 GLP10-01-01, Interim Report 29: Analysis of PFOA in Groundwater Samples Collected at 

the Former Sludge Incorporation Area (FSIA) located in Decatur, AL, in March/April 2012

Study Title

Analysis of Perfluorooctanoic Acid (PFOA) 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, Bldg 260-05-N-17

Maplewood, MN 55144

Project Identification

GLP10-01-01-29 

 

Total Number of Pages

68

Testing Cert #2052.01

The testing reported herein meet the requirements of ANSI/ ISO/IEC 17025:2005 “General 

Requirements for the Competence of Testing and Calibration Laboratories”, in accordance with 

the A2LA Testing Certificate # 2052.01. Testing that complies with this International Standard 

also meets principles of ISO 9001:2000. 
This page has been reserved for specific country requirements. 

GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 2 of 68
GLP10-01-01; Interim Report 29 

Analysis of PFOA In Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012 

GLP COMPLIANCE STATEMENT 

Report Title: GLP10-01-01, Interim Report 29. Analysis of PFOA in Groundwater Samples Collected 

at the Fomrier Sludge Incorporation Area (FSIA) at Decatur, AL, in March/April 2012 

Study: Analysis of Perfluorooctanoic Acid (PFOA) 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 specific 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 detennined under GLPs. 

5/ 

'/ 

V2L Gary Hohaflstein, Sponsor Representative Date 

m hi/ mli2^ 

Jaisimha^sari, P.E., DEE, Study Director ( Date 

Page 3 of 68 
GLPI 0-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012 

QUALITY ASSURANCE STATEMENT 

Report Title: GLP10-01-01, Interim Report 29. Analysis of PFOA in Groundwater Samples Collected 

at the Former Sludge Incorporation Area (FSIA) at Decatur, AL, in March/April 2012 

Study: Analysis of Perfluorooctanoic Acid (PFOA) in Groundwater, Soil and Sediment for the 3M 

Decatur Phase 3 Site-Related Monitoring Program. 

This report and the accompanying data were audited by the 3M Environmental Laboratory Quality 

Assurance Unit (QAU), as indicated below. The findings were reported to the principal investigator 

(P.I.), laboratory management and study director. 

Inspection Dates Phase 

Date Reported to 

Inspection Dates Phase Testing Facility 

Management 

Study Director 

4/17/12 Data / Interim Report 4/26/12 4/26/12 

QAU Represenaitive Date 

Page 4 of 68 
TABLE OF CONTENTS 

GLP Compliance Statement...................................................................................................................... 3

Quality Assurance Statement.................................................................................................................... 4

Table of Contents....................................................................................................................................... 5

List of Tables .............................................................................................................................................. 6

1 Study Information................................................................................................................................ 8

2 Summary ............................................................................................................................................. 9

3 Introduction........................................................................................................................................10

4 Test & Control Substances ..............................................................................................................11

5 Reference Substances .....................................................................................................................11

6 Test System ......................................................................................................................................11

7 Method Summary .............................................................................................................................12

7.1 Methods ............................................................................................................................12

7.2 Sample Collection.............................................................................................................12

7.3 Sample Preparation..........................................................................................................12

7.4 Analysis.............................................................................................................................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 .........................................................................................15

8.8 Field Matrix Spikes (FMS)................................................................................................15

GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

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9 Data Summary and Discussion .......................................................................................................16

10 Conclusion.........................................................................................................................................25

11 Data/Sample Retention ....................................................................................................................25

12 Attachments ......................................................................................................................................25

13 Signatures .........................................................................................................................................26

LIST OF TABLES

Table 1. Summarized PFOA Results (FSIA Groundwater, Decatur, AL, March/April 2012)...............10

Sample Description Key Code.................................................................................................................12

Table 2. Instrument Parameters.............................................................................................................13

Table 3. Liquid Chromatography Conditions. ........................................................................................13

Table 4. Mass Transitions.......................................................................................................................13

Table 5. Limit of Quantitation (LOQ).......................................................................................................14

Table 6. Laboratory Control Spike Recovery.........................................................................................15

Table 7. Analytical Method Uncertainty.................................................................................................. 15

Table 8. Field Matrix Spike Levels..........................................................................................................16

Table 9. DAL GW 130R 120329 ............................................................................................................17

Table 10. DAL GW 130S 120329...........................................................................................................17

Table 11. DAL GW 130L 120329...........................................................................................................17

Table 12. DAL GW 131R 120328 ..........................................................................................................17

Table 13. DAL GW 131S 120328...........................................................................................................18

Table 14. DAL GW 131L 120328...........................................................................................................18

Table 15. DAL GW 133R 120328 ..........................................................................................................18

Table 16. DAL GW 133S 120328...........................................................................................................18

Table 17. DAL GW 133L 120328...........................................................................................................19

Table 18. DAL GW 134R 120328 ..........................................................................................................19

Table 19. DAL GW 134S 120327...........................................................................................................19

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Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

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Table 20. DALGW 134L 120327............................................................................................................19

Table 21. DAL GW 135R 120329 ..........................................................................................................20

Table 22. DAL GW 135S 120329...........................................................................................................20

Table 23. DAL GW 135L 120329...........................................................................................................20

Table 24. DAL GW 136S 120328...........................................................................................................20

Table 25. DAL GW 136L 120328............................................................................................................21

Table 26. DAL GW 137S 120328............................................................................................................21

Table 27. DAL GW 137L 120328............................................................................................................21

Table 28. DAL GW 138S 120329............................................................................................................21

Table 29. DAL GW 138L 120330............................................................................................................22

Table 30. DAL GW 140R 120329 ...........................................................................................................22

Table 31. DAL GW 141R 120403 ...........................................................................................................22

Table 32. DAL GW 142R 120328 ...........................................................................................................22

Table 33. DAL GW 143R 120329 ...........................................................................................................23

Table 34. DAL GW 144R 120328 ...........................................................................................................23

Table 35. DAL GW 145R 120328 ...........................................................................................................23

Table 36. Trip Blank 1.............................................................................................................................23

Table 37. Rinseate Blanks......................................................................................................................24

GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 7 of 68
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.

West Chester, 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

Maplewood, MN 55106

Study Personnel

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

Cleston Lange, Ph.D., Principal Analytical Investigator. (clange@mmm.com); phone (651)-733-9860

Susan Wolf, 3M Analyst

Chelsie Grochow, Analyst

Kelly Ukes, Analyst

Study Dates

Study Initiation: March 8, 2010

Interim Report 29 Experimental Termination: April 10, 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

GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 8 of 68
2 Summary

The 3M Environmental Laboratory received groundwater samples from wells located at the Former 

Sludge Incorporation Area (FSIA) in Decatur, AL for perfluorooctanoate (PFOA) analysis under 3M 

project GLP10-01-01-29. A total of seventy-seven sample bottles were prepared for thirty-two different 

sampling locations. Samples were not collected from five of the specified sampling locations; DAL GW 

136R, DAL GW 137R, DAL GW 138R, DAL GW CW26C, and DAL GW CW26L. Samples were 

collected March 27 - April 3, 2012 and received from Weston personnel on April 4, 2012.

Based on previous sampling of the FSIA (GLP10-01-01-07, GLP10-01-01-11, GLP10-01-01-18, and 

GLP10-01-01-24), the 3M Environmental Laboratory has demonstrated through the use of field matrix 

spikes, that 3M Environmental Laboratory Method ETS-8-044.1 used for the analysis of the samples is 

appropriate for the sample matrix. Therefore, for this sampling event, field matrix spike (FMS) samples 

were prepared for six of the twenty-seven sampling locations collected. In addition, a trip blank set

containing Milli-QTM water and appropriate trip blank spikes were prepared, as well as two equipment 

rinseate blanks. The equipment rinseate blanks did not have FMS samples prepared for determination 

of PFOA recovery. All of the samples were prepared and analyzed for PFOA following 3M 

Environmental Laboratory Method ETS-8-044.1. Many of the groundwater samples required dilution to 

attain PFOA concentrations within the range of the curve, in some instances up to 100-fold dilution

were required. The average measured PFOA concentrations are summarized in Table 1. The 

equipment rinseate blanks and trip blank were below the lower limit of quantitation (LLOQ) of 0.0240

ng/mL, indicating adequate control of sample contamination during shipping and sample collection. The

PFOA concentration results for all groundwater samples ranged over four orders of magnitude from 

0.313 ng/mL to 3400 ng/mL. The analytical uncertainty was estimated at ± 23%. 

GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

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Table 1. Summarized PFOA Results (FSIA Groundwater, Decatur, AL, March/April 2012) 

Sample ID

Avg. PFOA 

Concentration 

(ng/mL)

Relative 

Percent 

Difference

DAL GW 130R 120329 789 1.9%

DAL GW 130S 120329 162 0.62%

DAL GW 130L 120329 61.8 1.1%

DAL GW 131R 120328 1770 7.4%

DAL GW 131S 120328 23.9 1.3%

DAL GW 131L 120328 87.6 1.4%

DAL GW 133R 120328 58.0 2.2%

DAL GW 133S 120328 273 0.37%

DAL GW 133L 120328 185 2.7%

DAL GW 134R 120328 1930 1.0%

DAL GW 134S 120327 14.2 4.9%

DAL GW 134L 120327 499 0.80%

DAL GW 135R 120329 3400 2.9%

DAL GW 135S 120329 57.3 1.6%

DAL GW 135L 120329 305 7.2%

DAL GW 136S 120328 86.1 6.0%

DAL GW 136L 120328 79.2 1.3%

DAL GW 137S 120328 0.313 2.9%

DAL GW 137L 120328 0.328 0.92%

DAL GW 138S 120329 181 1.7%

DAL GW 138L 120330 0.566 1.2%

DAL GW 140R 120329 133 0.75%

DAL GW 141R 120403 1.59 0.63%

DAL GW 142R 120328 52.4 0.19%

DAL GW 143R 120329 22.8 1.8%

DAL GW 144R 120328 64.6 3.3%

DAL GW 145R 120328 48.1 1.9%

Trip Blanks (Milli-QTM Water) < 0.0240 N/A

GLP10-01-01-29 Equipment rinseate blanks: 

DAL GW 130R and DAL GW 135R < 0.0240 N/A

N/A: not applicable

The analytical uncertainty for PFOA was estimated at ±23%.

