/mL (100 ng/mL) mixed standard—Add 0.05 mL of the 100 |jg/mL SSSs to a 50 mL 

volumetric flask and bring up to volume with solvent. 

Storage Conditions—Store all SSSs and worthing standards in accordance with laboratory 

standard operating procedure or in a refrigerator at 4°±2°C for a maximum period of 6 months 

from the date of preparation. 

7.5 Calibration Standards 

Calibration can be performed by IS or external calibration. Using the wori<ing standards 

described above, prepare calibration solutions in ASTM Type I water, HPLC water, other 

suitable water, or a mixture of solvent and water using the information in Table 2 as a 

guideline. Note: Volumes of water or water/solvent mixtures and wori<ing standards may be 

adjusted to meet the data quality objectives addressed in the general project outline. 

Calibrafion levels other than those listed below can be prepared as needed. 

For the quantitation of PFOA and PFOS, reference materials of certified mixed linear and 

branched isomer are prefen-ed. Alternately, reference materials of primarily linear isomers of 

PFOA and/or PFOS may be used, however, when quantitating with predominantly linear 

reference standards, additional LCS samples containing both linear and branched isomers of 

PFOA and PFOS are required^. 

7.5.1 Intemal Standard (IS) and Surrxigate Recovery Standartl (SRS) 

For IS calibration, stable isotope internal standards of each target analyte or appropriate 

surrogate ISs should be spiked at the same level in all calibration standards. Once the 

calibration standards have been prepared as stated above in Section 7.5, all calibration 

standards are spiked with a separate internal standard spiking solution. Typically the 

' A report summarizing an assessment of the use of reference standards containing certified linear and branched isomers of 

PFOA/PFOS can be found in 3M report El 1-0560. 

ETS-8-044.1 Page 8 of 22 

Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; 

Direct Injection Analysis 

Page 63 of 77 
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Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

concentration of the intemal standard is consistent with the intemal standard concentration 

expected in the samples being prepared, usually 1 ng/mL. The concentration of the intemal 

standard spiking solution is typically 2 [iglmL. A separate zero point or method blank is 

typically prepared at the same time as the calibration standards, using the same solufion 

used to prepare the standards (ASTM Type I water, HPLC water, other suitable water, or a 

solvent/water mixture), and is spiked with the internal standard at the same concentration as 

the calibration curve, typically at 1 ng/mL. 

If the samples being analzyed were pre-spiked with SRSs, the calibration curve prepared in 

Section 7.5 is spiked with a separate SRS spiking solution. Typically, the sample bottles are 

spiked with a SRS at 0.1 ng/mL. The final calibration curve must consist of at least six 

calibration points after analysis. The following table provides an example of spike 

concentrations and volumes used to achieve a multi-point extracted calibration curve with 

intemal standard and sun-ogate standard. 

Table 1 lists recommended stable isotope intemal standards for several PFSA and PFCA 

target compounds. A custom mix of isotopically labeled target analytes in a methanolic 

solution containing ([1,2,3,4-"C4]PFBA, [1,2 -^XJPFHxA, [1,2,3,4,5,6 7,8-"C8]PFOA, 

[1,2,3,4,5,6,7,8,9-^^C9]PFNA, [1,2,3,4,5,6 -"CeJPFDA, [1,2,3,4,5,6,7 -^^C7]PFUnA, [1,2 -

^^CJPFDoA, [1,2,3-"C3]PFHS, [1,2,3,4,5,6,7,8-"C8]PFOS, and [1,2,3,4,5,6,7,8-"C8]FOSA 

(Wellington Laboratories, Guelph, ON) in combination with added ([1,2,3,4,5-"C5]PFPeA, 

([1,2,3,4-"C4]PFHpA, and [^^OJPFBS can be used to prepare a stock IS solution. 

Alternative sources of certified stable isotope labeled target analytes are applicable. 

Alternatively, individual stable isotope ISs can be used to prepare a stock IS mixture. The 

table below lists the recommended stable isotope ISs and SRSs applied in the method. 

Other stable isotope ISs and SRSs of target analytes not listed in the table may be used if 

supported by validation and/or analysis batch QCs meeting method acceptance criteria (e.g., 

[^^CJ-PFOA). The same intemal standard should be used for a given analyte throughout the 

entire project/study. Note: some of the compounds listed below are appropriate to use as 

surrogate ISs when a stable isotope IS of a target analyte is not available. Generally, 

surrogate isotopically labeled PFCAs are used for PFCAs, and sun-ogate isotopically labeled 

PFSAs are used for PFSAs. 

Table 2 provides examples of spike concentrafions and volumes used to achieve a multi-point 

calibration curve with ISs and SRSs. 

ETS-8-044.1 Page 9 of 22 

Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; 

Direct Injection Analysis 

Page 64 of 77 
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Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

Table 1. Stable Isotope PFCAs and PFSAs used for ISs and SRSs 

Compound Name Synonym or Acronym Analytical Purpose Reference Standard 

Source 

"C4-Perfluorobutanoic acid [1,2,3,4-"C4]PFBA IS for PFBA 

Wellington Labs 

(Mix or Individual) 

"C4-Perfluoropentanoic acid [l,2,3,4,5-"C5]PFPeA IS for PFPeA 

Wellington Labs 

(Mix or Individual) 

"C2-Perfluorohexanoic acid [l,2-"C2]PFHxA IS for PFHxA 

Wellington Labs 

(Mix or Individual) 

"C4-Perfluoroheptanoic acid [l,2,3,4-"C4]PFHpA IS for PFHpA 

Wellington Labs 

(Mix or Individual) 

"Cs-Perfluorooctanoic acid [l,2,3,4,5,6,7,8-"C8]PFOA IS for PFOA and [1,2,3,4 

"C4]PF0A 

Wellington Labs 

(Mix or Individual) 

"CrPerfluorononanoic acid [1,2,3,4,5,6 J,8,9-"C9]PFNA IS for PFNA 

Wellington Labs 

(Mix or Individual) 

