GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

GLP10-01-01. Interim Report 24: Analysis of PFOA In Groundwater Samples Collected at 

the Former Sludge Incorporation Area (FSIA) located in Decatur. AL. in December 2011 

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 

Westchester, PA 19380 

Phone: 610-701-3761 

Author 

Susan Wolf 

3M Environmental Laboratory 

Interim Report Completion Date 

Date of signing 

Performing Laboratory 

3M Environmental Health and Safety Operations 

Environmental Laboratory 

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

Maplewood, MN 55144 

Project Identification 

GLPlO-01-01-24 

Total Number of Pages 

70 

The testing reported herein meet the requirements of ANSI/ iSO/lEC 17025:2005 "Generai 

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

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

aiso meets principles of ISO 9001:2000. 

Testing Cert #2052.01 

Page 1 of 70 
GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

This page has been reserved for specific country requirements. 

Page 2 of 70 
GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

GLP COMPLIANCE STATEMENT 

Report Title: GLPI 0-01-01, Interim Report 24. Analysis of PFOA in Groundwater Samples Collected 

at the Fomner Sludge Incorporation Area (FSIA) at Decatur, AL, in December 2011 

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. 

Gary Hohe/isteifW Sponsor Representative Date 

Jaisimha I^Cesari, P.E., DEE, Study Director - ' 'Date 

Page 3 of 70 
.GLP10-01-01; Interim Report 24 

Analysis of PFOA In Groundwater 

Decatur, AL - December 2011 

QUALITY ASSURANCE STATEMENT 

Report Title: GLPI0-01-01, Interim Report 24. Analysis of PFOA in Groundwater Samples Collected 

at the Fonner Sludge Incorporation Area (FSIA) at Decatur, AL, in December 2011 

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 

1/9/2012-1/12/2012 Data / Interim Report 1/24/2012 1/24/2012 

QAU Repre|g6fe{ive Date 

Page 4 of 70 
GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

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 12 

7 Method Summary 12 

7.1 Methods 12 

7.2 Sample Collection 12 

7.3 Sample Preparation 12 

7.4 Analysis 12 

8 Analytical Resu Its 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 

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GLPI 0-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

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, December 2011) 10 

Table 2. Instalment 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 111208 17 

Table 10. DAL GW 130S 111208 17 

Table 11. DAL GW 130L 111208 17 

Table 12. DAL GW 131R 111214 17 

Table 13. DALGW 131S 111214 18 

Table 14. DAL GW 131L111214 18 

Table 15. DAL GW 133R 111214 18 

Table 16. DALGW 133S 111214 18 

Table17. DAL GW 133L 111214 ;.19 

Table 18. DALGW 134R 111209 ^..19 

Table 19. DAL GW 134S 111209 19 

Table 20. DALGW 134L 111209 ' 20 

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GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

Table 21. DAL GW 135R 111214 20 

Table22. DALGW 135S 111214 20 

Table23. DAL GW 135L 111214 20 

Table 24. DAL GW 136S 111213 21 

Table 25. DAL GW 136L 111213 21 

Table26. DALGW 137S 111209 21 

Table 27. DAL GW 137L 111209 21 

Table 28. DAL GW 138R 111214 22 

Table 29. DAL GW 138S 111214 22 

Table 30. DAL GW 138L111214 22 

Table 31. DAL GW 140R 111213 22 

Table32. DALGW 141R 111214.. 23 

Table 33. DAL GW 142R 111213 23 

Table 34. DAL GW 143R 111209 23 

Table35. DALGW 144R 111213 23 

Table 36. Trip Blank 1 24 

Table 37. Rinseate Blanks 24 

Page 7 of 70 
GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

1 Study Information 

Sponsor 

3M Company 

Sponsor Representative 

Gary Hohenstein 

3M EHS Operations 

3M Building 224-5W-03 

Saint Paul, MN 55144-1000 

Phone: (651) 737-3570 

Study Director 

Jaisimha Kesari, P.E., DEE 

Weston Solutions, Inc. 

Westchester, PA 19380 

Phone:(610)701-3761 

Fax:(610)701-7401 

j.kesari@westonsolutions.com 

Study Location 

Testing Facility 

3M EHS Operations 

3M Environmental Laboratory 

Building 260-5N-17 

Maplewood, MN 55106 

Study Personnel 

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

Cleston Lange, Ph.D., Principal Analytical Investigator. (clanqe(a:)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 18 Experimental Tennination: January 2, 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 

resen/e samples are archived at the 3M Environmental Laboratory according to 40 CFR Part 792 

Page 8 of 70 
GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

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

Sludge Incorporation Area (FSIA) in Decatur, AL, representing twenty-seven different sampling 

locations. A total of eighty-eight sample bottles were received at the 3M Environmental Laboratory for 

perfluorooctanoate (PFOA) analysis, and included duplicate groundwater samples from each sampling 

location. Samples also included one field matrix spike (FMS) sample for each location, one trip blank 

set containing Milli-QTM water and appropriate trip blank spikes, and two equipment rinseate blanks. 

The equipment rinseate blanks did not have FMS samples prepared for detennination of PFOA 

recovery. The groundwater samples, trip blanks, and two equipment rinseate blanks were received 

from Weston personnel on December 20, 2011. All of the samples were prepared and analyzed for 

PFOA following 3M Environmental Laboratory Method ETS-8-044.1 under 3M project GLP10-01-01-

24. 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 0.0287 ng/mL, indicating adequate control of sample 

contamination during shipping and sample collection. The PFOA concentration results for all 

groundwaters ranged over four orders of magnitude from 0.341 ng/mL to 3210 ng/mL. The analytical 

uncertainty was estimated at ±19%. 

Page 9 of 70 
GLPI0-01-01; Interim Report 24 

Analysis of PFOA In Groundwater 

Decatur, AL - December 2011 

Table 1. Summarized PFOA Results (FSIA Groundwater, Decatur, AL, December 2011) 

Avg. PFOA Relative 

Sample ID Concentration Percent 

(ng/mL) Difference 

DAL GW130R 111208 783 1.8% 

DAL GW130S 111208 145 3.5% 

DAL GW130L 111208 58.0 2.8% 

DAL GW131R 111214 1430 0.70% 

DAL GW131S 111214 22.7 0.44% 

DAL GW131L 111214 77.5 0.77% 

DAL GW133R 111214 64.4 20% 

DAL GW133S 111214 292 2.7% 

DAL GW133L 111214 275 1.5% 

DALGW134R111209 2080 [a] 1.4% 

DAL GW134S 111209 12.5 1.6% 

DAL GW134L111209 518 0.0% 

DAL GW135R 111214 3210 0.0% 

DAL GW135S 111214 18.9 3.2% 

DAL GW135L 111214 172 4.7% 

DAL GW136S 111213 54.7 1.5% 

DAL GW136L 111213 64.4 1.7% 

DAL GW137S 111209 0.341 2 1% [b] 

DALGW 137L 111209 0.363 4.7% 

DAL GW138R 111214 251 0.80% 

DAL GW138S 111214 123 1.6% 

DAL GW138L 111214 0.473 14% 

DAL GW140R 111213 113 0.89% 

DALGW 141R 111214 1.45 4.1% 

DAL GW142R 111213 51.7 0.58% 

DALGW143R111209 12.9 0.78% 

DAL GW144R 111213 61.4 1.3% 

Trip Blanks (Milli-QTM Water) < 0.0287 N/A 

GLPlO-01-01-24 Equipment rinseate blanks: 

DAL GW 140R and DAL GW 133L < 0.0287 N/A 

N/A: not applicable 

The analytical uncertainty for PFOA was estimated at +19%. 