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 

information regarding concentrations of perfluorooctanoate (PFOA) 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 ground water samples collected from various wells located 

at the Former Sludge Incorporation Area (FSIA) in Decatur, AL for PFOA in an effort to characterize 

regional groundwater conditions. 

The 3M Environmental Laboratory prepared sample bottles (250 mL high-density polyethylene) which 

were shipped to Decatur, AL Weston personnel prior to field sampling. Sample bottle sets for each 

groundwater sampling location included a field sample and field sample duplicate. A field matrix spike 

GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 10 of 68
samples was prepared for six of the twenty-seven sampling locations collected. Each empty container 

for groundwater sampling was marked with a “fill to here” line to produce a final sample volume of 200 

mL. Containers designated for field matrix samples were fortified with an appropriate matrix spike 

solution containing PFOA prior to being sent to the field for sample collection. 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 method ETS-8-044.1 “Method of Analysis for the Determination of Perfluorinated 

Compounds in Water by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection 

Analysis”. 

Table 1 summarizes the average PFOA concentrations for the duplicate groundwater samples

collected, the trip blank, and equipment rinseate blank samples. Tables 10-38 summarize the 

individual sample results and the associated FMS recoveries. All results for the quality control samples 

prepared and analyzed with the samples are reported and discussed elsewhere in this 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. 

5 Reference Substances

The analytical reference substances used for this study are listed below.

Reference 

Substance

PFOA 

(Branched and Linear isomers)

PFOA 

(Branched and Linear isomers)

Chemical Name Perfluorooctanoate Perfluorooctanoate

Chemical Formula C7F15COO- C7F15COOIdentifier CAS # 335-67-1 CAS # 95328-99-7 

Use FMS Reference Standard Target Analyte and LCS Reference 

Standard

Source Sigma Aldrich Wellington

Expiration Date 07/27/2016 03/17/2014

Storage Conditions Ambient Frozen

Chemical Lot Number MKBD4574V TPFOA0311

TCR Number TCR11-0029 TCR11-0009, TCR11-0042

Physical Description Powder Liquid

Purity 96.8% 98.3%

6 Test System

There was not a test system for this study in the classic sense of a GLP study. This study was 

conducted for analysis of ground water samples collected from wells located in Decatur, AL by Weston 

Solutions, Inc. personnel. Samples for this study are “real world” environmental samples.

GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Formwe Sludge Incorporation Area - March/April 2012

Page 11 of 68
Table 2. Sample Description Key Code.

String Number String Descriptor Example

Example DAL GW 131R 0 120328

1 Sample Location DAL= Decatur, Alabama

2 Well ID Example: 131

3 Well Level R = Residuum shallow water-bearing zone 

L = Bedrock water-bearing zone

S = Epikarst middle water-bearing zone

4 Sampling Date 120328 – March 28, 2012 

5 Sample Type 0=primary sample 

DB=duplicate sample

FMS = Field Matrix Spike

7 Method Summary

7.1 Methods

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

“Method of Analysis for the Determination of Perfluorinated Compounds In Water by High Performance 

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 GLP10-01-01-29 were returned to the 

laboratory at ambient conditions on April 4, 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. 

Samples that required dilution were prepared by diluting 1mL of sample with 9 mLs of Milli Q water 

(dilution 1:10). Samples requiring a 1:100 dilution were prepared by diluting 0.1 mL of sample with 9.9 

mLs of MilliQ water. 

7.4 Analysis

All study samples and quality control samples were analyzed for PFOA using high performance liquid 

chromatography/ tandem mass spectrometry (HPLC/MS/MS). Detailed instrument parameters, the 

liquid chromatography gradient program, and the specific mass transitions analyzed are described in the 

raw data hard copies placed in the final data packet, and are briefly described below in Table 3, Table 4

and Table 5. 

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Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 12 of 68
Table 3. Instrument Parameters. 

Instrument Name ETS Buster

Analytical Method Followed ETS-8-044.1

Analysis Date 4/5/12

Liquid Chromatograph Agilent 1100

Guard column Betasil C18 (4.6 mm X 100 mm), 5μ

Analytical column Betasil C18 (4.6 mm X 100 mm), 5μ

Injection Volume 2 or 10 μL

Mass Spectrometer Applied Biosystems API 4000

Ion Source Turbo Spray

Electrode Turbo ion electrode

Polarity Negative

Software Analyst 1.4.2

Table 4. Liquid Chromatography Conditions. 

Step 

Number

Total Time 

(min)

Flow Rate 

(μL/min)

Percent A

(2 mM ammonium acetate)

Percent B

(Methanol)

ETS-8-044.1 Analysis

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

PFOA

413/369

413/219 Linear + Branched

413/169

Dwell time was 100 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

All samples were analyzed against an external standard calibration curve. Calibration standards were 

prepared by spiking known amounts of the stock solution containing PFOA into Milli Q water. A total of 

fifteen spiked standards ranging from 0.0250 ng/mL to 100 ng/mL (nominal) were prepared and 

analyzed. A quadratic, 1/x weighted, calibration curve of the peak area counts was used to fit the data 

for PFOA. The data were not forced through zero during the fitting process. Calculating the standard 

concentrations using the peak area confirmed accuracy of each curve point. Each curve point was 

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

GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 13 of 68
requirements of 100±25% (100±30% for the lowest curve point) were met. The correlation coefficient (r) 

was greater than 0.995 for PFOA. 

8.2 System Suitability

A calibration standard was analyzed four times at the beginning of the 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 PFOA. 

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 are at least twice those of the appropriate 

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

Table 6. Limit of Quantitation (LOQ). 

Analysis Date(s) PFOA

LOQ, ng/mL(1)

4/5/12 0.0240

(1) Analytical LOQ without sample dilution factions applied.

8.4 Continuing Calibration 

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

analyzed to confirm that the instrument response and the initial calibration curve were still in control. All 

CCVs met method criteria of 100% ± 25% for PFOA.

8.5 Blanks

Three types of blanks were prepared and analyzed with the samples: procedural blanks, trip blanks, and 

equipment rinseate blanks. Procedural blank results were reviewed and used to evaluate method 

performance and to determine the LOQ for PFOA. Trip blanks reflect the shipping and sample collection 

conditons the sample bottles and samples experience. Equipment rinseate blanks are aqueous 

samples that reflect the efficiency of equipment cleaning in the field between different sample collections 

to ensure no cross contamination of samples from the equipment.

8.6 Lab Control Spikes (LCSs) 

Low, mid, and high-level lab control spikes were prepared and analyzed in triplicate with each 

preparation set. LCSs were prepared by spiking known amounts of the analyte into 10 mL of laboratory 

Milli Q water or synthetic groundwater, to produce the desired concentration. The spiked water samples 

were then analyzed in the same manner as the samples. The method acceptance criteria, average of 

LCSs at each level should be within 100% ± 20% with an RSD ≤20%, were met for PFOA. All LCS 

samples were used in the determination of method uncertainty in section 8.7.

The following calculations were used to generate data in Table 7 for laboratory control spikes: 

* 100%

Spike Concentration

Calculated Concentration LCSPercent Recovery =

* 100%

average LCS recovery

standard deviation LCS replicates LCS% RSD =

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Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

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Table 7. Laboratory Control Spike Recovery. 

ETS-8-044.1 

Analyzed 4/5/12 PFOA (Branched and Linear isomers)

Lab ID

Spiked 

Concentration 

(ng/mL)

Calculated 

Concentration 

(ng/mL) %Recovery

LCS-120405-1 0.477 0.433 90.7

LCS-120405-2 0.477 0.428 89.7

LCS-120405-3 0.477 0.431 90.3

Average ± %RSD 90.2% ± 0.56%

LCS-120405-4 4.77 4.53 94.9

LCS-120405-5 4.77 4.60 96.4

LCS-120405-6 4.77 4.58 96.0

Average ± %RSD 95.8% ± 0.81%

LCS-120405-7 28.7 25.0 87.1

LCS-120405-8 28.7 24.6 85.8

LCS-120405-9 28.7 25.1 87.5

Average ± %RSD 86.8% ± 1.0%

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 

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

corresponds to a confidence level of 95%. 

Table 8. Analytical Method Uncertainty.

Analyte Method Standard Deviation Method 

Uncertainty

PFOA ETS-8-044.1 11.7 ±23%

 

8.8 Field Matrix Spikes (FMS)

A field matrix spike was collected at six sampling locations 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 the target analytes 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. 

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Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 15 of 68
Table 9. Field Matrix Spike Levels.

100%*

Concentrat Spike on

Concentrat (Sample ofion FMS Concentrat Average Dup.) Sample Field & Sample Field:ion FMSRecovery − =

9 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 Blanks and rinseate blanks. 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. 

Sampling Location (Well ID) Spike Level PFOA, ng/mL

137S and 138L FMS 1.00

141R FMS 5.00

134S FMS 10.0

130L FMS 50.0

133L FMS 200

Trip Blank

Low 1.00

Mid 10.0

Mid-High 50.0

High 200

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Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

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Table 10. DAL GW 130R 120329

PFOA

3M LIMS ID Description

Concentration 

(ng/mL)

GLP10-01-01-29-001 DAL-GW-130R-0-120329 796

GLP10-01-01-29-002 DAL-GW-130R-DB-120329 781

Average Concentration (ng/mL) ± %RPD 789 ng/mL ± 1.9%

Samples diluted 1:100

Table 11. DAL GW 130S 120329

PFOA

3M LIMS ID Description

Concentration 

(ng/mL)

GLP10-01-01-29-003 DAL-GW-130S-0-120329 161

GLP10-01-01-29-004 DAL-GW-130S-DB-120329 162

Average Concentration (ng/mL) ± %RPD 162 ng/mL ± 0.62%

Samples diluted 1:10

Table 12. DAL GW 130L 120329

PFOA

3M LIMS ID Description

Concentration 

(ng/mL) %Recovery

GLP10-01-01-29-005 DAL-GW-130L-0-120329 62.1 NA

GLP10-01-01-29-006 DAL-GW-130L-DB-120329 61.4 NA

GLP10-01-01-29-007 DAL-GW-130L-FMS-120329 102 80.5

Average Concentration (ng/mL) ± %RPD 61.8 ng/mL ± 1.1%

NA = Not Applicable

Samples diluted 1:10

Table 13. DAL GW 131R 120328

PFOA

3M LIMS ID Description

Concentration 

(ng/mL)