"C6-Perfluorodecanoic acid [1,2,3,4,5,6 -"CslPFDA IS for PFDA 

Wellington Labs 

(Mix or Individual) 

"C7-Perfluoroundecanoic acid [1,2,3,4,5,6,7 -"ClPFUnA IS for PFUnA 

Wellington Labs 

(Mix or Individual) 

"Ci-Perfluorododecanoic acid [1,2 -"C2]PFDoA IS for PFDoA, *PFTA 

Wellington Labs 

(Mix or Individual) 

'*02-Ammonium Perfluorobutane sulfonate ["OjJPFBS IS for PFBS RTI Intemational 

(Individual) 

"Cj-iAmmonium Perfluorohexane sulfonate [1,2,3-"C3]PFHS IS for PFHS 

Wellington Labs 

(Mix or Individual) 

"Cg-Sodium Perfluorooctane sulfonate [l,2,3,4,5,6,7,8-"C8]PFOS IS for PFOS and 

PFOS[l,2,3,4 ''€4], 

Wellington Labs 

(Mix or Individual) 

"Cg-Perfluorooctanesulfonamide [l,2,3,4,5,6,7,8-"Cg]FOSA IS for FOSA 

Wellington Labs (mix) 

RTI Intemational 

(Individual) 

''C4-Perfluorooctanoic acid [l,2,3,4-"C4]PFOA SRS for all PFCAs: C4-C8 Wellington 

"Cj-Perfluoroundecanoic acid [!,2-"C2]PFUnA SRS for all PFCAs C9-C13 Wellington 

"Cg-Perfluorooctane sulfonate [l,2,3,4-"C4]PFOS SRS for all PFSAs; 04, 

€6, and 08 Wellington 

ETS-8-044.1 Page 10 of 22 

Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; 

Direct Injection Analysis 

Page 65 of 77 
GLPl 0-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

Table 2. Example Preparation of Calibration Curve with ISs and SRSs 

Sample Description Concentration 

ofWS,pg/mL 

Volume of 

WS,/JL 

Volume of IS 

(2 fjg/mL),/d. 

Concentration of 

Surrogate, yg/mL 

Volume of 

Surrogate, /d. 

Volume of ASTM Type 1 Water, or 

other suitable solvent mL 

0.025 ng/mL curve point 0.10 25 50 0.20 12.5 100 

0.030 ng/mL curve point 0.10 30 50 0.20 15 100 

0.04 ng/mL curve point 0.10 40 50 0.20 20 100 

0.05 ng/mL curve point 0.10 50 50 0.20 25 100 

0.1 ng/mL curve point 0.10 100 50 0.20 50 100 

0.25 ng/mL curve point 0.10 250 50 0.20 125 100 

0.5 ng/mL curve point 1.0 50 50 0.20 250 100 

1 ng/mL curve point 1.0 100 50 0.20 500 100 

2.5 ng/mL curve point 10.0 25 50 10.0 25 100 

5.0 ng/mL curve point 10.0 50 50 10.0 50 100 

10.0 ng/mL cun/e point 10.0 100 50 10.0 100 100 

25.0 ng/mL cun/e point 10.0 250 50 10.0 NA 100 

50.0 ng/mL curve point 10.0 500 50 10.0 NA 100 

75.0 ng/mL curve point 10.0 750 50 10.0 NA 100 

100 ng/mL curve point 10.0 1000 50 10.0 NA 100 

N/A - Not Applicable 

(1) Samples requiring analysis for PFUnA, PFDoA, PFTrDA, and FOSA should be analyzed against a calibration curve prepared in 1:1 synthetic groundwater;MeOH. 

ETS-8-044.1 Page 11 of 22 

Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis 

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Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

8 Sample Collection and Bottle Preparation 

Sample collection bottles are prepared by 3M Environmental Laboratory (or subcontract supplier) personnel for 

shipment at ambient temperature to the collection site. Typically, four separate collecfion bottles are 

associated with a single collection site: sample, field duplicate sample, low field matrix spike, and high field 

matrix spike. Altematively, the sample and field duplicate sample may contain SRSs in lieu of additional target 

analyte low field matrix spike and target analyte high field matrix spike samples. Depending on the scope of 

the project, additional replicates of the field sample and field matrix spikes may be added. Also, it is not 

uncommon for additional mid-level field matrix spikes to be collected if the expected sample concentrations are 

truly unknown or could span a large concentration range. 

High-density polyethylene (HDPE) wide-mouth Nalgene bottles are used for the sample collection containers. 

(Volumes of the bottles may vary depending on how much sample is required to meet data quality objectives.) 

Sample collection volumes are project specific and based on data quality objectives. The Nalgene bottles do 

not require any pretreatment prior to use. Typically, placement of a sample bottle volumetric "fill to here" line is 

done by using a sample bottle mari<er template. Alternatively, bottles may be weighed prior to bottle 

preparafion and weighed again after samples have been collected. 

All bottles should be cleariy labeled to indicate its intended use as a sample, field sample duplicate, low field 

matrix spike, high field matrix spike, sample/SRS field matrix spike, field duplicate sample/SRS field matrix 

spike, trip blank, or trip blank matrix spike. If each location has different designated spike levels, the label 

should also cleariy indicate the sample location designation. Generally, a set of bottles for a given collection 

site are prepared then grouped together in plastic bags for organizational purposes. For each sample 

collection event, at least one set of trip blank and trip blank matrix spikes are prepared. 

Bottle preparation should be documented in a Note to File or on a sample preparation wori<sheet and should 

include the following information: date prepared, total number of bottles prepared, number of sample sites, the 

standard identification numbers and spike volumes used to prepare spiked bottles, the "fill to here" volume, and 

any other pertinent infonnafion needed for reconstructibility of the data. The Note to File will be included in the 

final data package for the project. 

Samples are collected in the field and shipped to the laboratory at ambient temperature. 