[a] The analytical uncertainty has been expanded to + 37%. 

[b] Sample/sample duplicate RPD did not meet acceptance criteria of <20%. 

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 

infoimation 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 Fonner Sludge Incorporation Area (FSIA) in Decatur, AL for PFOA in an effort to characterize 

regional groundwater conditions. 

Page 10 of 70 
GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

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, field sample duplicate, and a field spike sample. 

Each empty container for groundwater samplings 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 ah 

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 Detennination 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 9-37 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 C7F15COOH C7F15COOH 

Identifier CAS #95328-99-7 

Ammonium Salt 

CAS #335-67-1 

Use Target Analyte Reference Standard FMS Reference Standard 

Source Wellington Sigma Pidnch 

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

Storage Conditions Frozen /\mbient 

Chemical Lot Number TPFOA0311 MKBD4574V 

TCR Number TCR11-0009 TCR11-0029 

Physical Description Liquid Powder 

Purity NA<^> 96.8% 

(1) Reference standard at a concentration of 50 ± 2.5 |jg/mL 

Page 11 of 70 
GLP10-01-01; Interim Report 24 

Analysis of PFOA In Groundwater 

Decatur, AL - December 2011 

6 Tesf 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 worid" environmental samples. 

Sample Description Key Code. 

string Number String Descriptor Example 

Example DAL GW 131R 0111214 

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 111214-December 14,2011 

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 Detemnination of Perfluorinated Compounds In Water by High Perfomiance 

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 -24 were returned to the 

laboratory at ambient conditions on December 20, 2011. 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 dilutions ImL sample with 9 mLs of Milli-Q water 

(dilution 1:10). Samples that required dilution were prepared by diluting ImLof 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 instmment 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 2, Table 3 

and Table 4. 

Page 12 of 70 
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Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

Table 2. Instrument Parameters. 

Instrument Name ETS Buster 

Analytical Method Followed ETS-8-044.1 

Analysis Date 12/30/11-1/2/12 

Liquid Chromatograph Agilent 1100 

Guard column Prism RP (2.1 mm X 50 mm), 5 n 

Analytical column Betasil C18 (2.1 mm X 100 mm), 5n 

Injection Volume 10 nL 

iVIass Spectrometer Applied Biosystems API 4000 

Ion Source Turto Spray 

Electrode Turt30 ion electrode 

Polarity Negative 

Software Analyst 1.4.2 

Table 3. Liquid Chromatography Conditions. 

step Total Time Flow Rate PercentA Percent B 

Number (min) (^min) (2 mM ammonium acetate) (MethanoO 

ETS-8-044.1 Analysis 

0 0.0 300 97.0 3.0 

1 2.0 300 97.0 3.0 

2 14.5 300 5.0 95.0 

3 15.5 300 5.0 95.0 

4 16.5 300 97.0 3.0 

5 20.0 300 97.0 3.0 

Table 4. Mass Transitions. 

Analyte 

Mass Transition 

Q1/Q3 

PFOA 

413/369 

413/219 

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 laboratory-Milli Q water. 

A total of fifteen spiked standards ranging from 0.025 ng/mL to 100 ng/mL (nominal) were prepared and 

analzyed. 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. 

Page 13 of 70 
GLPI 0-01-01; Interim Report 24 

Analysis of PFOA In Groundwater 

Decatur, AL - December 2011 

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

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

conelation 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 5. 

Table 5. Limit of Quantitation (LOQ). 

Analysis Date(s} PFOA 

LOQ, ng/mL 

12/30/11 0.0287 

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 detennine 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 detennination of method uncertainty in section 8.7. 

The following calculations were used to generate data in Table 6 for laboratory control spikes: 

, „ „ „ . o Calculated Concentration , , 

LCS Percent Recovery = 100% 

Spike Concentration 

LCS% RSD = standard deviation LCS replicates . ^ Q^^^ 

average LCS recovery 

Page 14 of 70 
GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

Table 6. Laboratory Control Spike Recovery. 

ETS-8-044.1 

Analyzed 12/30/11 PFOA (Branched and Linear isomers) 

Lab ID 

Spiked 

Concentration 

(ng/mL) 

Calculated 

Concentration 

(ng/mL) YoRecovery 

LCS-111221^ 0.477 0.504 106 

LCS-111221-5 0.477 0.515 108 

LCS-111221-6 0.477 0.511 107 

Average ± %RSD 107% ±0.93% 

LCS-111221-7 4.77 5.35 112 

LCS-111221-8 4.77 5.37 113 

LCS-111221-9 4.77 5.37 113 

Average ± %RSD 113% ±0.51% 

LCS-111221-10 28.7 21.1 73.5 

LCS-111221-11 28.7 24.0 83.8 

LCS-111221-12 28.7 24.4 84.9 

Average ± %RSD 80.7% ±7.8% 

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 7. Analytical Method Uncertainty. 

Analyte Method Standard Deviation 

Method 

Uncertainty 

PFOA ETS-8-044.1 9.74 ±19% 

8.8 Field Matrix Spikes (FMS) 

A field matrix spike was collected at each sampling point to verify that the analytical method is applicable 

to the collected matrix. Field matrix spikes were generated by adding a measured volume of field 

sample to a container spiked by the laboratory with 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. 

Page 15 of 70 
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Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

Table 8. Field Matrix Spike Levels. 

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

136R, 137R, 137S, 137L, 138L, 141R FMS 0.974 

131S, 134S, 135S, 143R FMS 19.5 

130L, 142R, 144R FMS 48.7 

130S, 131L, 133R, 136S, 136L, 140R FMS 97.4 

133S, 133L, 135L, 138R, 138S FMS 195 

130R, 134L, CW26C, CW26L FMS 487 

131R, 134R, 135R FMS 1950 

Trip Blank 

Low 0.974 

Trip Blank Mid 19.5 Trip Blank Mid-High 97.4 Trip Blank 

High 487 

(Sample Concentration of FMS - Average Concentration : Field Sample & Field Sample Dup.) , „„„, 

FMS Recovery = J-^* 100% 

Spike Concentraton 

9 Dats0ummaiy^h^ Discussion ,'l;\'..;.Jv-l •^g-;:'-'--! 

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. 