GLP10-01-01-29-008 DAL-GW-131R-0-120328 1700

GLP10-01-01-29-009 DAL-GW-131R-DB-120328 1830

Average Concentration (ng/mL) ± %RPD 1770 ng/mL ± 7.4%

Samples diluted 1:100

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Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 17 of 68
Table 14. DAL GW 131S 120328

PFOA

3M LIMS ID Description

Concentration 

(ng/mL)

GLP10-01-01-29-010 DAL-GW-131S-0-120328 24.0

GLP10-01-01-29-011 DAL-GW-131S-DB-120328 23.7

Average Concentration (ng/mL) ± %RPD 23.9 ng/mL ± 1.3%

Table 15. DAL GW 131L 120328

PFOA

3M LIMS ID Description

Concentration 

(ng/mL)

GLP10-01-01-29-012 DAL-GW-131L-0-120328 87.0

GLP10-01-01-29-013 DAL-GW-131L-DB-120328 88.2

Average Concentration (ng/mL) ± %RPD 87.6 ng/mL ± 1.4%

Samples diluted 1:10

Table 16. DAL GW 133R 120328

PFOA

3M LIMS ID Description

Concentration 

(ng/mL)

GLP10-01-01-29-014 DAL-GW-133R-0-120328 58.6

GLP10-01-01-29-015 DAL-GW-133R-DB-120328 57.3

Average Concentration (ng/mL) ± %RPD 58.0 ng/mL ± 2.2%

Samples diluted 1:10

Table 17. DAL GW 133S 120328

PFOA

3M LIMS ID Description

Concentration 

(ng/mL)

GLP10-01-01-29-016 DAL-GW-133S-0-120328 272

GLP10-01-01-29-017 DAL-GW-133S-DB-120328 273

Average Concentration (ng/mL) ± %RPD 273 ng/mL ± 0.37%

Samples diluted 1:10

GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 18 of 68
Table 18. DAL GW 133L 120328

PFOA

3M LIMS ID Description

Concentration 

(ng/mL) %Recovery

GLP10-01-01-29-018 DAL-GW-133L-0-120328 182 NA

GLP10-01-01-29-019 DAL-GW-133L-DB-120328 187 NA

GLP10-01-01-29-020 DAL-GW-133L-FMS-120328 372 93.8

Average Concentration (ng/mL) ± %RPD 185 ng/mL ± 2.7%

NA = Not Applicable

Sample and sample duplicate diluted 1:10. FMS diluted 1:100.

Table 19. DAL GW 134R 120328

PFOA

3M LIMS ID Description

Concentration 

(ng/mL)

GLP10-01-01-29-021 DAL-GW-134R-0-120328 1940

GLP10-01-01-29-022 DAL-GW-134R-DB-120328 1920

Average Concentration (ng/mL) ± %RPD 1930 ng/mL ± 1.0%

Samples diluted 1:100

Table 20. DAL GW 134S 120327

PFOA

3M LIMS ID Description

Concentration 

(ng/mL) %Recovery

GLP10-01-01-29-023 DAL-GW-134S-0-120327 14.5 NA

GLP10-01-01-29-024 DAL-GW-134S-DB-120327 13.8 NA

GLP10-01-01-29-025 DAL-GW-134S-FMS-120327 22.0 78.5

Average Concentration (ng/mL) ± %RPD 14.2 ng/mL ± 4.9%

NA = Not Applicable

Table 21. DALGW 134L 120327

PFOA

3M LIMS ID Description

Concentration 

(ng/mL)

GLP10-01-01-29-026 DAL-GW-134L-0-120327 501

GLP10-01-01-29-027 DAL-GW-134L-DB-120327 497

Average Concentration (ng/mL) ± %RPD 499 ng/mL ± 0.80%

Samples diluted 1:100

GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 19 of 68
Table 22. DAL GW 135R 120329

PFOA

3M LIMS ID Description

Concentration 

(ng/mL)

GLP10-01-01-29-028 DAL-GW-135R-0-120329 3450

GLP10-01-01-29-029 DAL-GW-135R-DB-120329 3350

Average Concentration (ng/mL) ± %RPD 3400 ng/mL ± 2.9%

Samples diluted 1:100

Table 23. DAL GW 135S 120329

PFOA

3M LIMS ID Description

Concentration 

(ng/mL)

GLP10-01-01-29-030 DAL-GW-135S-0-120329 56.8

GLP10-01-01-29-031 DAL-GW-135S-DB-120329 57.7

Average Concentration (ng/mL) ± %RPD 57.3 ng/mL ± 1.6%

Table 24. DAL GW 135L 120329

PFOA

3M LIMS ID Description

Concentration 

(ng/mL)

GLP10-01-01-29-032 DAL-GW-135L-0-120329 316

GLP10-01-01-29-033 DAL-GW-135L-DB-120329 294

Average Concentration (ng/mL) ± %RPD 305 ng/mL ± 7.2%

Samples diluted 1:10

Table 25. DAL GW 136S 120328

PFOA

3M LIMS ID Description

Concentration 

(ng/mL)

GLP10-01-01-29-036 DAL-GW-136S-0-120328 88.7

GLP10-01-01-29-037 DAL-GW-136S-DB-120328 83.5

Average Concentration (ng/mL) ± %RPD 86.1 ng/mL ± 6.0%

Samples diluted 1:10

GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 20 of 68
Table 26. DAL GW 136L 120328

PFOA

3M LIMS ID Description

Concentration 

(ng/mL)

GLP10-01-01-29-038 DAL-GW-136L-0-120328 79.7

GLP10-01-01-29-039 DAL-GW-136L-DB-120328 78.7

Average Concentration (ng/mL) ± %RPD 79.2 ng/mL ± 1.3%

Samples diluted 1:10

Table 27. DAL GW 137S 120328

PFOA

3M LIMS ID Description

Concentration 

(ng/mL) %Recovery

GLP10-01-01-29-042 DAL-GW-137S-0-120328 0.317 NA

GLP10-01-01-29-043 DAL-GW-137S-DB-120328 0.308 NA

GLP10-01-01-29-044 DAL-GW-137S-FMS-120328 1.20 88.8

Average Concentration (ng/mL) ± %RPD 0.313 ng/mL ± 2.9%

NA = Not Applicable

Table 28. DAL GW 137L 120328

PFOA

3M LIMS ID Description

Concentration 

(ng/mL)

GLP10-01-01-29-045 DAL-GW-137L-0-120328 0.326

GLP10-01-01-29-046 DAL-GW-137L-DB-120328 0.329

Average Concentration (ng/mL) ± %RPD 0.328 ng/mL ± 0.92%

Table 29. DAL GW 138S 120329

PFOA

3M LIMS ID Description

Concentration 

(ng/mL)

GLP10-01-01-29-049 DAL-GW-138S-0-120329 182

GLP10-01-01-29-050 DAL-GW-138S-DB-120329 179

Average Concentration (ng/mL) ± %RPD 181 ng/mL ± 1.7%

Samples diluted 1:10

GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 21 of 68
Table 29. DAL GW 138L 120330

PFOA

3M LIMS ID Description

Concentration 

(ng/mL) %Recovery

GLP10-01-01-29-051 DAL-GW-138L-0-120330 0.569 NA

GLP10-01-01-29-052 DAL-GW-138L-DB-120330 0.562 NA

GLP10-01-01-29-053 DAL-GW-138L-FMS-120330 1.47 90.5

Average Concentration (ng/mL) ± %RPD 0.566 ng/mL ± 1.2%

NA = Not Applicable

Table 30. DAL GW 140R 120329

PFOA

3M LIMS ID Description

Concentration 

(ng/mL)

GLP10-01-01-29-058 DAL-GW-140R-0-120329 133

GLP10-01-01-29-059 DAL-GW-140R-DB-120329 132

Average Concentration (ng/mL) ± %RPD 133 ng/mL ± 0.75%

Samples diluted 1:10

Table 31. DAL GW 141R 120403

PFOA

3M LIMS ID Description

Concentration 

(ng/mL) %Recovery

GLP10-01-01-29-060 DAL-GW-141R-0-120403 1.59 NA

GLP10-01-01-29-061 DAL-GW-141R-DB-120403 1.58 NA

GLP10-01-01-29-062 DAL-GW-141R-FMS-120403 5.29 74.1

Average Concentration (ng/mL) ± %RPD 1.59 ng/mL ± 0.63%

NA = Not Applicable

Table 32. DAL GW 142R 120328

PFOA

3M LIMS ID Description

Concentration 

(ng/mL)

GLP10-01-01-29-063 DAL-GW-142R-0-120328 52.3

GLP10-01-01-29-064 DAL-GW-142R-DB-120328 52.4

Average Concentration (ng/mL) ± %RPD 52.4 ng/mL ± 0.19%

Samples diluted 1:10

GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 22 of 68
Table 33. DAL GW 143R 120329

PFOA

3M LIMS ID Description

Concentration 

(ng/mL)

GLP10-01-01-29-065 DAL-GW-143R-0-120329 23.0

GLP10-01-01-29-066 DAL-GW-143R-DB-120329 22.6

Average Concentration (ng/mL) ± %RPD 22.8 ng/mL ± 1.8%

Table 34. DAL GW 144R 120328

PFOA

3M LIMS ID Description

Concentration 

(ng/mL)

GLP10-01-01-29-067 DAL-GW-144R-0-120328 65.6

GLP10-01-01-29-068 DAL-GW-144R-DB-120328 63.5

Average Concentration (ng/mL) ± %RPD 64.6 ng/mL ± 3.3%

Samples diluted 1:10

Table 35. DAL GW 145R 120328

PFOA

3M LIMS ID Description

Concentration 

(ng/mL)

GLP10-01-01-29-069 DAL-GW-145R-0-120328 48.5

GLP10-01-01-29-070 DAL-GW-145R-DB-120328 47.6

Average Concentration (ng/mL) ± %RPD 48.1 ng/mL ± 1.9%

Samples diluted 1:10

Table 36. Trip Blank 1

PFOA

3M LIMS ID Description

Concentration 

(ng/mL) %Recovery

GLP10-01-01-29-073 DAL-GW-TRIP01-0- <0.0240 NA

GLP10-01-01-29-074 DAL-GW-TRIP01-LS- 0.934 93.4

GLP10-01-01-29-075 DAL-GW-TRIP01-MS- 9.55 95.5

GLP10-01-01-29-076 DAL-GW-TRIP01-MHS- 47.5 95.0

GLP10-01-01-29-077 DAL-GW-TRIP01-HS- 189 94.5

NA = Not Applicable

Sample GLP10-01-01-29-076 diluted 1:10

Sample GLP10-01-01-29-077 diluted 1:100

GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 23 of 68
Table 37. Rinseate Blanks

PFOA

3M LIMS ID Description

Concentration 

(ng/mL)

GLP10-01-01-29-071 DAL-GW-130R-RB-120329 <0.0240

GLP10-01-01-29-072 DAL-GW-135R-RB-120329 <0.0240

GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 24 of 68
10 Conclusion

Laboratory control spikes and field matrix spikes were used to determine the analytical method 

accuracy and precision for PFOA. 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 electronic) will be archived according 

to 3M Environmental Laboratory standard operating procedures. 