8.1 Field Matrix Spike Sample (FMS) 

Field matrix spike samples are a requirement of the method. A FMS sample is defined as a QC sample to 

which known quantities of appropriate target analytes are added to the sample bottle in the field or in the 

laboratory before the bottles are sent to the field. The sample and field duplicate sample may contain 

appropriate SRSs in lieu of target analyte FMS samples. Sample quantities are determined volumetrically or 

gravimetrically. A known, specific volume or weight of sample is added to the sample container without 

rinsing. Volumetric sample measurements may be acquired by a laboratory applied "fill to this level" line on the 

outside of the sample container. Target analyte FMS samples should be spiked at approximately 0.5-10 times 

the expected analyte concentration in the sample. If the expected range of analyte concentrations is unknown, 

multiple spikes at varying levels may be prepared to increase the likelihood that a spike at an appropriate level 

is made. Typically a low and a high target analyte spike are prepared for each sampling location. In those 

instances where SRSs are to be used in lieu of target analyte FMS samples, the sample and field duplicate 

sample are spiked at approximately 2-5 times the target LOQ- The FMS is analyzed to ascertain if matrix 

effects or sample holding time contributes bias to the analytical results. For the sample bottles designated for 

matrix spikes, an appropriate volume of matrix spiking solution is added to the empty bottle prior to sampling. 

The volume of spike solution added should produce the desired final concentration of target analytes once the 

bottle is filled with sample to the "fill to here line". The matrix spiking solution(s) should be prepared in a 

suitable solvent and contain all of the appropriate target analytes, ISs, and SRSs. The target analyte matrix 

spiking solution is often the same as the working standards used to create the calibration standards. An 

example of a bottle spike is given below. 

"Fill to here" volume = 200 mL (A 250 mL Nalgene bottle is used) 

Desired Field Spike Concentration = 0.25 ng/mL 

ETS-8-044.1 Page 12 of 22 

Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection 

Analysis 

Page 67 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

500 [iL of a 0.1 (ig/mL spiking solution (containing the target analytes) is added to the bottle and the bottle cap 

promptly sealed. 

8.2 Internal Standard and Surrogate Recovery Standard 

If analysis of a surrogate recovery standard (SRS) is included in the project objectives, an appropriate volume 

of a sun-ogate standard solution is added to all the bottles prior to sampling and SPE. Typically sample bottles 

are spiked with surrogate recovery standards at a final desired spike concentration of 0.1 ng/mL. 

If quantitation by intemal standard (IS) is included in the project objective, an appropriate volume of intemal 

standard solution is added to all the bottles prior to sampling and SPE. Typically sample bottles are spiked 

with internal standard at a final desired spike concentrafion of 1 ng/mL. 

For the trip blank, the SRS spike and IS spike is added to the bottle and then ASTM Type I water (HPLC grade 

reagent water or other suitable water may used) is added to the "fill to here" line. The bottle is capped and 

sealing tape may be placed around the outer edge of the cap. Trip blank matrix spikes are prepared by adding 

the appropriate volume of target analyte spiking solution, IS, and SRS spiking solutions and filling the bottle to 

the desired volume with the appropriate water and capping and sealing the cap. 

9 Quality Control and Data Quality Objectives 

9.1 Data Quality Objectives 

This method and required quality control samples is designed to generate data accurate to ±30% with a 

targeted LOQ of 0.025 ng/mL. Any deviations from the quality control measures spelled out below will be 

documented in the raw data and footnoted in the final report. 

9.2 Method/Procedural Blanks 

The method/procedural blank is zero point calibration standard (which includes ISs) analyzed in a regular basis 

with each analysis batch. At a minimum, method blanks are analyzed prior to instmment calibration, prior to 

the analysis of CCV samples, after every 10 sample injections, and at the end of the analytical mn. 

The mean area count or area ratios when using internal standard calibration, for each analyte in the method 

blanks must be less than 50% of the area count counts or area ratios when using internal standard calibration, 

of the LOQ standard. The standard deviation of the area counts, or area ratios when using intemal standard 

calibration, of these method blanks should be calculated. A specific %RSD acceptance criteria is not specified 

but is assessed on an analytical batch basis. If the mean area counts or area ratios when using intemal 

standard calibration, of the method blanks exceed 50% of the LOQ standard, then the LOQ must be raised to 

the first standard level in the curve that meets criteria. Method blanks may be eliminated if technical 

justification can be provided (e.g. the procedural blank was analyzed after an unexpectedly high level sample). 

If any procedural blanks are removed from the LOQ determination, document in the raw data and report as 

appropriate. Laboratory Sample Replicates / Field Duplicate Sample 

Typically, samples are collected in duplicates in the field. The relative percent difference (RPD) of duplicate 

samples should be ^20% for the precision of sample preparation and analysis to be considered in control. 

Replicate samples not meeting the ^20% RPD criteria are flagged and reported as outside of QC acceptance 

criteria. 

9.3 Laboratory Matrix Spikes (LMSs) 

LMSs may be performed in lieu of FMSs if FMSs have previously been perfonned for the sample matrix. 

Additionally, LMSs may be performed in lieu of FMSs for a sample matrix if the FMS levels were not 

appropriate for detennining spike recoveries relative to endogenous levels of target analytes and appropriate 

SRSs. Generally, each sample location represents a different sample and sample matrix. LMSs are prepared 

for each sample and analyzed to determine the matrix effect on spike recovery efficiency of each target analyte 

and appropriate SRSs. LMSs should be prepared at a minimum of one level and in duplicate. LMS 

concentrations should be prepared at approximately 0.5-10 times the endogenous concentration or 

approximately 4-10 times the LOQ concentration of each target analyte. 

ETS-8-044.1 Page 13 of 22 

Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection 

Analysis 

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GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

Lab matrix spike recoveries should fall within ± 30% of expected values. Sample data with LMS recovery 

outside of ±30% but within ±50% of the expected value are fiagged and reported as outside of QC acceptance 

criteria. Data with LMS recovery outside of ±50% of the expected value are reported as NR, where NR is 

defined as "Not Reportable" data outside of QC acceptance criteria. 