DAL GW 134R111209 - The PFOA FMS recovery was 62.8%. Based on the recovery of the FMS 

sample, the method uncertainty for this sample was expanded to ± 37%. 

Page 16 of 70 
Tables. DAL GW 130R 111208 

NA = Not Applicable 

Samples diluted 1:100 

Table 10. DAL GW 1 SOS 111208 

NA = Not Applicable 

Samples diluted 1:10 

Table 11. DAL GW 1 SOL 111208 

NA = Not Applicable 

Samples diluted 1:10 

Table 12. DAL GW 1S1R 111214 

NA = Not Applicable 

Samples diluted 1:100 

GLPI 0-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

PFOA 

Concentration 

3M LIMS ID Description (ng/mL) YoRecovery 

GLP10-01-01-24-001 DAL-GW-130R-0-111208 790 NA 

GLP10-01-01-24-002 DAL-GW-130R-DB-111208 776 NA 

GLPI 0-01-01-24-003 DAL-GW-130R-FMS-111208 1170 79.5 

Average Concentration (ng/mL) ± %RPD 783 ng/mL ±1.8% 

PFOA 

Concentration 

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

GLP10-01-01-24-004 DAL-GW-130S-0-111208 142 NA 

GLP10-01-01-24-005 DAL-GW-130S-DB-111208 147 NA 

GLP10-01-01-24-006 DAL-GW-130S-FMS-111208 215 72.4 

Average Concentration (ng/mL) ± %RPD 145 ng/mL ±3.5% 

PFOA 

Concentration 

3M LIMS ID Description (ng/mL) YoRecovery 

GLPI 0-01-01-24-007 DAL-GW-130L-0-111208 57.2 NA 

GLP10-01-01-24-008 DAL-GW-130L-DB-111208 58.8 NA 

GLP10-01-01-24-009 DAL-GW-130L-FMS-111208 100 86.2 

Average Concentration (ng/mL) ± %RPD 58.0 ng/mL ±2.8% 

PFOA 

Concentration 

3M LIMS ID Description (ng/mL) YoRecovery 

GLP10-01-01-24-010 DAL-GW-131 R-0-111214 1420 NA 

GLPI 0-01-01-24-011 DAL-GW-131R-DB-111214 1430 NA 

GLPI 0-01-01-24-012 DAL-GW-131 R-FMS-111214 2820 71.5 

Average Concentration (ng/mL) ± YoRPD 1430 ng/mL ±0.70% 

Page 1.7 of 70 
Table IS. DAL GW ISIS 111214 

NA = Not Applicable 

Samples diluted 1:10 

Table 14. DAL GW 1S1L 111214 

NA= Not Applicable 

Samples diluted 1:10 

Table 15. DAL GW 1S3R 111214 

NA = Not Applicable 

Samples diluted 1:10 

Table 16. DAL GW 1 SSS 111214 

NA = Not Applicable 

Samples diluted 1:10 

GLP10-01-01; Interim Report 24 

Analysis of PFOA In Groundwater 

Decatur, AL - December 2011 

PFOA 

Concentration 

3M LIMS ID Description (ng/mL) YoRecovery 

GLPI 0-01-01-24-013 DAL-GW-131S-0-111214 22.7 NA 

GLP10-01-01-24-014 DAL-GW-131S-DB-111214 22.6 NA 

GLPI 0-01-01-24-015 DAL-GW-131 S-FMS-111214 39.7 87.5 

Average Concentration (ng/mL) ± YoRPD 22.7ng/mL ±0.44Yo 

PFOA 

Concentration 

3M LIMS ID Description (ng/mL) YoRecovery 

GLPI 0-01-01-24-016 DAL-GW-131L-0-111214 77.8 NA 

GLP10-01-01-24-017 DAL-GW-131L-DB-111214 77.2 NA 

GLPI 0-01-01-24-018 DAL-GW-131 L-FMS-111214 158 82.6 

Average Concentration (ng/mL) ± YoRPD 77.5ng/mL ±0.77Yo 

PFOA 

Concentration 

3M LIMS ID Description (ng/mL) YoRecovery 

GLP10-01-01-24-019 DAL-GW-133R-0-111214 70.8 NA 

GLP10-01-01-24-020 DAL-GW-133R-DB-111214 57.9 NA 

GLP10-01-01-24-021 DAL-GW-133R-FMS-111214 134 71.5 

Average Concentration (ng/mL) ± YoRPD 64.4 ng/mL ±20Yo 

PFOA 

Concentration 

3M LIMS ID Description (ng/mL) YoRecovery 

GLPI 0-01-01-24-022 DAL-GW-133S-0-111214 296 NA 

GLPI 0-01-01-24-023 DAL-GW-133S-DB-111214 288 NA 

GLP10-01-01-24-024 DAL-GW-133S-FMS-111214 508 111 

Average Concentration (ng/mL) ± YoRPD 292 ng/mL ±2.7Yo 

Page 18 of 70 
Table 17. DAL GW 1 SSL 111214 

NA = Not Applicable 

Samples diluted 1:10 

Table 18. DAL GW 1S4R 111209 

NA= Not Applicable 

Samples diluted 1:100 

(1) FMS did not meet acceptance criteria of 100 ± 30%. 

(2) Method uncertainty has been expanded to ±37%. 