12 Attachments

Attachment A: Protocol Amendment 29 (General Project Outline)

Attachment B: Representative Chromatograms and Calibration Curves

Attachment C: Analytical Method – ETS-8-044.1 

GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 25 of 68
GLP10-01-01; Interim Report 29 

Analysis of PFOA In Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012 

13 Signatures 

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

y^ M Jry ^o/^ 

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

Gary Hohenstein, 3M Sponsor Representative Date 

Jaisimha Kesari, Study Director 5ate 

Page 26 of 68 
ATTACHMENT A: PROTOCOL AMENDMENT

GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 27 of 68
GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 28 of 68
GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 29 of 68
GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 30 of 68
GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 31 of 68
GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 32 of 68
GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 33 of 68
ATTACHMENT B: REPRESENTATIVE SAMPLE CHROMATOGRAMS AND 

CALIBRATION CURVE(S) 

GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 34 of 68
b120405a.rdb (PFOA): "Quadratic" Regression ("1 / x" weighting): y = -9.27e+003 x^2 + 1.24e+006 x + 1.74e+004 (r = 0.9989)

0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 

Concentration, ng/mL

0.0

5.0e61.0e71.5e72.0e72.5e73.0e73.5e74.0e74.5e75.0e75.5e76.0e76.5e7

Area, counts

Workstation: ETSGINGER Batch Name: b120405a.dab*Data worked up by KJU Page 1 of 1Printing Time: 2:26:16 PMPrinting Date: Tuesday, April 10, 2012

G

Analysis of P

Former Sludge Incorpo
Sample Name: "b120405a018" Sample ID: "11012-10-9" File: "b120405a.wiff"

Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "2.5 ng/mL FC std in Milli Q Water" Annotation: ""

Sample Index: 18 Sample Type: Standard Concentration: 2.40 ng/mL Calculated Conc: 2.62 ng/mL Acq. Date: 4/5/2012 Acq. Time: 10:13:24 PM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.7 minArea: 3211528 countsHeight: 8.32e+005 cpsStart Time: 15.3 minEnd Time: 15.8 min

13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0

Time, min

0.0

5.0e41.0e51.5e52.0e52.5e53.0e53.5e54.0e54.5e55.0e55.5e56.0e56.5e57.0e57.5e58.0e5

Intensity, cps

15.66

16.15

15.52

16.64

Sample Name: "b120405a028" Sample ID: "Solvent Blank" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "Milli Q Water TN12-0125" Annotation: ""

Sample Index: 28 Sample Type: Unknown Concentration: N/A Calculated Conc: < 0 Acq. Date: 4/6/2012 Acq. Time: 1:43:47 AM Modified: No Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 minPeak-Split. Factor: 4 Report Largest Peak: No Min. Peak Height: 0.00 cpsMin. Peak Width: 0.00 secSmoothing Width: 3 pointsRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Base To Base Retention Time: 15.6 minArea: 2180 countsHeight: 9.04e+002 cpsStart Time: 15.6 minEnd Time: 15.7 min

13.5 14.0 14.5 15.0 15.

T

0.0

1.0e42.0e43.0e44.0e45.0e46.0e47.0e48.0e49.0e41.0e51.1e51.2e51.3e51.4e51.5e51.6e51.7e51.8e51.9e52.0e52.1e52.2e52.3e5

Intensity, cps

Sample Name: "b120405a029" Sample ID: "LCS-120405-1" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "0.5ppb LCS" Annotation: ""

Sample Index: 29 Sample Type: QC Concentration: 0.477 ng/mL Calculated Conc: 0.433 ng/mL Acq. Date: 4/6/2012 Acq. Time: 2:04:48 AM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.7 minArea: 553522 countsHeight: 1.52e+005 cpsStart Time: 15.4 minEnd Time: 15.7 min

13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0

Time, min

0.0

1.0e42.0e43.0e44.0e45.0e46.0e47.0e48.0e49.0e41.0e51.1e51.2e51.3e51.4e51.5e51.6e51.7e51.8e51.9e52.0e52.1e52.2e52.3e5

Intensity, cps

16.13

15.66

15.51

Sample Name: "b120405a032" Sample ID: "LCS-120405-4" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "5ppb LCS" Annotation: ""

Sample Index: 32 Sample Type: QC Concentration: 4.77 ng/mL Calculated Conc: 4.53 ng/mL Acq. Date: 4/6/2012 Acq. Time: 3:08:03 AM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.7 minArea: 5455248 countsHeight: 1.38e+006 cpsStart Time: 15.3 minEnd Time: 15.8 min

13.5 14.0 14.5 15.0 15.5 

Tim

0.0

5.0e41.0e51.5e52.0e52.5e53.0e53.5e54.0e54.5e55.0e55.5e56.0e56.5e57.0e57.5e58.0e58.5e59.0e59.5e51.0e61.1e61.1e61.2e61.2e61.3e61.3e61.4e6

Intensity, cps

1

15.51 

*** Buster J2930203 Batch Name: b120405a.dabData printed by STWPrinting Time: 3:09:33 PMPrinting Date: Tuesday, May 01, 2012

Page 1 of 10

G

Analysis of P

Former Sludge Incorpo
Sample Name: "b120405a035" Sample ID: "LCS-120405-7" File: "b120405a.wiff"

Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "30ppb LCS" Annotation: ""

Sample Index: 35 Sample Type: QC Concentration: 28.7 ng/mL Calculated Conc: 25.0 ng/mL Acq. Date: 4/6/2012 Acq. Time: 4:11:14 AM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.7 minArea: 25307984 countsHeight: 5.53e+006 cpsStart Time: 15.3 minEnd Time: 15.9 min

13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0

Time, min

0.0

2.0e54.0e56.0e58.0e51.0e61.2e61.4e61.6e61.8e62.0e62.2e62.4e62.6e62.8e63.0e63.2e63.4e63.6e63.8e64.0e64.2e64.4e64.6e64.8e65.0e65.2e65.4e6

Intensity, cps

15.65

15.51

16.13

Sample Name: "b120405a042" Sample ID: "GLP10-01-01-29-071" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-130R-RB-" Annotation: ""

Sample Index: 42 Sample Type: Unknown Concentration: N/A Calculated Conc: < 0 Acq. Date: 4/6/2012 Acq. Time: 6:38:47 AM Modified: No Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 minPeak-Split. Factor: 4 Report Largest Peak: No Min. Peak Height: 0.00 cpsMin. Peak Width: 0.00 secSmoothing Width: 3 pointsRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Base To Base Retention Time: 15.7 minArea: 3135 countsHeight: 1.22e+003 cpsStart Time: 15.6 minEnd Time: 15.7 min

13.5 14.0 14.5 15.0 15.

T

0.00

5000.00

1.00e41.50e42.00e42.50e43.00e43.50e44.00e44.50e45.00e45.50e46.00e46.50e47.00e47.50e48.00e48.50e49.00e49.50e41.00e5

Intensity, cps

Sample Name: "b120405a057" Sample ID: "GLP10-01-01-29-001" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-130R-0-" Annotation: ""

Sample Index: 57 Sample Type: Unknown Concentration: N/A Calculated Conc: 796. ng/mL Acq. Date: 4/6/2012 Acq. Time: 11:54:54 AM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 9331457 countsHeight: 2.29e+006 cpsStart Time: 15.3 minEnd Time: 15.8 min

13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0

Time, min

0.0

1.0e52.0e53.0e54.0e55.0e56.0e57.0e58.0e59.0e51.0e61.1e61.2e61.3e61.4e61.5e61.6e61.7e61.8e61.9e62.0e62.1e62.2e6

Intensity, cps

15.64

15.50

16.12

Sample Name: "b120405a059" Sample ID: "GLP10-01-01-29-003" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-130S-0-" Annotation: ""

Sample Index: 59 Sample Type: Unknown Concentration: N/A Calculated Conc: 161. ng/mL Acq. Date: 4/6/2012 Acq. Time: 12:37:05 PM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 17650075 countsHeight: 4.11e+006 cpsStart Time: 15.3 minEnd Time: 15.9 min

13.5 14.0 14.5 15.0 15.5 

Tim

0.0

2.0e54.0e56.0e58.0e51.0e61.2e61.4e61.6e61.8e62.0e62.2e62.4e62.6e62.8e63.0e63.2e63.4e63.6e63.8e64.0e6

Intensity, cps

15

15.49

*** Buster J2930203 Batch Name: b120405a.dabData printed by STWPrinting Time: 3:09:33 PMPrinting Date: Tuesday, May 01, 2012

Page 2 of 10

G

Analysis of P

Former Sludge Incorpo
Sample Name: "b120405a064" Sample ID: "GLP10-01-01-29-005" File: "b120405a.wiff"

Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-130L-0-" Annotation: ""

Sample Index: 64 Sample Type: Unknown Concentration: N/A Calculated Conc: 62.1 ng/mL Acq. Date: 4/6/2012 Acq. Time: 2:22:30 PM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 7383534 countsHeight: 1.88e+006 cpsStart Time: 15.3 minEnd Time: 15.8 min

13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0

Time, min

0.0

1.0e52.0e53.0e54.0e55.0e56.0e57.0e58.0e59.0e51.0e61.1e61.2e61.3e61.4e61.5e61.6e61.7e61.8e6

Intensity, cps

15.63

15.48

Sample Name: "b120405a066" Sample ID: "GLP10-01-01-29-007" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-130L-FMS-" Annotation: ""

Sample Index: 66 Sample Type: Unknown Concentration: N/A Calculated Conc: 102. ng/mL Acq. Date: 4/6/2012 Acq. Time: 3:04:43 PM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 11735967 countsHeight: 3.10e+006 cpsStart Time: 15.3 minEnd Time: 15.8 min