9.4 Lab Control Sample 

Lab control spikes are prepared for each analysis batch to detemnine method accuracy and precision. LCSs 

should be prepared at three levels in triplicate for each target analyte and at a minimum of two levels in 

triplicate for appropriate SRSs. Low lab control spikes should be prepared at a concentration in the range of 

approximately four to ten times higher than the targeted lower LOQ, the mid lab control spikes should be 

prepared at a concentration near the mid-point of the calibration curve and the high lab control spikes at 

approximately 80% of the upper LOQ. For each target analyte and SRSs, the percent relative standard 

deviation (method precision) for each control spike level must be less than or equal to 20% and the average 

recovery (method accuracy) for each control spike level must be 80-120%). Sample data for target analytes 

outside of the laboratory control spike acceptance criteria will be handled as follows: 

If the average recovery of a spiking level falls outside method acceptance, but at least 67% (6 out of 9) of LCS 

samples are within 20% of their respective nominal value (33% of the QC samples, not all replicates at the 

same concentration, may be outside 20%> of nominal value), the average recovery will be flagged as outside 

method acceptance criteria. All LCS samples will be control charted as per ETS-4-026. If the average 

recovery of one of the spiking levels exceeded the analytical method uncertainty as detennined by ETS-12-

012, that analytical batch uncertainty will be expanded for that particular study. 

If more than 67% of the LCS samples fail to meet method acceptance criteria, the data will not be reported. 

Calibration standards consisting of mixed branched and linear isomer PFOS/PFOA are preferred. However, 

for PFOS/PFOA target analytes, if the calibration standards are comprised of predominantly linear isomers 

only, at least one level of triplicate LCSs should be prepared using PFOS/PFOA which contains a mix of linear 

and branched isomers. These LCSs will be used to demonstrate quantitative equivalency (or quantitative bias) 

of the isomeric mix when using a predominantly linear standard for calibration. The mixed linear and branched 

isomer PFOS/PFOA LCSs recoveries should fall within + 30% of expected values. Alternatively, in lieu of 

mixed branched and linear isomer PFOS/PFOA LCSs, mixed branched and linear isomer PFOS/PFOA 

TBMSs may be applied to demonstrate method accuracy and precision. 

9.5 Field Matrix Spikes (FMSs) / Surrogate Recovery Standards (SRSs) 

FMSs are prepared for each sampling location and analyzed to detennine the matrix effect and sample holding 

time on the spike recovery of each target analyte and/or appropriate SRS. Generally, each sample location 

represents a different sample and sample matrix. 

FMSs are QC samples to which known quantities of appropriate target analytes are added to the sample bottle 

in the laboratory before the bottles are sent to the field. Typically a low and a high target analyte FMS are 

prepared for each sampling location. The sample and field duplicate sample may contain appropriate SRSs in 

lieu of target analyte low field matrix spike and target analyte high field matrix spike samples. 

Field matrix spike method acceptance criteria are recoveries within ±30% of the expected value. If FMS 

recovery (target analyte or SRS spike) is outside of ±30% of the expected value or could not be assessed 

because the FMS (target analyte) was spiked at an inappropriate level, the sample result is reported as follows: 

1. ) If target analyte FMS recovery could not be assessed because the FMS's were at an inappropriate level, 

then Laboratory Matrix Spikes (LMS) may be substituted. If LMS recoveries are within ±30% the data are 

reportable and flagged to indicate that the FMS spikes levels were inappropriate. 

2. ) If multiple target analyte FMS's were prepared on a sample and the closest FMS level to the reported 

sample meets the ±30% acceptance criteria but additional FMS's are outside the ±30%i acceptance range, the 

data are reportable and flagged to indicate that while there were failing FMS's, the uncertainty will not be 

expanded since the most appropriate spike level passed. 

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Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

3. ) If the target analyte FMS recoveries are outside of the ±30% acceptance range but at least 30 acceptable 

historical reportable FMS sample results are available, the data may be reported but flagged with an expanded 

uncertainty and as not meeting FMS criteria. 

4. ) Sample data with FMS recovery outside of ±30% but within ±50% of the expected value are flagged and 

reported as outside of QC acceptance criteria with an expanded uncertainty. 

5. ) If FMS recovery is outside of ±50%, the sample result is reported as NR, where NR is defined as "Not 

Reportable" due to noncompliant QC results. 

The targeted fortification levels should be at least 50% of the endogenous level and less than 10 times the 

endogenous level to be used without justification to detemnine the statement of accuracy for analytical results. 

Note: It is possible for bottles utilized for Field Matrix Spike samples to be under-filled or over-filled during 

sample collection. Since this scenario will effect the actual concentration of the FMS sample (sun-ogate and 

intemal standard concentrations will also be effected, if used), it is important that any obvious under-filling or 

over-filling of sample bottles be documented in the data package and taken into account in the FMS, ISs, or 

SRSs recovery calculations. Samples over-filled or under-filled by more than 10% will be require recalculation 

of the FMS, ISs, and SRS tme values. 

The average of the sample and the field duplicate should be used to calculate the recovery. 

10 Procedures 

10.1 Water Sample Preparation 

This method is applicable to water samples. Samples containing heavy particulate may not be suitable for 

analysis by this method. Samples containing suspended particulate should be centrifuge prior to removing a 

sample aliquot, or filtered. 

• Thoroughly mix sample before removing an aliquot and placing in a labeled autovial. 

• Dilute sample, if necessary, with ASTM Type I water, HPLC water, other suitable water, or solvent 

(methanol). 

• Lab control spikes are prepared for each analysis batch to detennine method accuracy and precision. 

LCSs should be prepared at three levels in triplicate for each target analyte and at a minimum of two 

levels in triplicate for appropriate SRSs. Low lab control spikes should be prepared at a concentrafion 

in the range of approximately four to ten times higher than the targeted lower LOQ, the mid lab control 

spikes should be prepared at a concentration near the mid-point of the calibration curve and the high 

lab control spikes at approximately 80% of the upper LOQ. For IS quantitation, stable isotope intemal 

standards of each target analyte or appropriate sun-ogate ISs should be spiked at the same level as the 

samples being analyzed, in all LCSs. 