Table 19. DAL GW 1S4S 111209 

GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

PFOA 

Concentration 

3M LIMS ID Description (ng/mL) YoRecovery 

GLP10-01-01-24-025 DAL-GW-133L-0-111214 277 NA 

GLPI 0-01-01-24-026 DAL-GW-133L-DB-111214 273 NA 

GLPI 0-01-01-24-027 DAL-GW-133L-FMS-111214 467 98.6 

Average Concentration (ng/mL) ± YoRPD 275 ng/mL ±1.5Yo 

PFOA 

3M LIMS ID Description 

Concentration 

(ng/mL) YoRecovery 

GLP10-01-01-24-028 

GLPI 0-01-01-24-029 

GLP10-01-01-24-030 

DAL-GW-134R-0-111209 

DAL-GW-134R-DB-111209 

DAL-GW-134R-FMS-111209 

2060 

2090 

3300 

NA 

NA 

62.8 

Average Concentration (ng/mL) ± YoRPD 2080 ng/mL ±1.4%'^ 

PFOA 

Concentration 

3M LIMS ID Description (ng/mL) YoRecovery 

GLPI 0-01-01-24-031 DAL-GW-134S-0-111209 12.6 NA 

GLPI 0-01-01-24-032 DAL-GW-134S-DB-111209 . 12.4 NA 

GLP10-01-01-24-033 DAL-GW-134S-FMS-111209 26.3 70.8 

Average Concentration (ng/mL) ± YoRPD 12.5 ng/mL ±1.6% 

NA = Not Applicable 

Page 19 of 70 
Table 20. DALGW 1S4L 111209 

NA = Not Applicable 

Samples diluted 1:100 

Table 21. DAL GW 1S5R 111214 

NA = Not Applicable 

Samples diluted 1:100 

Table 22. DAL GW 1S5S 111214 

NA = Not Applicable 

Table 2S. DAL GW 1 SSL 111214 

NA= Not Applicable 

Samples diluted 1:10 

GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

PFOA 

Concentration 

3M LIMS ID Description (ng/mL) YoRecovery 

GLP10-01-01-24-034 DAL-GW-134L-0-111209 518 NA 

GLP10-01-01-24-035 DAL-GW-134L-DB-111209 518 NA 

GLPI 0-01-01-24-036 DAL-GW-134L-FMS-111209 927 84.0 

Average Concentration (ng/mL) ± YoRPD 518ng/mL±0.0Yo 

PFOA 

Concentration 

3M LIMS ID Description (ng/mL) YoRecovery 

GLP10-01-01-24-037 DAL-GW-135R-0-111214 3210 NA 

GLP10-01-01-24-038 DAL-GW-135R-DB-111214 3210 . NA 

GLPI 0-01-01-24-039 DAL-GW-135R-FMS-111214 4570 69.7 

Average Concentration (ng/mL) ± YoRPD 3210 ng/mL ±0.0% 

PFOA 

Concentration 

3M LIMS ID Description (ng/mL) YoRecovery 

GLPI 0-01-01-24-040 DAL-GW-135S-0-111214 18.6 NA 

GLP10-01-01-24-041 DAL-GW-135S-DB-111214 19.2 NA 

GLP10-01-01-24-042 DAL-GW-135S-FMS-111214 . 32.7 70.8 

Average Concentration (ng/mL) ± YoRPD 18.9 ng/mL ±3.2Yo 

PFOA 

Concerrtration 

3M LIMS ID Description (ng/mL) YoRecovery 

GLP10-01-01-24-043 DAL-GW-135L-0-111214 176 NA 

GLP10-01-01-24-044 DAL-GW-135L-DB-111214 168 NA 

GLPI 0-01-01-24-045 DAL-GW-135L-FMS-111214 317 74.4 

Average Concentration (ng/mL) ± YoRPD 172ng/mL ±4.7% 

Page 20 of 70 
Table 24. DAL GW 1S6S 11121S 

NA= Not Applicable 

Samples diluted 1:10 

Table 25. DAL GW 1S6L 111213 

NA = Not Applicable 

Samples diluted 1:10 

Table 26. DAL GW 137S 111209 

NA= Not Applicable 

(1) RPD did not meet acceptance criteria of S20%. 