13.5 14.0 14.5 15.0 15.5 

Tim

0.0

2.0e54.0e56.0e58.0e51.0e61.2e61.4e61.6e61.8e62.0e62.2e62.4e62.6e62.8e63.0e6

Intensity, cps

15

15.48

Sample Name: "b120405a067" Sample ID: "GLP10-01-01-29-008" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-131R-0-" Annotation: ""

Sample Index: 67 Sample Type: Unknown Concentration: N/A Calculated Conc: 1700. ng/mL Acq. Date: 4/6/2012 Acq. Time: 3:25:49 PM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 18507045 countsHeight: 4.44e+006 cpsStart Time: 15.3 minEnd Time: 15.8 min

13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0

Time, min

0.0

2.0e54.0e56.0e58.0e51.0e61.2e61.4e61.6e61.8e62.0e62.2e62.4e62.6e62.8e63.0e63.2e63.4e63.6e63.8e64.0e64.2e64.4e6

Intensity, cps

15.62

15.48

Sample Name: "b120405a069" Sample ID: "GLP10-01-01-29-010" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-131S-0-" Annotation: ""

Sample Index: 69 Sample Type: Unknown Concentration: N/A Calculated Conc: 24.0 ng/mL Acq. Date: 4/6/2012 Acq. Time: 4:07:53 PM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 24518074 countsHeight: 5.33e+006 cpsStart Time: 15.2 minEnd Time: 15.9 min

13.5 14.0 14.5 15.0 15.5 

Tim

0.0

2.0e54.0e56.0e58.0e51.0e61.2e61.4e61.6e61.8e62.0e62.2e62.4e62.6e62.8e63.0e63.2e63.4e63.6e63.8e64.0e64.2e64.4e64.6e64.8e65.0e65.2e6

Intensity, cps

15

15.48

*** Buster J2930203 Batch Name: b120405a.dabData printed by STWPrinting Time: 3:09:33 PMPrinting Date: Tuesday, May 01, 2012

Page 3 of 10

G

Analysis of P

Former Sludge Incorpo
Sample Name: "b120405a071" Sample ID: "GLP10-01-01-29-012" File: "b120405a.wiff"

Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-131L-0-" Annotation: ""

Sample Index: 71 Sample Type: Unknown Concentration: N/A Calculated Conc: 87.0 ng/mL Acq. Date: 4/6/2012 Acq. Time: 4:50:02 PM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 10133261 countsHeight: 2.43e+006 cpsStart Time: 15.2 minEnd Time: 15.9 min

13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0

Time, min

0.0

1.0e52.0e53.0e54.0e55.0e56.0e57.0e58.0e59.0e51.0e61.1e61.2e61.3e61.4e61.5e61.6e61.7e61.8e61.9e62.0e62.1e62.2e62.3e62.4e6

Intensity, cps

15.62

15.48

Sample Name: "b120405a076" Sample ID: "GLP10-01-01-29-014" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-133R-0-" Annotation: ""

Sample Index: 76 Sample Type: Unknown Concentration: N/A Calculated Conc: 58.6 ng/mL Acq. Date: 4/6/2012 Acq. Time: 6:35:20 PM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 6981621 countsHeight: 1.78e+006 cpsStart Time: 15.3 minEnd Time: 15.8 min

13.5 14.0 14.5 15.0 15.5 

Tim

0.0

1.0e52.0e53.0e54.0e55.0e56.0e57.0e58.0e59.0e51.0e61.1e61.2e61.3e61.4e61.5e61.6e61.7e6

Intensity, cps

15

15.47

Sample Name: "b120405a078" Sample ID: "GLP10-01-01-29-016" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-133S-0-" Annotation: ""

Sample Index: 78 Sample Type: Unknown Concentration: N/A Calculated Conc: 272. ng/mL Acq. Date: 4/6/2012 Acq. Time: 7:17:25 PM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 26980388 countsHeight: 5.65e+006 cpsStart Time: 15.2 minEnd Time: 15.9 min

13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0

Time, min

0.0

5.0e51.0e61.5e62.0e62.5e63.0e63.5e64.0e64.5e65.0e65.5e6

Intensity, cps

15.62

15.47

16.08

Sample Name: "b120405a080" Sample ID: "GLP10-01-01-29-018" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-133L-0-" Annotation: ""

Sample Index: 80 Sample Type: Unknown Concentration: N/A Calculated Conc: 182. ng/mL Acq. Date: 4/6/2012 Acq. Time: 7:59:29 PM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 19567286 countsHeight: 4.39e+006 cpsStart Time: 15.2 minEnd Time: 15.9 min

13.5 14.0 14.5 15.0 15.5 

Tim

0.0

2.0e54.0e56.0e58.0e51.0e61.2e61.4e61.6e61.8e62.0e62.2e62.4e62.6e62.8e63.0e63.2e63.4e63.6e63.8e64.0e64.2e6

Intensity, cps

15

15.47

*** Buster J2930203 Batch Name: b120405a.dabData printed by STWPrinting Time: 3:09:33 PMPrinting Date: Tuesday, May 01, 2012

Page 4 of 10

G

Analysis of P

Former Sludge Incorpo
Sample Name: "b120405a082" Sample ID: "GLP10-01-01-29-020" File: "b120405a.wiff"

Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-133L-FMS-" Annotation: ""

Sample Index: 82 Sample Type: Unknown Concentration: N/A Calculated Conc: 372. ng/mL Acq. Date: 4/6/2012 Acq. Time: 8:41:40 PM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 4518300 countsHeight: 1.24e+006 cpsStart Time: 15.3 minEnd Time: 15.8 min

13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0

Time, min

0.00

5.00e41.00e51.50e52.00e52.50e53.00e53.50e54.00e54.50e55.00e55.50e56.00e56.50e57.00e57.50e58.00e58.50e59.00e59.50e51.00e61.05e61.10e61.15e61.20e6

Intensity, cps

15.62

Sample Name: "b120405a083" Sample ID: "GLP10-01-01-29-021" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-134R-0-" Annotation: ""

Sample Index: 83 Sample Type: Unknown Concentration: N/A Calculated Conc: 1940. ng/mL Acq. Date: 4/6/2012 Acq. Time: 9:02:44 PM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 20672304 countsHeight: 4.54e+006 cpsStart Time: 15.3 minEnd Time: 15.9 min

13.5 14.0 14.5 15.0 15.5 

Tim

0.0

2.0e54.0e56.0e58.0e51.0e61.2e61.4e61.6e61.8e62.0e62.2e62.4e62.6e62.8e63.0e63.2e63.4e63.6e63.8e64.0e64.2e64.4e6

Intensity, cps

15

15.48

Sample Name: "b120405a088" Sample ID: "GLP10-01-01-29-023" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-134S-0-" Annotation: ""

Sample Index: 88 Sample Type: Unknown Concentration: N/A Calculated Conc: 14.5 ng/mL Acq. Date: 4/6/2012 Acq. Time: 10:48:03 PM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 16066777 countsHeight: 3.68e+006 cpsStart Time: 15.3 minEnd Time: 15.9 min

13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0

Time, min

0.0

2.0e54.0e56.0e58.0e51.0e61.2e61.4e61.6e61.8e62.0e62.2e62.4e62.6e62.8e63.0e63.2e63.4e63.6e6

Intensity, cps

15.61

15.47

Sample Name: "b120405a090" Sample ID: "GLP10-01-01-29-025" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-134S-FMS-" Annotation: ""

Sample Index: 90 Sample Type: Unknown Concentration: N/A Calculated Conc: 22.0 ng/mL Acq. Date: 4/6/2012 Acq. Time: 11:30:14 PM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 22871769 countsHeight: 5.30e+006 cpsStart Time: 15.2 minEnd Time: 15.9 min

13.5 14.0 14.5 15.0 15.5 

Tim

0.0

2.0e54.0e56.0e58.0e51.0e61.2e61.4e61.6e61.8e62.0e62.2e62.4e62.6e62.8e63.0e63.2e63.4e63.6e63.8e64.0e64.2e64.4e64.6e64.8e65.0e65.2e6

Intensity, cps

15

15.47

*** Buster J2930203 Batch Name: b120405a.dabData printed by STWPrinting Time: 3:09:34 PMPrinting Date: Tuesday, May 01, 2012

Page 5 of 10

G

Analysis of P

Former Sludge Incorpo
Sample Name: "b120405a091" Sample ID: "GLP10-01-01-29-026" File: "b120405a.wiff"

Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-134L-0-" Annotation: ""

Sample Index: 91 Sample Type: Unknown Concentration: N/A Calculated Conc: 501. ng/mL Acq. Date: 4/6/2012 Acq. Time: 11:51:17 PM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 6009305 countsHeight: 1.45e+006 cpsStart Time: 15.3 minEnd Time: 15.8 min

13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0

Time, min

0.0

1.0e52.0e53.0e54.0e55.0e56.0e57.0e58.0e59.0e51.0e61.1e61.2e61.3e61.4e6

Intensity, cps

15.61

15.47

Sample Name: "b120405a093" Sample ID: "GLP10-01-01-29-028" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-135R-0-" Annotation: ""

Sample Index: 93 Sample Type: Unknown Concentration: N/A Calculated Conc: 3450. ng/mL Acq. Date: 4/7/2012 Acq. Time: 12:33:31 AM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 31880878 countsHeight: 6.54e+006 cpsStart Time: 15.2 minEnd Time: 15.9 min

13.5 14.0 14.5 15.0 15.5 

Tim

0.0

5.0e51.0e61.5e62.0e62.5e63.0e63.5e64.0e64.5e65.0e65.5e66.0e66.5e6

Intensity, cps

15

15.47

Sample Name: "b120405b234" Sample ID: "GLP10-01-01-29-030" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-135S-0-" Annotation: ""

Sample Index: 247 Sample Type: Unknown Concentration: N/A Calculated Conc: 56.8 ng/mL Acq. Date: 4/10/2012 Acq. Time: 10:48:04 AM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 12938723 countsHeight: 3.12e+006 cpsStart Time: 15.2 minEnd Time: 15.8 min