• If LCSs are being prepared using synthetic groundwater, allow the LCSs samples to equilibrate for a 

minimum of 4 hours before aliquoting for analysis or diluting with solvent (methanol). 

11 Sample Analysis - LC/MS/MS 

11.1 Instrument Setup 

Note: In this example, an Applied Biosystems Sciex API 4000 (API 5000 or API 5500) Tandem Mass 

Spectrometer (LC/MS/MS) is used. Other brands/models of LC/MS/MS instruments as well as single 

quadrupole mass spectrometers (LC/MS) may be used as long as the method acceptance criteria are met. 

Brand names, suppliers, part numbers, and models are for illustrative purposes only. Equivalent performance 

may be achieved using apparatus and materials other than those specified here, but demonstration of 

equivalent perfomnance that meets the requirements of this method is the responsibility of the laboratory. The 

operator must optimize and document the equipment and settings used. 

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Bert Jeffries Landfill - February 2012 

Establish the LC/MS/MS system and operating conditions equivalent to the following: 

Mass Spec: Applied Biosystems API 4000, API 5000, or API 5500 

Ion Source: Turiao Ion Spray (ABS) 

Mode: Electrospray Negative 

Scan Type: MRM (Multiple Reaction Monitoring) 

Computer: Dell DHM 

Software: Windows 2000 or Windows XP, Analyst 1.4.2 or higher versions 

HPLC: Agilent Series 1100,1200, or 1290 

Agilent Quaternary Pump 

Agilent Vacuum Degasser 

Agilent Autosampler 

Agilent Column Oven 

Note: One or more CI 8 HPLC analytical columns (2.1 mm x 100 mm, 5nm or 2.1 mm x50 mm, 5|im) maybe 

attached on-line after the purge valve and before the sample injection port to retard and separate any residue 

contaminants that may be in the mobile phase and/or HPLC system. 

HPLC Column: Betasil C18, 4.6mm x 100mm, 5nm (ThennoElectron Corporation) 

Column Temperature: 35°C 

Injection Volume: 5pL 

Mobile Phase (A): 2mM Ammonium Acetate in ASTM Type I water (See 7.3) 

Mobile Phase (B): Methanol 

Table 3. Liquid Chromatography Gradient Program. 

step 

Number 

Total Time 

(min) 

Flow Rate 

(/iUrnin) 

Percent A 

(2 mM ammonium 

acetate) 

Percent B 

(Methanol) 

0 0 750 97.0 3.0 

1 2.0 750 97.0 3.0 

2 14.5 750 5.0 95.0 

3 15.5 750 5.0 95.0 

4 16.5 750 97.0 3.0 

5 20.0 750 97.0 3.0 

Note: Other HPLC gradients may be used as long as the method criteria and project data quality objectives are 

met. 

It may be necessary to adjust the HPLC gradient in order to optimize instrument perfomiance. Columns with 

different dimensions (e.g. 2.1mm x 30mm) and columns from different manufacturers (Keystone Betasil C18 

etc.) may be used. 

ETS-8-044.1 Page 16 of 22 

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Analysis 

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GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

Table 4 Suggested MRIVI Transitions for Target Analytes, Surrogates, and Internal Standards 

Analyte 

Analyte Description Mass Transition 

01 (amu) 

Mass Transition 

03 (amu) 

PFBA (04 Acid) Target 213 169 

PFPeA (05 Acid) Target 263 219 

PFHxA (06 Acid) Target 313 269,119 

PFHpA (07 Acid) Target 363 319, 169 

PFOA (08 Acid) Target 413 369,219, 169 

PFNA (09 Acid) Target 

463 419, 169,219 

PFDA (CIO Acid) Target 513 469, 269,219 

PFUnA (Oil Acid) Target 563 519,269,219 

PFDoA (012 Acid) Target 613 569, 169,319 

PFTA(C13 Acid) Target 663 619, 369,319 

FBSA (04 Sulfonamide) Target 298 78 

FOSA (08 Sulfonamide) Target 498 78 

PFBS (04 Sulfonate) Target 299 99, 80 

PFHS (06 Sulfonate) Target 399 99, 80 

PFOS (08 Sulfonate) Target 499 80, 99, 130 

[1,2,3,4-"C4IPFBA IS for PFBA 217 172 

r 1,2,3,4,5-''CslPFPeA IS for PFPeA 268 223 

fl,2-"C2lPFHxA IS for PFHxA 315 270 

fl,2,3,4- "C4IPFHPA IS for PFHpA 367 322 

[1,2,3,4,5,6,7,8-"CslPFOA IS for PFOA 421 376 

[1,2,3,4,5,6,7,8,9-"CIPFNA IS for PFNA 472 427 

[1,2,3,4,5,6-"CslPFDA IS for PFDA 519 474 

[1,2,3,4,5,6,7-"CTlPFUnA IS for PFUnA 570 525 

[l,2-"C2lPFDoA IS for PFDoA and PFTA 615 570 

["O2IPFBS IS for PFBS 303 84 

[l,2,3-"C3lPFHS IS for PFHS 402 80 

[1,2,3,4- "C4IPFOS IS for PFOS 503 80 

[l,2,3,4,5,6,7,8-"C8lF0SA IS for FOSA 507 80 

[l,2,3,4-"C4lPF0A Surrogate (04-08 Acids) 417 372 

[1,2,3,4- "C4IPFOS Surrogate(Sulfonates, FOSA) 503 80 

[l,2-"C2]PFUnA Surrogate (09-013 Acids) 565 520 

Multiple transitions for monitoring the analytes is an option. The use of one daughter ion is acceptable if data 

sensitivity and selectivity is achieved and provided that retention time criteria are met to assure adequate 

specificity. While the daughter ions may be chosen at the discretion of the analyst, mass transition 99 is 

suggested for PFOS. Quantitation may be performed using the total ion chromatogram (TIC, or summed 

MRMs) for a given analyte. For example, the PFOA TIC would sum all three of the monitored transitions. Use 

of the suggested primary ion is recommended. Retention times may vary slightly, on a day-to-day basis, 

depending on the batch of mobile phase and the gradient, column, guard column(s) used etc. Drift in retention 

times is acceptable within an analytical njn, as long as the drift confinues through the enfire analysis and the 

standards are interspersed throughout the analytical run. 