Table 27. DAL GW 1S7L 111209 

GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

PFOA 

Concentration 

3M LIMS ID Description (ng/mL) YoRecovery 

GLP10-01-01-24-049 DAL-GW-136S-0-111213 55.1 NA 

GLPI 0-01-01-24-050 DAL-GW-136S-DB-111213 54.3 NA 

GLP10-01-01-24-051 DAL-GW-136S-FMS-111213 140 87.6 

Average Concentration (ng/mL) ± YoRPD 54.7ng/mL ±1.5Yo 

PFOA 

Concerrtration 

3M LIMS ID Description (ng/mL) YoRecovery 

GLP10-01-01-24-052 DAL-GW-136L-0-111213 64.9 NA 

GLPI 0-01-01-24-053 DAL-GW-136L-DB-111213 63.8 NA 

GLPI 0-01-01-24-054 DAL-GW-136L-FMS-111213 153 91.0 

Average Concentration (ng/mL) ± YoRPD 64.4 ng/mL ±17% 

• PFOA 

Concerrtration 

3M LIMS ID Description (ng/mL) YoRecovery 

GLP10-01-01-24-058 DAL-GW-137S-0-111209 0.376 NA 

GLP10-01-01-24-059 DAL-GW-137S-DB-111209 0.306 NA 

GLPI 0-01-01-24-060 DAL-GW-137S-FMS-111209 1.14 82.0 

Average Concentration (ng/mL) ± YoRPD 0.34* ng/mL ± 21%, 

PFOA 

Concentration 

3M LIMS ID Description (ng/mL) YoRecovery 

GLP10-01-01-24-061 DAL-GW-137L-0-111209 0.371 NA 

GLPI 0-01-01-24-062 DAL-GW-137L-DB-111209 0.354 NA 

GLPI 0-01-01-24-063 DAL-GW-137L-FMS-111209 1.36 102 

Average Concentration (ng/mL) ± YoRPD 0.363 ng/mL ±4.7% 

NA = Not Applicable 

Page 21 of 70 
GLP10-01-01; Interim Report 24 

Analysis of PFOA In Groundwater 

Decatur, AL - December 2011 

Table 28. DAL GW 1S8R 111214 

PFOA 

Concerrtration 

3M LIMS ID Description (ng/mL) YoRecovery 

GLP10-01-01-24-064 DAL-GW-138R-0-111214 252 NA 

GLP10-01-01-24-065 DAL-GW-138R-DB-111214 250 NA 

GLPI 0-01-01-24-066 DAL-GW-138R-FMS-111214 397 74.9 

Average Concentration (ng/mL) ± YoRPD 251 ng/mL ±0.80% 

NA = Not Applicable 

Samples diluted 1:10 

Table 29. DAL GW 138S 111214 

PFOA 

Concentration 

3M LIMS ID Description (ng/mL) YoRecovery 

GLP10-01-01-24-067 DAL-GW-138S-0-111214 122 NA 

GLPI 0-01-01-24-068 DAL-GW-138S-DB-111214 124 NA 

GLP10-01-01-24-069 DAL-GW-138S-FMS-111214 281 81.1 

Average Concentration (ng/mL) ± YoRPD 123 ng/mL ± 1.6%, 

NA = Not Applicable 

Samples diluted 1:10 

Table SO. DAL GW 1S8L 111214 

PFOA 

Concentration 

3M LIMS ID Description (ng/mL) YoRecovery 

GLPI 0-01-01-24-070 DAL-GW-138L-C-111214 0.505 NA 

GLP10-01-01-24-071 DAL-GW-138L-DBr111214 0.440 NA 

GLPI 0-01-01-24-072 DAL-GW-138L-FMS-111214 1.45 100 

Average Concentration (ng/mL) ± YoRPD 0.473 ng/mL ± 14%, 

NA = Not Applicable 

Table SI. DAL GW 140R 111213 

PFOA 

Concentration 

3M LIMS ID Description (ng/mL) YoRecovery 

GLPI 0-01-01-24-073 DAL-GW-140R-0-111213 113 NA 

GLP10-01-01-24-074 DAL-GW-140R-DB-111213 112 NA 

GLP10-01-01-24-075 DAL-GW-140R-FMS-111213 199 88.8 

Average Concentration (ng/mL) ± YoRPD 113 ng/mL ±0.89Yo 

NA = Not Applicable 

Samples diluted 1:10 

Page 22 of 70 
Table 32. DAL GW 141R 111214 

NA = Not Applicable 

Table SS. DAL GW 142R 11121S 

NA = Not Applicable 

Samples diluted 1:10 

Table 34. DAL GW 14SR 111209 

NA = Not Applicable 

Samples diluted 1:10 

Table 35. DAL GW 144R 111213 

NA = Not Applicable 

Samples diluted 1:10 

GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

PFOA 

Concerrtration 

3M LIMS ID Description (ng/mL) YoRecovery 

GLPI 0-01-01-24-076 DAL-GW-141 R-0-111214 1.48 NA 

GLPI 0-01-01-24-077 DAL-GW-141R-DB-111214 1.42 NA 

GLPI 0-01-01-24-078 DAL-GW-141 R-FMS-111214 2.42 99.6 

Average Concentration (ng/mL) ± YoRPD 1.45 ng/mL ±4.1Yo 

PFOA 

Concentration 

3M LIMS ID Description (ng/mL) YoRecovery 

GLP10-01-01-24-079 DAL-GW-142R-0-111213 51.8 NA 

GLP10-01-01-24-080 DAL-GW-142R-DB-111213 51.5 NA 

GLPI 0-01-01-24-081 DAL-GW-142R-FMS-111213 • 96.1 91.3 

Average Concentration (ng/mL) ± YoRPD 51.7 ng/mL ±0.58%, 

PFOA 

Concerrtration 

3M LIMS ID Description (ng/mL) YoRecovery 

GLP10-01-01-24-082 DAL-GW-143R-0-111209 12.8 NA 

GLPI 0-01-01-24-083 DAL-GW-143R-DB-111209 12.9 NA 

GLP10-01-01-24-084 DAL-GW-143R-FMS-111209 32.1 98.8 

Average Concentration (ng/mL) ± YoRPD 12.9 ng/mL ±0.78%, 

PFOA 

Concentration 

3M LIMS ID Description (ng/mL) YoRecovery 

GLP10-01-01-24-085 DAL-GW-144R-0-111213 61.8 , NA 

GLPI 0-01-01-24-086 DAL-GW-144R-DB-111213 61.0 NA 

GLP10-01-01-24-087 DAL-GW-144R-FMS-111213 107 93.6 

Average Concentration (ng/mL) ± YoRPD 61.4 ng/mL ±1.3Yo 

Page 23 of 70 
Table 36. Trip Blank 1 

NA = Not Applicable 

Sample GLPI 0-01-01-24-097 diluted 1:10 

Sample GLP10-01-02-24-098 diluted 1:100 

Table 37. Rinseate Blanks 

GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

PFOA 

Concerrtration 

3M LIMS ID Description (ng/mL) YoRecovery 

GLPI 0-01-01-24-094 DAL-GW-TRIP01-0 <0.0287 NA 

GLP10-01-01-24-095 DAL-GW-TRIP01-LS 0.950 97.5 

GLP10-01-01-24-096 DAL-GW-TRIPOl-MS 17.1 87.8 

GLPI 0-01-01-24-097 DAL-GW-TRIP01-MHS 89.4 91.8 

GLPI 0-01-01-24-098 DAL-GW-TR1P01-HS 450 92.4 

PFOA 

3M LIMS ID Description 

Concerrtration 

(ng/mL) YoRecovery 

GLP10-01-01-24-099 

GLPI 0-01-01-24-100 

DAL-GW-140R-RB-111213 

DAL-GW-133L-RB-111214 

<0.0287 

<0.0287 

NA 

NA 

NA = Not Applicable 

Page 24 of 70 
GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

10 Conclusion 

Laboratory control spikes and field matrix spikes were used to detennine 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 24 (General Project Outline) 

Attachment B: Representative Chromatograms and Calibration Curves 

Attachment C: Analytical Method - ETS-8-044.1 

Attachment D: Method Deviation 

Page 25 of 70 
GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

13 Signatures 

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

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

Gary Hohensftein^M Sponsor Representative Date 

Jaisimha Kesan, Study Director 'Date 

Page 26 of 70 

GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

ATTACHMENT A: PROTOCOL AMENDMENT 

Page 27 of 70 
GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur. AL - December 2011 

Analytical Protocol: GLPIO-01-01 

Amendment 24 

Study Title 

Analysis of Perfluorooctanoic Acid (PFOA) in Groundwater, Soil and Sediment for the 

3M Decatur Phase 3 Site-Related Monitoring Program 

PROTOCOL AMENDMENT NO. 24 

Amendment Date: 

December 1, 2011 

Performing Laboratory 

3M Environmental, Health, and Safety Operations 

3M Environmental Laboratory 

Building 260-5N-17 

Maplewood, MN 55144-1000 

Laboratory Project Identification 

GLPIO-01-01 

Sampling Event 

Former Sludge Incorporation Area (FSIA) Groundwater 

Page 1 of 7 

Page 28 of 70 
GLPIO-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

Analytical Protocol: GLP10-01-01 

Amendment 24. 

This amendment modifies the following portion of protocol: 

"Analysis of Perfluorooctanoic Acid (PFOA) in Groundwater, Soil and Sediment for the 

3M Decatur Phase 3 Site-Related Monitoring Program" 

PROTOCOL READS: 

No changes to the wording of the protocol are required. 

AMEND TO READ: 

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

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

at Decatur, AL, and conducted as part of the 3M Decatur Phase 3 Program for PFOA (GLPIO-01-01). 

The anticipated sample collection will occur around the timeframe during the week of December 5, 2011. 

The groundwater samples for this sampling event will be entered into the 3M Environmental Laboratory 

LIMS as project GLPlO-01-01-24 and reported as interim report GLP10-01-G1-24, (reflecting study 

GLP10-01-01 and amendment-24). 

Reason; 

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

anticipate groundwater sample collection event to be conducted for the 3M Decatur. AL facility. 

The GPO is four pages in length and included as attached to this amendment form. 

Page 2 of 7 

Page 29 of 70 
GLPIO-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL-, December 2011 

Analytical Protocol: GLFlO-Ul-or 

Amendment 24 

Amendment Approval 

0. 

Gary Hohenstein, Sponsor Representative Date 

Cleston C. Lange, Principal Analytical Investigator 

]zo. 