13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0

Time, min

0.0

2.0e54.0e56.0e58.0e51.0e61.2e61.4e61.6e61.8e62.0e62.2e62.4e62.6e62.8e63.0e6

Intensity, cps

15.56

15.41

Sample Name: "b120405a100" Sample ID: "GLP10-01-01-29-032" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-135L-0-" Annotation: ""

Sample Index: 100 Sample Type: Unknown Concentration: N/A Calculated Conc: 316. ng/mL Acq. Date: 4/7/2012 Acq. Time: 3:01:15 AM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 30068502 countsHeight: 6.04e+006 cpsStart Time: 15.2 minEnd Time: 15.9 min

13.5 14.0 14.5 15.0 15.5 

Tim

0.0

5.0e51.0e61.5e62.0e62.5e63.0e63.5e64.0e64.5e65.0e65.5e66.0e6

Intensity, cps

15

15.47

*** Buster J2930203 Batch Name: b120405a.dabData printed by STWPrinting Time: 3:09:34 PMPrinting Date: Tuesday, May 01, 2012

Page 6 of 10

G

Analysis of P

Former Sludge Incorpo
Sample Name: "b120405a102" Sample ID: "GLP10-01-01-29-036" File: "b120405a.wiff"

Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-136S-0-" Annotation: ""

Sample Index: 102 Sample Type: Unknown Concentration: N/A Calculated Conc: 88.7 ng/mL Acq. Date: 4/7/2012 Acq. Time: 3:43:26 AM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 10317687 countsHeight: 2.47e+006 cpsStart Time: 15.2 minEnd Time: 15.8 min

13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0

Time, min

0.0

1.0e52.0e53.0e54.0e55.0e56.0e57.0e58.0e59.0e51.0e61.1e61.2e61.3e61.4e61.5e61.6e61.7e61.8e61.9e62.0e62.1e62.2e62.3e62.4e6

Intensity, cps

15.61

15.46

Sample Name: "b120405a104" Sample ID: "GLP10-01-01-29-038" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-136L-0-" Annotation: ""

Sample Index: 104 Sample Type: Unknown Concentration: N/A Calculated Conc: 79.7 ng/mL Acq. Date: 4/7/2012 Acq. Time: 4:25:37 AM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 9338180 countsHeight: 2.28e+006 cpsStart Time: 15.2 minEnd Time: 15.8 min

13.5 14.0 14.5 15.0 15.5 

Tim

0.0

1.0e52.0e53.0e54.0e55.0e56.0e57.0e58.0e59.0e51.0e61.1e61.2e61.3e61.4e61.5e61.6e61.7e61.8e61.9e62.0e62.1e62.2e6

Intensity, cps

15

15.47

Sample Name: "b120405a106" Sample ID: "GLP10-01-01-29-042" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-137S-0-" Annotation: ""

Sample Index: 106 Sample Type: Unknown Concentration: N/A Calculated Conc: 0.317 ng/mL Acq. Date: 4/7/2012 Acq. Time: 5:07:40 AM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 410217 countsHeight: 1.01e+005 cpsStart Time: 15.4 minEnd Time: 15.7 min

13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0

Time, min

0.0

1.0e42.0e43.0e44.0e45.0e46.0e47.0e48.0e49.0e41.0e51.1e51.2e51.3e51.4e51.5e5

Intensity, cps

16.08

Sample Name: "b120405a112" Sample ID: "GLP10-01-01-29-045" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-137L-0-" Annotation: ""

Sample Index: 112 Sample Type: Unknown Concentration: N/A Calculated Conc: 0.326 ng/mL Acq. Date: 4/7/2012 Acq. Time: 7:14:30 AM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 421611 countsHeight: 1.10e+005 cpsStart Time: 15.4 minEnd Time: 15.7 min

13.5 14.0 14.5 15.0 15.5 

Tim

0.0

1.0e42.0e43.0e44.0e45.0e46.0e47.0e48.0e49.0e41.0e51.1e51.2e51.3e51.4e51.5e51.6e51.7e5

Intensity, cps

15

15.47

*** Buster J2930203 Batch Name: b120405a.dabData printed by STWPrinting Time: 3:09:34 PMPrinting Date: Tuesday, May 01, 2012

Page 7 of 10

G

Analysis of P

Former Sludge Incorpo
Sample Name: "b120405a114" Sample ID: "GLP10-01-01-29-049" File: "b120405a.wiff"

Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-138S-0-" Annotation: ""

Sample Index: 114 Sample Type: Unknown Concentration: N/A Calculated Conc: 182. ng/mL Acq. Date: 4/7/2012 Acq. Time: 7:56:43 AM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 19542890 countsHeight: 4.42e+006 cpsStart Time: 15.2 minEnd Time: 15.9 min

13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0

Time, min

0.0

2.0e54.0e56.0e58.0e51.0e61.2e61.4e61.6e61.8e62.0e62.2e62.4e62.6e62.8e63.0e63.2e63.4e63.6e63.8e64.0e64.2e64.4e6

Intensity, cps

15.61

15.47

16.08

15.31

Sample Name: "b120405a116" Sample ID: "GLP10-01-01-29-051" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-138L-0-" Annotation: ""

Sample Index: 116 Sample Type: Unknown Concentration: N/A Calculated Conc: 0.569 ng/mL Acq. Date: 4/7/2012 Acq. Time: 8:38:57 AM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 722026 countsHeight: 1.85e+005 cpsStart Time: 15.4 minEnd Time: 15.7 min

13.5 14.0 14.5 15.0 15.5 

Tim

0.0

1.0e42.0e43.0e44.0e45.0e46.0e47.0e48.0e49.0e41.0e51.1e51.2e51.3e51.4e51.5e51.6e51.7e51.8e5

Intensity, cps

Sample Name: "b120405a118" Sample ID: "GLP10-01-01-29-053" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-138L-FMS-" Annotation: ""

Sample Index: 118 Sample Type: Unknown Concentration: N/A Calculated Conc: 1.47 ng/mL Acq. Date: 4/7/2012 Acq. Time: 9:21:05 AM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 1829764 countsHeight: 5.09e+005 cpsStart Time: 15.4 minEnd Time: 15.7 min

13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0

Time, min

0.0

2.0e44.0e46.0e48.0e41.0e51.2e51.4e51.6e51.8e52.0e52.2e52.4e52.6e52.8e53.0e53.2e53.4e53.6e53.8e54.0e54.2e54.4e54.6e54.8e55.0e5

Intensity, cps

15.62

16.08

15.48

Sample Name: "b120405a119" Sample ID: "GLP10-01-01-29-058" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-140R-0-" Annotation: ""

Sample Index: 119 Sample Type: Unknown Concentration: N/A Calculated Conc: 133. ng/mL Acq. Date: 4/7/2012 Acq. Time: 9:42:06 AM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 14964436 countsHeight: 3.48e+006 cpsStart Time: 15.2 minEnd Time: 15.9 min

13.5 14.0 14.5 15.0 15.5 

Tim

0.0

2.0e54.0e56.0e58.0e51.0e61.2e61.4e61.6e61.8e62.0e62.2e62.4e62.6e62.8e63.0e63.2e63.4e6

Intensity, cps

15

15.48

*** Buster J2930203 Batch Name: b120405a.dabData printed by STWPrinting Time: 3:09:34 PMPrinting Date: Tuesday, May 01, 2012

Page 8 of 10

G

Analysis of P

Former Sludge Incorpo
Sample Name: "b120405a124" Sample ID: "GLP10-01-01-29-060" File: "b120405a.wiff"

Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-141R-0-" Annotation: ""

Sample Index: 124 Sample Type: Unknown Concentration: N/A Calculated Conc: 1.59 ng/mL Acq. Date: 4/7/2012 Acq. Time: 11:27:35 AM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 1974811 countsHeight: 4.82e+005 cpsStart Time: 15.3 minEnd Time: 15.7 min

13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0

Time, min

0.0

2.0e44.0e46.0e48.0e41.0e51.2e51.4e51.6e51.8e52.0e52.2e52.4e52.6e52.8e53.0e53.2e53.4e53.6e53.8e54.0e54.2e54.4e54.6e54.8e5

Intensity, cps

15.62

Sample Name: "b120405a127" Sample ID: "GLP10-01-01-29-063" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-142R-0-" Annotation: ""

Sample Index: 127 Sample Type: Unknown Concentration: N/A Calculated Conc: 52.3 ng/mL Acq. Date: 4/7/2012 Acq. Time: 12:30:51 PM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 6269133 countsHeight: 1.58e+006 cpsStart Time: 15.2 minEnd Time: 15.8 min

13.5 14.0 14.5 15.0 15.5 

Tim

0.0

1.0e52.0e53.0e54.0e55.0e56.0e57.0e58.0e59.0e51.0e61.1e61.2e61.3e61.4e61.5e6

Intensity, cps

15

15.46

Sample Name: "b120405a129" Sample ID: "GLP10-01-01-29-065" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-143R-0-" Annotation: ""

Sample Index: 129 Sample Type: Unknown Concentration: N/A Calculated Conc: 23.0 ng/mL Acq. Date: 4/7/2012 Acq. Time: 1:13:02 PM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 23727851 countsHeight: 5.09e+006 cpsStart Time: 15.2 minEnd Time: 15.9 min

13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0

Time, min

0.0

2.0e54.0e56.0e58.0e51.0e61.2e61.4e61.6e61.8e62.0e62.2e62.4e62.6e62.8e63.0e63.2e63.4e63.6e63.8e64.0e64.2e64.4e64.6e64.8e65.0e6

Intensity, cps

15.61

15.46

16.08

Sample Name: "b120405a131" Sample ID: "GLP10-01-01-29-067" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-144R-0-" Annotation: ""

Sample Index: 131 Sample Type: Unknown Concentration: N/A Calculated Conc: 65.6 ng/mL Acq. Date: 4/7/2012 Acq. Time: 1:55:08 PM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 7775035 countsHeight: 1.88e+006 cpsStart Time: 15.2 minEnd Time: 15.8 min

13.5 14.0 14.5 15.0 15.5 

Tim

0.0

1.0e52.0e53.0e54.0e55.0e56.0e57.0e58.0e59.0e51.0e61.1e61.2e61.3e61.4e61.5e61.6e61.7e61.8e6

Intensity, cps

15

15.46

*** Buster J2930203 Batch Name: b120405a.dabData printed by STWPrinting Time: 3:09:34 PMPrinting Date: Tuesday, May 01, 2012

Page 9 of 10

G

Analysis of P

Former Sludge Incorpo
Sample Name: "b120405a136" Sample ID: "GLP10-01-01-29-069" File: "b120405a.wiff"

Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-145R-0-" Annotation: ""

Sample Index: 136 Sample Type: Unknown Concentration: N/A Calculated Conc: 48.5 ng/mL Acq. Date: 4/7/2012 Acq. Time: 3:40:32 PM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 5827281 countsHeight: 1.42e+006 cpsStart Time: 15.3 minEnd Time: 15.8 min

13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0

Time, min

0.0

1.0e52.0e53.0e54.0e55.0e56.0e57.0e58.0e59.0e51.0e61.1e61.2e61.3e61.4e6

Intensity, cps

15.63

15.48

Sample Name: "b120405a045" Sample ID: "GLP10-01-01-29-073" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-TRIP01-0-" Annotation: ""

Sample Index: 45 Sample Type: Unknown Concentration: N/A Calculated Conc: < 0 Acq. Date: 4/6/2012 Acq. Time: 7:42:01 AM Modified: No Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 minPeak-Split. Factor: 4 Report Largest Peak: No Min. Peak Height: 0.00 cpsMin. Peak Width: 0.00 secSmoothing Width: 3 pointsRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Base To Base Retention Time: 15.6 minArea: 4848 countsHeight: 1.38e+003 cpsStart Time: 15.6 minEnd Time: 15.7 min

13.5 14.0 14.5 15.0 15.