11.2 Calibration Curve 

Quantitation is by internal standard or external standard calibration. Calibration standards may be prepared in 

ASTM Type I, HPLC water, other suitable water, or a solvent/water mixture. If internal standard calibration 

does not meet calibration acceptance criteria, extemal calibration can be applied. See Table 1 for 

ETS-8-044.1 Page 17 of 22 

Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection 

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Page 72 of 77 
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Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

recommended application of available intemal standards. Quantitation of PFOA and PFOS is by summed 

analyte-specific mass transitions. 

Analyze the standard curve prior to each set of samples. If internal standards were added to the calibration 

standards area rafios are used to generate the calibration curve. The standard curve may be plotted using a 

linear regression (y = mx + b), weighted 1/x or unweighted, or by quadratic fit (y = ax^ + bx + c), weighted 1/x or 

unweighted, using suitable software. The mathematical method used to calculate the calibration curve should 

be applied consistently throughout a study. Any change should be thoroughly documented in the raw data. 

High and/or low points may be excluded from the calibration curves to provide a better fit over the range 

appropriate to the data or because they did not meet the pre-detemnined acceptance criteria. Low-level curve 

points should also be excluded if their area counts (or area ratio if quantitating by IS) are not at least twice that 

of the average area counts (or area ratio if quantitafing by IS) of method and/or solvent blanks. The coefficient 

of determination (r^) value for the calibration curve must be greater than or equal to 0.990 (or a con-elation 

coefficient (r) of 0.995). Each point in the curve must be within ±25% of the theoretical concentration with the 

excepfion of the LLOQ, which may be within ±30%. Justification for exclusion of calibration curve points will be 

noted in the raw data. A minimum of 6 points will be used to construct the calibration curve. 

If the calibration curve does not meet acceptance criteria, perfomn routine maintenance or prepare a new 

standard curve (if necessary) and reanalyze. 

11.3 Continuing Calibration Verification (CCV) 

Continuing calibration verifications (CCV) are analyzed to verify the accuracy of the calibrafion curve. Analyze 

a mid-range calibration standard, one of the same standards used to construct the calibration curve, at a 

minimum after every tenth sample, not including solvent blanks, with a minimum of one per sample set. 

Calibrafion verificafion injections must be within +25%) to be considered acceptable. The calibration curve and 

the last passing CCV will then bracket acceptable samples. Multiple CCV levels may be used. Samples must 

be bracketed by passing CCVs or the calibration curve and a passing CCV to be reportable. 

11.4 System Suitability 

A minimum of three system suitability samples should be injected at the beginning of each analytical mn, prior 

to the analysis of the calibration curve. Typically these samples are at a concentration near the mid-level of the 

calibration curve and are repeated injections from one autosampler vial. It is suggested that the system 

suitability injections have area counts or area ratios when using internal standard calibration, with a target RSD 

of <5%> and a target retention time RSD of <2%. There is no defined acceptability limit on these results as the 

%)RSD value is dependent on the number of MRM transitions being monitored in the LCIMSMS run or time 

period. Ultimately, any effects on these parameters for the System Suitability samples will also be evident on 

all standards and QC samples analyzed as part of the analysis batch. Any effect of system suitability is 

incorporated within QC acceptance criteria. 

11.5 Sample Analysis and QC s 

For each analysis batch, the instrument analysis run sequence should include an initial calibration curve, 

samples, FDSs, interspersed blanks, interspersed CCVs, appropriate QCs (i.e., LCSs, LMSs, FMSs, TBMSs, 

and TBs), and a final CCV or calibration curve bracketing samples and appropriate QCs 

Inject the same volume (between 5 -1 00|JL) of each standard, analytical sample and blank into the instrument 

(unless an on-instrument sample dilution is desired). 

Samples containing analytes that are quantitated above the concentration of the highest standard in the curve 

should be further diluted and reanalyzed. 

' 3M Environmental Laboratory study E08-0096 evaluated the effect on these results as a flinction of the number of MRMs being monitored. 

ETS-8-044.1 Page 18 of 22 

Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection 

Analysis 

Page 73 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

12 Data Analysis and Calculations 

The chromatography analysis software will typically calculate the amount of target analyte in the sample 

extracts using the established calibration curve. 

Calculate the percent recovery of the LCS using the following equation: 

LCS Concentration (—) 

LCS% recovery = * 100% 

ne Spike Concentration (—^) 

mL 

Calculate the percent recovery of the LMS using the following equation: 

LMS Concentration (-^) - Concentration of Sample (-^) 

LMS % recovery = ^ — * 100% 

Spike Concentration (-^ ) 

mL 

For samples fortified with known amounts of analyte prior to extraction, use the following equation to calculate 

the percent recovery. 

_ Total analyte found (ng/mL) - Average analyte found in sample (ng/mL) ^ 

Analyte added (ng/mL) 

13 Analysis Batch Method Performance Criteria 

Any method performance parameters that are not achieved must be considered in the evaluation of the data. 

Nonconformance to any specified parameters must be described and discussed in the final report if the 

Technical Manager (non-GLP study) or Study Director (GLP study) chooses to report the data. 

If criteria listed in this method perfomnance section are not met, maintenance may be perfonned on the system 

and samples reanalyzed, or other actions taken as appropriate. Document all actions in the raw data. 

If data are to be reported when performance criteria have not been met, the data must be footnoted on tables 

and discussed in the text of the report. 

13.1 System Suitability - Analysis Batch 

A minimum of three system suitability samples should be injected at the beginning of each analytical njn. 