Date 

S2 /P^CXC^// 

William Reagen, BHS Opns Environmental Lab Management 

Jaisimha Kesari P.E., DEE. Study Director 

Date 

Ml I 

Date 

Page 3 of 7 

Page 30 of 70 
GLPIO-01-01; Interim Report 24 

Analysis of PFOA In Groundwater 

Decatur, AL - December 2011 

Analytical Protocol: GLPIO-01-01 

Amendment 24 

Environmental Health & Safety Operations, Environmental Laboratory 

General Project Outline 

To: Gary Hohenstein, 3M EHS&Opns 

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

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

Cleston Lange, 3M EHS&Opns; Environmental Lab 

Jai Kesari, Weston Solutions 

Date: December 1, 2011 

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

Decatur Phase 3 Site-Related Monitoring Program; GLP Interim Report 24 - Former Sludge 

Incorporation Area (FSIA) Groundwater - December 2011 Sampling 

1 General Project Information 

3M Sponsor Representative 

Gary Hohenstein 

3M EHS Operations 

3M Building 224-5W-03 

Saint Paul, MN 55144-1000 

Phone; (651) 737-3570 

Qahohenst8in(S;mmm.com 

3M Environmental Laboratory Management 

William K. Reagen 

3IV1 EHS Opns, Environmental Laboratory 

260-5N-17 

651 733-9739 

Contacts wkreaaenffSmmm.com 

Principal Analytical Investigator 

Cleston Lange 

3M EHS Opns, Environmental Laboratory 

260-5N-17 

651 733-9860 

cclanQe®mmm.com 

Sampling Coordinator 

Timothy Frinak 

Weston Solutions 

Timothv.frinak@wesionsolutions.com 

Phone: (334)-332-9123 

Lab Request Number GLP10-01-01-24 

Six Digit Department Number Dept #530711. Project #0022674449 

Project Schedule/Test Dates Sampling scheduled for the week of December 5, 2011 

All verbal and written correspondence will be directed to Gary l-iohenstein. 

Page 4 of 7 

Page 31 of 70 
GLPIO-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

Analytical Protocol: GLPIO-01-01 

Amendment 24 

2 Background Information and Project Objective(s) 

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

samples collected from twenty-seven groundwater wells for Perfluorooctanoic Acid (PFOA) from the 

Former Sludge Incorporation Area (FSIA). Analyses will be conducted under the GLP requirements of 

EPA TSCA Good Laboratory Practice Standards 40 CFR 792. 

Groundwater samples from Decatur, AL will be collected by Weston Solutions personnel the week of 

December 5, 2011. The 3M Environmental Laboratory will prepare the sample bottles with all required 

spikes to ensure that results for PFOA are of a known precision and accuracy. The final report will be 

submitted to Gary Hohenstein and Jai Kesari upon completion under interim report GLPlO-01-01-24. 

3 Project Schedule 

Sample collection bottles will be prepared by 3M Environmental Laboratory for sampling the week of December 

5, 2011. Sample bottles will be shipped in coolers to 3M Decatur for arrival by Monday, December 5, 2011. 

Sample bottles should be stored refrigerated on-site until sample collection. 

Martin Smith \ Weston Trailer 

3M Decatur Plant 

1400 State Docks Road 

Decatur, Alabama 35601 

4 Test Parameters 

The targeted limit of quantitation will be 0.025 ng/mL (ppb) for PFOA. 

A total of thirty-one sampling locations have been specified. For each sampling location, a sample, sample 

duplicate and field matrix spike will be collected. Table 1 indicates the well ID and corresponding field spike 

level. The "fill to here" line on each 250 mL Nalgene bottle will be 200 mL. One sets of trip blanks consisting of 

reagent-grade water, a low-level trip blank spike, mid-level field spike, mid-high field spike, and a high-level trip 

blank spike will be prepared at the 3M Environmental Laboratory and sent to the sampling location with the 

other bottles. 

Based on previous sampling of the FSIA (GLP10-01-01-07, GLP10-01-01-011. and GLP10-01-01-18), more 

than half of the sample locations are expected to have PFOA levels greater than 100 ng/mL. To aid in the 

quantitation of sampling locations with PFOA levels at expected concentrations of <50 ng/mL, sample bottles 

will contain the addition of internal standard ^^Cs-PFOA and "C^-PFOA surrogate.^^The trip blank sample, trip 

blank low and mid spikes will also include the addition of internal standard Cg-PFOA and C^-PFOA 

surrogate. Two additional bottles will be prepared to be used for the preparation of the equipment rinseate 

blanks and will aiso contain the addition of internal standard ''^Cg-PFOA and '^C4-PF0A surrogate. A 1-L 

bottle of laboratory reagent water will be provided to be used to collect the rinseate blanks. 

Page 5 of 7 

Page 32 of 70 
GLPIO-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

Analytical Protocol: GLPIO-01-01 

Amendment 24 

Table 1. Sampling Locations and Field Matrix Spike levels. 

Set# Well No. Spike Cone. (ng/mL) 

1 * 136R, 137R, 137S, 137L, 

138L, 141R 

1.0 

2* 131S,134S,135S, 143R 20 

3* 130L, 142R,144R 50 

4 130S, 131L, 133R, 136S, 

136L. 140R 

100 

5 133S, 133L, 135L, 138R, 138S 200 

6 130R, 134L, CW26C, CW26L 500 

7 131R,134R,135R 2000 

Trip Blank 1 * 

20* 

Trip Blank 

100 

Trip Blank 

500 

Sample bottles will contain '-"Cs-PFOA internal standard and C4-PFOA surrogate. 

5 Test Methods 

Samples will be prepared and analyzed by LC/MS/MS following 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". The data quality objectives for these studies are quantitative results for 

the target analytes with an analytical accuracy of 100±30%. Field matrix spikes not yielding recoveries within 

100±30% will be addressed in the report and the final accuracy statement may be adjusted accordingly. Based 

on the results from previously collected samples from the FSIA, most sampling locations will require dilution with 

laboratory reagent water prior to sample analysis by ETS-8-044.1. 

6 Reporting Requirements 

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

spike. Trip blank and trip blank spikes will be reported for the sampling event as will any equipment/rinseate 

blanks prepared in the field. Laboratory control spikes of reagent water prepared at the time of sample 

preparation will also be reported and used to evaluate the overall method accuracy and precision. Method 

blanks of reagent water prepared at the time of sample preparation will be used to determine the method 

detection limit. For those sampling locations where the field matrix spike level was not appropriate, due to 

higher or lower than expected analyte concentrations, a laboratory matrix spike may be prepared and included 

in the final report. 

7 Email Correspondence 

Attachment A: Sampling Bottle Request 

Page 6 of 7 

Page 33 of 70 
GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur. AL - December 2011 

Analytical Protocol: GLPiO-01-01 

Amendment 24 

Attachment A 

"4^ 

Bottle request for 4th quarter 2011 FSIA well sampling 

Young, Charles 1'. 