T

0.0

5000.0

1.0e41.5e42.0e42.5e43.0e43.5e44.0e44.5e45.0e45.5e46.0e46.5e47.0e47.5e4

Intensity, cps

Sample Name: "b120405a047" Sample ID: "GLP10-01-01-29-075" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-TRIP01-MS-" Annotation: ""

Sample Index: 47 Sample Type: Unknown Concentration: N/A Calculated Conc: 9.55 ng/mL Acq. Date: 4/6/2012 Acq. Time: 8:24:07 AM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 11043237 countsHeight: 3.23e+006 cpsStart Time: 15.4 minEnd Time: 15.9 min

13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0

Time, min

0.0

2.0e54.0e56.0e58.0e51.0e61.2e61.4e61.6e61.8e62.0e62.2e62.4e62.6e62.8e63.0e63.2e6

Intensity, cps

15.64

15.49 16.11

Sample Name: "b120405a049" Sample ID: "GLP10-01-01-29-077" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-TRIP01-HS-" Annotation: ""

Sample Index: 49 Sample Type: Unknown Concentration: N/A Calculated Conc: 189. ng/mL Acq. Date: 4/6/2012 Acq. Time: 9:06:16 AM Modified: Yes RT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: No Int. Type: Manual Retention Time: 15.6 minArea: 2334251 countsHeight: 7.33e+005 cpsStart Time: 15.4 minEnd Time: 15.8 min

13.5 14.0 14.5 15.0 15.5 

Tim

0.0

5.0e41.0e51.5e52.0e52.5e53.0e53.5e54.0e54.5e55.0e55.5e56.0e56.5e57.0e5

Intensity, cps

15

*** Buster J2930203 Batch Name: b120405a.dabData printed by STWPrinting Time: 3:09:34 PMPrinting Date: Tuesday, May 01, 2012

Page 10 of 10

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Analysis of P

Former Sludge Incorpo
ATTACHMENT C: ANALYTICAL METHOD(S) 

GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 46 of 68
Page 47 of 68
ETS-8-044.1 Page 2 of 22

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

Direct Injection Analysis

1 Scope and Application

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

water matrices using high-performance liquid chromatography tandem mass spectrometry 

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

perfluoroalkyl sulfonamides and perfluorinated alkyl 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 

“Determination of Perfluorinated 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 calibration1

. 

Table 1. Representative Target Analytes

Acronym Analyte

Chemical Abstract Services 

Registry Number (CASRN)

PFBA (C4 Acid) Perfluorobutanoic acid 375-22-4

PFPeA (C5 Acid) Perfluoropentanoic acid 2706-90-3

PFHxA (C6 Acid) Perfluorohexanoic acid 307-24-4

PFHpA (C7 Acid) Perfluoroheptanoic acid 375-85-9

PFOA (C8 Acid) Perfluorooctanoic acid 335-67-1

PFNA (C9 Acid) Perfluorononanoic acid 375-95-1

PFDA (C10 Acid) Perfluorodecanoic acid 335-76-2

PFUnA (C11 Acid) Perfluoroundecanoic acid 2058-94-8

PFDoA (C12 Acid) Perfluorododecanoic acid 307-55-1

PFTrDA (C13 Acid) Perfluorotridecanoic acid 72629-94-8

PFBS (C4 Sulfonate) Perfluorobutanesulfonic acid 375-73-5

PFHS (C6 Sulfonate) Perfluorohexanesulfonic acid 355-46-4

PFOS (C8 Sulfonate) Perfluorooctanesulfonic acid 1763-23-1

FBSA (C4 Sulfonamide Perfluorobutanesulfonamide 30334-69-1

FOSA (C8 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 performance-based method and may be generally applied to the 

determination of perfluorinated compounds in water matrices when analysis batch quality 

control (QC) criteria are met2

. Each set of samples are prepared in an analysis batch with 

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

the same instrument 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 performance or to meet data quality 

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

 

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

and C8 perfluoroalkane sulfonamide in laboratory control samples under 3M method validation E11-0667.

2 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).

GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 48 of 68
ETS-8-044.1 Page 3 of 22

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

Direct Injection Analysis

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 internal standard calibration in laboratory reagent water. All 

perfluorinated 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 forms. Alternatively, quantitation may be performed by external 

standard calibration. 

This is a performance-based method. Method uncertainty for each target analyte is 

determined 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 determined 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 groundwater:MeOH.

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 

predetermined 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.

GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 49 of 68
ETS-8-044.1 Page 4 of 22

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

Direct Injection Analysis

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 

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

sample is also referred 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 

samples. 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 

determine 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 internal 

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 surrogate 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 determine 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 determined in a separate aliquot and the measured values in the LMS corrected for 

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

GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 50 of 68
ETS-8-044.1 Page 5 of 22

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

Direct Injection Analysis

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 determine 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. Surrogate 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 performance 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 

determined; 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.

GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 51 of 68
ETS-8-044.1 Page 6 of 22

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

Direct Injection Analysis

The laboratory is responsible for maintaining a safe work 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 potential 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 0.0001g 

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

6.2 Supplies and Materials

Sample collection bottles—HDPE (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 

performance 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

GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 52 of 68
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

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 Perfluorinated Acid)

PFPeA, Nonafluoropentanoic Acid (C5 Perfluorinated Acid)

PFHxA, Perfluorohexanoic Acid (C6 Perfluorinated Acid)

PFHpA, Tridecafluoroheptanoic Acid, (C7 Perfluorinated Acid)

PFOA, Ammonium perfluorooctanoate, (C8 Perfluorinated Acid)

PFNA, Heptadecafluorononanoic Acid, (C9 Perfluorinated Acid)

PFDA, Nonadecafluorodecanoic Acid (C10 Perfluorinated Acid)

PFUnA, Perfluoroundecanoic Acid, (C11 Perfluorinated Acid)

PFDoA, Perfluorododecanoic Acid, (C12 Perfluorinated Acid)

PFTrDA, Perfluorotridecanoic Acid, (C13 Perfluorinated Acid)

FBSA, Perfluorobutanesulfonamide

FOSA, Perfluorooctanesulfonylamide 

PFBS, Potassium Perfluorobutanesulfonate

PFHS, Perfluorohexanesulfonate

PFOS, Potassium perfluorooctanesulfonate

PFOA [1,2, 3, 4-

13C], 13C4-isotopically labeled perfluorooctanoic acid (SRS)

PFOS [1,2, 3, 4-

13C], 13C4-isotopically labeled Perfluorooctanesulfonate (SRS)

PFUnA [1,2-

13C], 13C2-isotopically labeled Perfluoroundecanoic acid (SRS)

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

13C4]PFBA, [1,2 - 13C2]PFHxA, [1,2,3,4,5,6,7,8-

13C8]PFOA, [1,2,3,4,5,6,7,8,9-13C9]PFNA, [1,2 -13C2]PFDA, 

[1,2,3,4,5,6,7 -13C7]PFUnA, [1,2 -

13C2]PFDoA, [1,2,3 -13C3]PFHS, [1,2,3,4,5,6,7,8-13C8]PFOS, 

and [1,2,3,4,5,6,7,8-

13C8]PFOSA (Wellington Laboratories, Guelph, ON) in combination with 

added ([1,2,3,4,5-

13C5]PFPeA, ([1,2,3,4-13C4]PFHpA, and [18O2]PFBS 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: Alternative volumes may be prepared as long as the ratios of the solvent to solute ratios 

are maintained.

GLP10-01-01; Interim Report 29 

Analysis of PFOA in Groundwater Samples 

Former Sludge Incorporation Area - March/April 2012

Page 53 of 68
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

7.4 Stock Standard Solution (SSS) and Working Standard Solution 

Preparation

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

final volumes may be changed to suit the needs of a particular study. For example, μL 

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

levels.

100 μg/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.

moclecular salt of weight

molecular anion of weight factor correction salt =

9275.0

538

499 PFOS (K factor correction )salt == +

10 mg C8F17S03

-

K+ with purity 90% = 8.35 mg C8F17S03

– (10 mg*0.90*0.9275=8.35 mg)

10 μg/mL (10,000 ng/mL) mixed working standard—Add 5.0 mL each of the 100 μg/mL 

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

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

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

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

volumetric flask and bring up to volume with solvent. 

Storage Conditions—Store all SSSs and working 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 working 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 working standards may be 

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

Calibration 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 preferred. 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 required3

. 

7.5.1 Internal Standard (IS) and Surrogate Recovery Standard (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 

 

3 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 E11-0560.

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

Direct Injection Analysis

concentration of the internal standard is consistent with the internal standard concentration 

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

standard spiking solution is typically 2 μg/mL. A separate zero point or method blank is 

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

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 

internal standard and surrogate standard.