These samples are run prior to the calibration curve. It is suggested that the system suitability injections have 

area counts with a target RSD of <5% and a target retention time RSD of <2%. There is no defined 

acceptability limit on these results as the %RSDs are dependent on the number of MRM transitions being 

monitored in the LC/MS/MS run or time period. Any effect of system suitability is incorporated in the QC 

acceptance criteria. 

13.2 Calibration and Limit of Quantitation (LOQ) - Analysis Batch 

Calibration Curve: The coefficient of detennination (r^) value for the calibration curve must be greater than or 

equal to 0.990 con-esponding to a correlation coefficient (r) = 0.995. Each point in the curve must be within 

±25%) of the theoretical concentration with the exception of the LLOQ, which may be within +30%. 

CCV Performance: The calibration standards that are interspersed throughout the analytical sequence are 

evaluated as continuing calibration verifications in addition to being part of the calibration curve. The accuracy 

ETS-8-044.1 Page 19 of 22 

Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection 

Analysis 

Page 74 of 77 
GLP10-01-02; Interim Report 26 

Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

of each curve point must be within 25% of the theoretical value (within 30% for lowest curve point). Samples 

that are bracketed by CCVs not meeting these criteria must be reanalyzed. 

Limits of Quantitation (LOQ): The lower LOQ (LLOQ) is the lowest non-zero active standard in the 

calibration curve; the peak area of the LLOQ must be at least 2X that of the average area counts for all 

prepared procedural blank(s). By definition, the measured value of the LLOQ must be within 30% of the 

theoretical value. 

Demonstration of Specificity: Specificity is demonstrated by chromatographic retention time (within 4% of 

standard) and the mass spectral response of unique ions. 

13.3 Blanks - Method/Procedural Blanks and Trip 

H/lethod/Procedurai Blanks: Multiple procedural blanks should be interspersed throughout the analysis batch 

and the analytical sequence. At a minimum, method blanks are analyzed prior to instmment calibration, prior 

to the analysis of CCV samples, after every 10 sample injections, and at the end of the analytical run. 

The mean area counts (or area ratios when using IS calibration) for each analyte must be less than 50% of the 

area count of the LOQ standard. If the area counts of the procedural blanks exceed 50% of the LOQ standard, 

then the LOQ must be raised to the first standard level that meets criteria. 

Trip Blank: A trip blank of ASTM Type I water (or lab equivalent) is prepared in a sample container in the 

laboratory and treated as a sample, including exposure to shipping, sampling site conditions, storage, 

preservation and all analytical procedures. The trip blanks results for each analyte are included with the 

reported sample results. 

13.4 Data Accuracy and Precision - Analysis Batch 

Lab Control Spikes: The average recovery at each LCS level for each target analyte and appropriate SRS 

should be within 80-120%) and the percent relative standard deviation of the recoveries must be less than or 

equal to 20%. If the average recovery of a spiking level falls outside method acceptance, but at least 67%) (6 

out of 9) of LCS samples are within 20%o of their respective nominal value [33% of the QC samples, not all 

replicates at the same concentration, may be outside 20% of nominal value), the average recovery will be 

flagged as outside method acceptance criteria. All LCS samples will be control charted as per ETS-12-012. If 

the average recovery of one of the spiking levels exceeded the analytical method uncertainty as determined by 

ETS-12-012, that analytical batch uncertainty will be expanded for that particular study. The average recovery 

at each LCS level for mixed branched/linear isomer PFOA and PFOS should be within 70-130% and the 

percent relative standard deviation of the recoveries must be less than or equal to 20%. 

Field Duplicates: The relative percent difference (RPD) of duplicate samples should be less than 20% for the 

precision of sample preparation and analysis to be considered in control. Replicate samples not meeting the 

20%) RPD criteria are fiagged and reported as outside of QC acceptance criteria. 

Field Matrix Spikes: FMS acceptance criteria are recoveries within ±30% of the expected value for each 

target analyte and appropriate SRS. Sample data with FMS recovery outside of ±30% but within ±50% of the 

expected value are fiagged and reported as outside of QC acceptance criteria. Data with FMS recovery 

outside of ±50% of the expected value are reported as NR, where NR is defined as "Not Reportable" data 

outside of QC acceptance criteria. If FMS recovery could not be assessed because FMSs were at an 

inappropriate level, then Laboratory Matrix Spikes (LMSs) may be substituted. If LMS recoveries are within 

±30% for each target analyte and SRSs the data are reportable but fiagged as not meeting the FMS method 

acceptance criteria. 

13.5 Analytical Method Uncertainty 

Analytical method uncertainty for each target analyte and SRS is detennined with control charted historical 

analysis batch LCS data for the method and reported with each analysis batch.^ Uncertainty detenninations 

^ Method uncertainty based on INTERNATIONAL ANS/ISO/IED STANDARD 17025 reference (GUM, Guide to the Expression of 

Uncertainty in Measurement). Method application demonstrated in ETS-12-012, citing references: a.) EURACHEM/CITAC Guide, 

"Quantifying Uncertainty in Analytical Measurement," Second Edition; Editors: S.L.R. Ellison, M. Rosslein, and A. Williams. 

b.)Georgian, Thomas, "Estimation of Laboratory Analytical Uncertainty Using Laboratory Control Samples," Environmental Testing & 

ETS-8-044.1 Page 20 of 22 

Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection 

Analysis 

Page 75 of 77 
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Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

are based on INTERNATIONAL ANS/ISO/IED STANDARD 17025 reference (GUM, Guide to the Expression 

of Uncertainty in Measurement) and described in ETS-12-012. At least thirty data points are required for 

detemnining analytical method uncertainty. The method uncertainty is defined as 2x the standard deviation of 

the percent recoveries of the pooled lab control spikes. While all LCS data points are control charted, only the 

most recent fifty data points are used for determining the method uncertainty. 

When less than thirty LCS data points have been generated for a given analyte, the analysis batch LCSs are 

used to detennine the data uncertainty. If FMSs meet the ±30% recovery criteria at a level appropriate to the 

endogenous level, and the LCS meet the ±20% recovery criteria, then the uncertainty of the data is determined 

as within ^00±20%. 