'7 lo:stwoli(@mnim.com 

11/29/2011 03:10 PM 

Cc:"Frinak, Timothy R.", "Smith, Martin" 

Froin: "Young, Charles T." <Charlcs.Young@WestonSolutions.com> 

Sue: 

Tim Frinak and Martin Smith are setting up for groundwater sampling commencing next week at the 

following Former Sludge Incorporation Area monitoring wells: 

130R 133L 136S 140R 

130S 134R 136L 141R 

130L 134S 137R 142R 

131R 134L 137S 143R 

131S 135R 137L 144R 

131L 135S 138R CW26C 

133R 135L 138S CW26L 

133S 136R 138L 

Can you prepare a bottle set for shipment to Martin Smith's attention at Decatur with arrival by Tuesday, 

December 6, 2011? As with eariier rounds, analysis will be performed under GLPIO-01-01 and GLPIO01-02. 

Due to the relatively low GW levels at the site, some of the above wells may be dry and therefore will not 

be sampled. Martin will return any unused bottle sets should some of the locations have insufficient water 

for sampling. 

Thanks, 

Chariie 

Charles T. Young 

Technical Director 

Weston Solutions, Inc. 

1400 Weston Way (5-2) 

West Chester, PA 19380 

(610) 701-3787 

Fax (610) 701-3401 

CONFIDENTIALITY: This email and attachments may contain infomiation which is 

confidential and proprietary. Disclosure or use of any such confidential or proprietary 

inlbrmation without the written permission of Weston Solutions, Inc. is strictly prohibited. If you 

received this email in error, please notify the sender by return e-mail and delete this email from 

your system. 'Fhimk you. 

Page 7 of 7 

Page 34 of 70 
GLPIO-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

ATTACHMENT B: REPRESENTATIVE SAMPLE CHROMATOGRAMS AND 

CALIBRATION CURVE(S) 

Page 35 of 70 
GLPIO-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

workstation: ETSBUSTER Batch Name: blll230b.dab 

b111230b.rdb (PFOA): "Quadratic" Regression ("1 / x" weighting): y = -5.83e+003 x''2 + 1.15e+006 x + 2.92e+004 (r = 0.9982) 

6.5e7-

6.0e7 

5.5e7 

5.0e7 

4.5e7 

4.0e7 

I 3.5e7 

8 

S 3.0e7 

< 

2.5e7 

2.0e7 

1.5e7 

1.0e7 

5.0e6 

10 15 25 30 35 40 45 50 55 

Concentration, ng/mL 

60 65 70 75 80 85 90 95 

*Data worked up by KJU 

Printin g Time: 10:25:47 AM 

Printin g Date: Wednesday, January 04, 2012 

Page 1 o f 1 

Page 36 of 70 
GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

Buster J2930203 Batch Name: blll230b.da b 

I

SarTvloNamo''b111230b029" Sample ID'TCS-11122M- F»B: T)111230b.wifr 

Peak Naine. TFOA" Massfes} -413.0/369.0 amu,413.0/219.0 amu.413.Q'169.0 amu 

Comment. "O-Sppb LCS" Annotation-" 

Sample Index^ 29 

I

Sampte Name: •b111230b032- Sampte ID:'LCS-111221-7" Fite' •b111230b.¥rtr 

Peak Name. 'PFOA" Masa(«s): "413.0/369.0 amu.413.0/219 Oamu,413.0/169.0 amu 

CommenL "Sppb LCS" Annotatkm " 

Sample Index: 32 

Sample TypeRT Window: 

Expected BT: 

Use Relativ e E 

O.SOA 

12/31/2( 

1:22:24 

Hanual 

[. 14.9 

609498 CI 

Calculated Cone; 5.35 ng/raL 

Acq. Date: 12/31/2011 1.3e6-

Acq. Tioe: 2:25:40 AH 

Hodified: ies ^.2B6• 

RT Hindow: 30.0 sec 

Expected BT: IS.O oi n 1.1»6-

ose Relativ e BT: , 

Int . Type: Hanual i.0e6-

RetenCion Time: 14.9 min 

Area: 6038490 counts 9.5e5-

End Time; 15.1 min S.5eS8.0e5 

7.5e5 

§• 7.0e5-

# 6.5«S' 

I 6.0e5 

5.5e5 

5.0e5-

4.5e5' 

4.De5' 

3.5e5 

3.0e5 

2.585-

2.0e5-

1.5e5 

I.OeS5.0e4-

15.2 15.4 14.6 14.8 15.0 

Data printe d by STW 

Printin g Time: 3:08:53 PM 

Printin g Date: Wednesday, January 25, 

Page 1 o f 9 

Page 37 of 70 
GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

Buste r J2930203 Batch Name: blll230b.da b 

Modified : 

RT Window: 

Expected RT: 

I

SampteNartia''b111230b036" Sampte ID, •LCS-111221.10- F 

Poak Nam*' "PFOA" Mass(es) "413.0/369.0 arT»j,413.0/219.0 ar 

Commeni- "30ppb LCS" Annotation. ~ 

Sample Index: 35 

Sample Type; QC 

4J)ee3.ee6' 

3.6rt3.4e6-

3.2ae< 

3.0e6-

2.8e6-

2.6B6-

2.4e6 

2.2ee 

2.0e6 

8.0e5-

6.0aS4,0e5< 

2.0e5-

I SampteNam9 "b111230bO42- Samplo ID:•GLPlO-01-01-24-099" File'•b111230bwir 

:ampla Type; 

:alculated Coi 

Hodified : 

RT Window: 

2.1e4 

2.0e4 

SOOO.C 

soooc 

7000.C 

600DC 

50DD.C 

4000.C 

3000 C 

2000.0-

1000.0 

I Sampte Name''b111230bO43' 

Peak Name, "PFOA" Mass(es)- "413.0/369.0 ai 

• Commeni: •DAL-GW-133L-RB-" ArwKrtatwn. " 

Sample Index: 43 

Sanple Type- Unknown 

Concentration: M/A 

Calculated Cone: < 0 

Use Relatl i 

Int . Typo: 

la ID: -GLP1&/)1-O1-24-100' Fde' t l 11230b.wir 

2.1e4 

2.0e4 

1.9e4 

13e4< 

1.7e4 

80000 

7000.0 

60000 

5000.0 

4000.0 

3000.0 

2000.0 

1000,0 

0.0 

I

Sampto Name' "b111230bO46" Sampte ID: 'GLP10-01-01-24-096' Fite' •b111230b.wir 

Paak Name; -pFOA" Mass{es): '413.0/369.0 amu,4130/219.0 amu,413.0/169.0 amu' 

CommenL "DAL-GW-TRIP01-MS-" Afinotatjon." 