Table 1 lists recommended stable isotope internal 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-

13C4]PFBA, [1,2 -13C2]PFHxA, [1,2,3,4,5,6,7,8-13C8]PFOA, 

[1,2,3,4,5,6,7,8,9-

13C9]PFNA, [1,2,3,4,5,6 -13C6]PFDA, [1,2,3,4,5,6,7 -13C7]PFUnA, [1,2 - 13C2]PFDoA, [1,2,3-

13C3]PFHS, [1,2,3,4,5,6,7,8-13C8]PFOS, and [1,2,3,4,5,6,7,8-13C8]FOSA 

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

13C5]PFPeA, 

([1,2,3,4-

13C4]PFHpA, and [18O2]PFBS 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., 

[

13C2]-PFOA). The same internal 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 surrogate isotopically labeled 

PFSAs are used for PFSAs.

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

calibration curve with ISs and SRSs. 

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Former Sludge Incorporation Area - March/April 2012

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

Direct Injection Analysis

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

Compound Name Synonym or Acronym Analytical Purpose Reference Standard 

Source

13C4-Perfluorobutanoic acid [1,2,3,4-13C4]PFBA IS for PFBA Wellington Labs 

(Mix or Individual)

13C4-Perfluoropentanoic acid [1,2,3,4,5-13C5]PFPeA IS for PFPeA Wellington Labs 

(Mix or Individual)

13C2-Perfluorohexanoic acid [1,2 -13C2]PFHxA IS for PFHxA Wellington Labs 

(Mix or Individual) 

13C4-Perfluoroheptanoic acid [1,2,3,4-13C4]PFHpA IS for PFHpA Wellington Labs 

(Mix or Individual)

13C8-Perfluorooctanoic acid [1,2,3,4,5,6,7,8-13C8]PFOA IS for PFOA and [1,2,3,4 13C4]PFOA

Wellington Labs 

(Mix or Individual)

13C9-Perfluorononanoic acid [1,2,3,4,5,6,7,8,9-13C9]PFNA IS for PFNA Wellington Labs 

(Mix or Individual)

13C6-Perfluorodecanoic acid [1,2,3,4,5,6 -13C6]PFDA IS for PFDA Wellington Labs 

(Mix or Individual)

13C7-Perfluoroundecanoic acid [1,2,3,4,5,6,7 -13C7]PFUnA IS for PFUnA Wellington Labs 

(Mix or Individual)

13C2-Perfluorododecanoic acid [1,2 -13C2]PFDoA IS for PFDoA, *PFTA Wellington Labs 

(Mix or Individual)

18O2-Ammonium Perfluorobutane sulfonate [18O2]PFBS IS for PFBS RTI International 

(Individual)

13C3-Ammonium Perfluorohexane sulfonate [1,2,3-13C3]PFHS IS for PFHS Wellington Labs 

(Mix or Individual)

13C8-Sodium Perfluorooctane sulfonate [1,2,3,4,5,6,7,8-13C8]PFOS IS for PFOS and 

PFOS[1,2,3,4 13C4], 

Wellington Labs 

(Mix or Individual)

13C8-Perfluorooctanesulfonamide [1,2,3,4,5,6,7,8-13C8]FOSA IS for FOSA

Wellington Labs (mix)

RTI International 

(Individual)

13C4-Perfluorooctanoic acid [1,2,3,4-13C4]PFOA SRS for all PFCAs: C4-C8 Wellington

13C2-Perfluoroundecanoic acid [1,2 -13C2]PFUnA SRS for all PFCAs C9-C13 Wellington

13C8-Perfluorooctane sulfonate [1,2,3,4-13C4]PFOS SRS for all PFSAs: C4, 

C6, and C8 Wellington 

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Former Sludge Incorporation Area - March/April 2012

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

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

Sample Description Concentration 

of WS, μg/mL

Volume of 

WS, μL 

Volume of IS 

(2 μg/mL), μL 

Concentration of 

Surrogate, μg/mL

Volume of 

Surrogate, μL 

Volume of ASTM Type I Water, or 

other suitable solvent (1), 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 curve point 10.0 100 50 10.0 100 100

25.0 ng/mL curve 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.

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Former Sludge Incorporation Area - March/April 2012

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

Analysis

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 collection bottles are 

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

matrix spike. Alternatively, 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 marker template. Alternatively, bottles may be weighed prior to bottle 

preparation and weighed again after samples have been collected.

All bottles should be clearly 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 clearly 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 worksheet 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 information 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

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Former Sludge Incorporation Area - March/April 2012

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

Analysis

500 μL of a 0.1 μg/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 surrogate 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 internal standard (IS) is included in the project objective, an appropriate volume of internal 

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 concentration 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 instrument calibration, prior to 

the analysis of CCV samples, after every 10 sample injections, and at the end of the analytical run.

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 internal 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 internal 

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 performed 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 determining 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. 

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Former Sludge Incorporation Area - March/April 2012

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

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

Analysis

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 determine 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 (surrogate and 

internal 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 true 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 determine 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 IS quantitation, stable isotope internal 

standards of each target analyte or appropriate surrogate 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 performance 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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Former Sludge Incorporation Area - March/April 2012

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

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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: Turbo 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 C18 HPLC analytical columns (2.1 mm x 100 mm, 5μm or 2.1 mm x 50 mm, 5μm) may be 

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, 5μm (ThermoElectron Corporation)

Column Temperature: 35°C 

Injection Volume: 5μL

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 

(μL/min)

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 performance. Columns with 

different dimensions (e.g. 2.1mm x 30mm) and columns from different manufacturers (Keystone Betasil C18 

etc.) may be used.

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Former Sludge Incorporation Area - March/April 2012

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

Analysis

Table 4 Suggested MRM Transitions for Target Analytes, Surrogates, and Internal Standards

Analyte Analyte Description Mass Transition

Q1 (amu)

Mass Transition

Q3 (amu)

PFBA (C4 Acid) Target 213 169

PFPeA (C5 Acid) Target 263 219

PFHxA (C6 Acid) Target 313 269, 119

PFHpA (C7 Acid) Target 363 319, 169

PFOA (C8 Acid) Target 413 369, 219, 169

PFNA (C9 Acid) Target

463 419, 169, 219

PFDA (C10 Acid) Target 513 469, 269, 219

PFUnA (C11 Acid) Target 563 519, 269, 219

PFDoA (C12 Acid) Target 613 569, 169, 319

PFTA (C13 Acid) Target 663 619, 369, 319

FBSA (C4 Sulfonamide) Target 298 78

FOSA (C8 Sulfonamide) Target 498 78

PFBS (C4 Sulfonate) Target 299 99, 80

PFHS (C6 Sulfonate) Target 399 99, 80

PFOS (C8 Sulfonate) Target 499 80, 99, 130

[1,2,3,4 -

13C4]PFBA IS for PFBA 217 172

[1,2,3,4,5 -

13C5]PFPeA IS for PFPeA 268 223

[1,2 -

13C2]PFHxA IS for PFHxA 315 270

[1,2,3,4- 13C4]PFHpA IS for PFHpA 367 322

[1,2,3,4,5,6,7,8-

13C8]PFOA IS for PFOA 421 376

[1,2,3,4,5,6,7,8,9-

13C9]PFNA IS for PFNA 472 427

[1,2,3,4,5,6 -

13C6]PFDA IS for PFDA 519 474

[1,2,3,4,5,6,7 -

13C7]PFUnA IS for PFUnA 570 525

[1,2 -

13C2]PFDoA IS for PFDoA and PFTA 615 570

[

18O2]PFBS IS for PFBS 303 84

[1,2,3-

13C3]PFHS IS for PFHS 402 80

[1,2,3,4- 13C4]PFOS IS for PFOS 503 80

[1,2,3,4,5,6,7,8-

13C8]FOSA IS for FOSA 507 80

[1,2,3,4-

13C4]PFOA Surrogate (C4-C8 Acids) 417 372

[1,2,3,4- 13C4]PFOS Surrogate(Sulfonates, FOSA) 503 80

[1,2 -

13C2]PFUnA Surrogate (C9-C13 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 run, as long as the drift continues through the entire 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, external calibration can be applied. See Table 1 for 

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

Analysis

recommended application of available internal 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 ratios 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 = ax2 + 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-determined 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 quantitating by IS) of method and/or solvent blanks. The coefficient 

of determination (r2

) value for the calibration curve must be greater than or equal to 0.990 (or a correlation 

coefficient (r) of 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%. 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, perform 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 calibration 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. 

Calibration verification 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 run, 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 LC/MS/MS 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.4

11.5 Sample Analysis and QCs

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 - 100μL) 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. 

 

4 3M Environmental Laboratory study E08-0096 evaluated the effect on these results as a function of the number of MRMs being monitored. 

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

Analysis

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:

100%*

) mL

ng Concentrat Spike (ion 

) mL

ng LCSConcentrat (ion 

LCS% recovery =

 

Calculate the percent recovery of the LMS using the following equation:

100%*

) mL

ng Spike Concentrat ( ion

) mL

ng -) Concentrat ( Sample of ion mLng LMS Concentrat ( ion

LMS recovery % =

For samples fortified with known amounts of analyte prior to extraction, use the following equation to calculate 

the percent recovery.

100 

(ng/mL) added Analyte

(ng/mL) sample in found analyte Average- (ng/mL) found analyte Total Recovery = ×

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 performance section are not met, maintenance may be performed 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 run. 

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 determination (r2) value for the calibration curve must be greater than or 

equal to 0.990 corresponding 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 

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

Analysis

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

Method/Procedural Blanks: Multiple procedural blanks should be interspersed throughout the analysis batch 

and the analytical sequence. At a minimum, method blanks are analyzed prior to instrument 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% 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 flagged 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 flagged 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 flagged as not meeting the FMS method 

acceptance criteria.

13.5 Analytical Method Uncertainty

Analytical method uncertainty for each target analyte and SRS is determined with control charted historical 

analysis batch LCS data for the method and reported with each analysis batch.5

 Uncertainty determinations 

 

5 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 & 

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

Analysis

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 

determining 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 determine 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 100±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 preferred. 

Quantitation is performed 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 predominantly 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 internal 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.

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Former Sludge Incorporation Area - March/April 2012

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

Analysis

15 Records

Each data package generated for a study must include all supporting information for reconstruction of the data. 

Information for the data package must include, but is not limited to the following items: study or project 

number, sample and standard prep sheets/records, instrument run log (instrument batch records, instrument 

acquisition method, summary pages), instrument results files, chromatograms, calibration curves, and data 

calculations.

16 Affected Documents

None.

17 Revisions

Revision 

Number Summary 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 internal 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 criteria 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 PFOA/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. 

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