Analysis batch sample data with FMS recovery outside of ±30% but within ±50% of the expected value are 

flagged and reported as outside of QC acceptance criteria with expanded uncertainties. Data with FMS 

recovery outside of ±50% of the expected value are reported as NR, where NR is defined as "Not Reportable" 

data outside of QC acceptance criteria. If FMS recovery could not be assessed because FMSs were at an 

inappropriate level, then Laboratory Matrix Spikes (LMSs) may be substituted. If LMS recoveries are within 

±30% for each target analyte and appropriate SRSs the data are reportable but flagged as not meeting the 

FMS method acceptance criteria with uncertainties of ±30%. If FMS do not meet the ±30% recovery criteria, 

and historical FMS data does not exist, the analytical uncertainty is evaluated on a sample-by-sample basis, 

the data may be reported with expanded uncertainty and are flagged. 

13.6 Quantitation of PFOA/PFOS - Analysis Batch 

Calibration standards consisting of mixed branched and linear isomer PFOS/PFOA are prefen-ed. 

Quantitation is perfomned by integrating the linear and branched isomers together. Alternately, the linear and 

branched isomers can be integrated separately, applying the appropriate true value to each calibration curve 

point for each isomer. The LCS and samples are then quantitated by integrating the linear and branched 

isomers separately (requires separate analytical results files) and quantitating the resulting peak against the 

linear or branched calibration curve. The results from both integrations are then summed to produce the final 

result. Integrating the linear and branched isomers separately may be helpful for those samples where the 

linear/branched ratios do not closely match those of the reference standards. 

However, for PFOS/PFOA target analytes, if the calibration standards are comprised of predominantiy linear 

isomers only the method requires the addition of LCSs of mixed branched/linear isomer PFOS/PFOA. The 

purpose of including these LCSs is to demonstrate quantitative equivalency (or quantitative bias) of the 

isomeric mix when using a predominantly linear PFOS or PFOA standard for calibration. Alternatively, in lieu 

of mixed branched and linear isomer PFOS/PFOA LCSs, mixed branched and linear isomer PFOS/PFOA 

TBMSs may be applied to demonstrate method accuracy and precision. 

An alternate method of quantitation can be performed whereby only the linear isomer of PFOS/PFOA is 

integrated and used for generating the calibration curve. The LCS and samples are then quantitated by 

integrating the linear and branched isomers separately (requires separate analytical results files) and 

quantitating the resulting peak against the linear calibration curve. The results from both integrations are then 

summed to produce the final result. Integrating the linear and branched isomers separately reduces the oncolumn concentration for those samples that contain both linear and branched isomers of PFOA/PFOS. This 

ensures that the concentration detected is within the a range of the calibration curve that is comparable 

regardless of whether the calibration curve was generated using predominantly linear isomers of PFOS/PFOA 

or linear plus branched isomers of PFOS/PFOA. 

14 Pollution Prevention and Waste Management 

Waste generated when performing this method will be disposed of appropriately. The original samples will be 

archived at the 3M Environmental Laboratory in accordance with intemal procedures. 

Analysis, November/December 2000. c.)Taylor, B.N. and CE. Kuyatt, NIST Technical Note 1297,1994 Edition; "Guidelines for 

Evaluating and Expressing the Uncertainty of NIST Measurement Results."d.)Adams, T.M., "A2LA Guide for the Estimation of 

Measurement Uncertainty in Testing", July 2002. 

ETS-8-044.1 Page 21 of 22 

Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection 

Analysis 

Page 76 of 77 
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Analysis of PFBS, PFHS, and PFOS 

Bert Jeffries Landfill - February 2012 

15 Records 

Each data package generated for a study must include all supporting information for reconstnjction of the data. 

Infomnation for the data package must include, but is not limited to the following items: study or project 

number, sample and stand_ard prep sheets/records, instrument run log (instrument batch records, instrument 

acquisition method, summary pages), instmment results files, chromatograms, calibration curves, and data 

calculations. 

16 Affected Documents 

None. 

17 Revisions 

Revision 

Number Summarv of Changes 

1 Section 1. Included the use of internal standard calibration by this method. 

Section 2. Included the use of internal standard calibration by this method. Included the 

use of a solvent/water mixture when analyzing for PFUnA, PFDoA, PFTrDA, and FOSA. 

Section 3. Added definitions for internal standard, surrogate internal standard, and 

surrogate recovery standard. 

Section 6. Removed the details regarding the instrument parameters to section 10 of the 

method. 

Section 7. Updated reference standards to include intemal standards and surrogates. 

Changed concentration levels for working standards and included the use of internal 

standards and surrogates. 

Section 8. Inserted a new section on sample bottle preparation. 

Section 9 Quality Control. This section was previously section 10 in ETS-8-044.0. Updated 

QC chteria to be consistent with method ETS-8-154.4. 

Section 10 Procedures. This section was previously section 8 (Sample Handling) in ETS-8-

044.0. Added detail regarding the preparation of LCSs. Included the use of methanol as a 

dilution solvent. 

Section 11 Sample Analysis. This section was previously section 10 in ETS-8-044.0. 

Included the details regarding the instrument parameters. 

Section 12 Data Analysis and Calculations. This section was previously section 11 in ETS8-044.0. Removed the equation for calculating the analytes concentration, indicating that 

this is done by the instrument software. 

Section 13 Method Performance. This section was previously section 12 in ETS-8-044.0. 

Updated QC criteria to be consistent with ETS-8-154.4. Added information on the 

determination of analytical method uncertainty and quantitation of PFOfi^/PFOS. 

Section 14 Pollution Prevention. This section was previously section 13 in ETS-8-044.0. 

Section 15 Records. This section was previously section 14 in ETS-8-044.0. 

Section 16 Affected Documents. This section was previously section 15 in ETS-8-044.0. 

Section 17 Revisions. This section was previously section 16 in ETS-8-044.0. 

ETS-8-044.1 Page 22 0^22 

Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection 

Analysis 

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