Sartipla Index: <6 

3.806-

3.6*6 

3.4ee 

3.2e6 

3.0e6 

2.8ee 

2.6ee 

2.4ee 

2.2e6 

2.0e6 

Height: 

Stai t TiitK 

End Tine : 

18067593 < 

3.9Se*a06 

14.7 

15.1 

B.0e5-

e.0e5-

4.0e5-

Data printe d by STW 

Printin g Time: 3:08:53 PM 

Printin g Date: Wednesday, January 25, 

Page 2 o f 9 

Page 38 of 70 
GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

Buste r J2930203 Batch Name: blll230b.da b 

• Sampte Name-'b111230bO49" Sampte ID''GLP10-01-01-24-001' Fie'*b111230b.wir 

I Peak Name'-PFOA' Mass(es) '413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu" 

I Commenr "DAL-GW-iaOR-O-" Annotation-"' 

Sample Index; 49 

Sample Type; Unknown 

Concentration: H/A 

Calculated Cone: 790. ng/nL 

Acq. Date; 12/31/2011 

Acq. Time: e;24;25 AM 1 

[ SampieName.'b111230b056' Sampte ID "GLPI0^01-01-24-004" Fito:'bin230t),»tfr 

SaniplB TypoCalculated Cc 

Acq. Date: 

Hodified : 

RT Hindow; 

iu,413.0/219.0 amu,413.0/169.0 ai 

2.BeB2.ee6 

24e6-

2.2e6-

2.0e6-

a 1 

i 1.<e6-

B.0e5-

6.0e5 

4.0e5 

2.De5-

I Sampte Name'"bill230bO59' Sampte ID: •GLP1tW11-01-24-O0r Fite: "blllZSOb.wir 

Peak Name: TFOA' Mass{es): "413.0/369.0 ar 

• Commeni "DAL-GW-130L-0-" Annotation. " 

Sample Index; 59 

Modified : 

RT Hindow: 

Expected RT; 

1,413.0/219.0 amu,413.0/169.0 amu" 

I Sampte Name: *b1112306062" Sampte ID:'GLP10-01-01-24-010' Fite'•bni230b.wrtr 

9.5«5 

9.0e5 

7.5e5 

7.0e5 

e.5e5 

6.0e5 

5.5e5 

5.0e5 

3.5e5 

3.0o5 

2£e5 

2.0e5 

Hodl 

RT W 

latlv e RT: 

iu,413.0/219.0 amu.413.0/169.0ai 

3.0e6 

2.eae 

2.eee 

2.4e6 

2.2ee 

2.0e6 

8.0e5 

6.0e5> 

Data printe d by STW 

Printin g Time: 3:08:54 PM 

Printin g Date: Wednesday, January 25, 

Page 3 o f 9 

Page 39 of 70 
GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

** Buster J2930203 Batc h Name: blll230b.da b 

• Sampte Name. •ti111230t)069' Sampte ID: '< 

I Peak Name, 'PFOA" Mass(e5)- -413.D/369.( 

1 Commeni, "DAL-^SW-13ISO-" Annotation'" 

Sample Type; Unk i 

H / A 

5.405 

5.2a5 

5.0e5 

43a5 

4.6e5 

4/4e5 

4Je5 

4.0e5 

3.8«5 

3.6e5 

3.4*5 

3.2e5 

3.0e5 

2.3e5 

2.6e5 

2>te5 

2.2o5 

2.0e5 

8.0e4 

6.0e4 

I SampteName. •b111230b072' Sampte ID,'GLP10-01-01-24.016" Fite'*b111230b,wifr 

. . . iu,413.0/219.0Bmu,413,0/169.0 

Acq. Tlrae: 

I t . Type : 

•tentio n T: 

jlgtic : 

1.5o6-

1.4e6 

9.0e5-

8.0e5-

7.0o5 

6.0e5 

5.0e5 

4.005-

3.0e5 

2.0e5 

I.OeS 

I Sampte Name. 'b111230I:>082' Sampte ID: "GLP10-01-01-24-022" Fite' •b111230b.wir I

Sampte Name:'bin230b075" Sampte ID''( 

Poak Name: "PFOA" Mass(os) "413.0/359.0 

Comn>ent. "DAL-GW-133R-0-* Annotation' ~ 

Sample Index; 75 

1.4ee 

iJe6 

1.2e6 

1.1e6 

1.0e6 

5.0e5-

tJ0«5 

3,0eS2Xle5 

Peak Name. 'PFOA' Mass(os): '413.0/369.01 

• Comment "DAL-GW-ISaS-O-* Annolation:" 

Sample Type; Unknown 

Hodified : 

RT Window: 

Expected RT; 

End Tine: 

4.0e6 

3.ee6 

3.6e6 

3.4ee 

3.2e6 

3.0e6 

2.eee 

2.6e6 

2.4e6 

2.2e6 

2.0e6 

8.0e5-

6.0e5-

4.DeS2.0e5 

14.6 U 3 15.0 15^ 15.4 15.6 15.8 16.i 

Data printe d by STW 

Printin g Time: 3:08:54 PM 

Printin g Date: Wednesday, January 25, 2012 

Page 4 o f 9 

Page 40 of 70 
GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

*** Buste r J2930203 Batch Name: blll230b.da b 

Sampte ID: 'GLP10-01-01-24-025' Fie. "b111230b.*ir 

0/219.0 amu,413.0/169.0 amuRT Kindow; 

Start T: 

End Timt 

4.ea6-

4.dee4.2e6-

4,0e6' 

3.ee6-

3.6e6-

3 4ee3.2e6-

3,0e6> 

2.ee6-

2.6e6 

2.4eS 

2.2e6-

2.0*6 

1.ee6 

1.2a6 

1.0e6> 

8.0e5-

B.OeS 

4.0aS2.0eS> 

I

Sampte Name' •b111230b088' Sampte ID- "GLPI 0-01-01-24-028" Fito. "b111230b.w 

Peak Name: "PFOA' Ma*s(es)"413Xin59.0amu.4i3.0/219.0amu,413.0/169.0amii' 

Comment: 'DAL-GW-WR-O-' Annotation- -

Sample Index- 88 

2060. nq 

12/31/2011 

10:06:53 PH 

Height: 

Start Time. 

End Time: 

3.ee6 

3.6e6 

3.4e6-

3.2e6-

3.0e6' 

2.6e6-

2.6e6-

2.4e6-

2.2e6 

2.006-

1.8e6' 

1.0o6-

8.0e5 

6.0e5-

4.005-

2.085-

I SampteNamo:"b111230b095" Sampte ID: •CLP1O-01-0l-24-O3r Fto'"b111230b.wrfr I Sampte Name'"b111230bO98" Sampte ID 'GLPI 0-01-01-24-034- Fite:*b111230b.wiir 

concentration: ti/A jg^ . 

Calculated Cone: 12.6 ng/roL 

Acq. Date; 1/1/2012 2.5e6-

12;3.:39AK 

Modified: Yea 2.3*6 

RT Hindow; 30.0 sec 

Expected RT: IS.O min 2.2e6-

°" •" 2.M 

Int . Type; Hanual 20o6-

Retention Time: 14.9 min 

Area: 13630528 counts 1.9e6-

Height; 2.63e*006 cps .. . 

Start Time: 14.5 min 

End Time: Ib.l min , 7^. 

Height: 

Start 1 

End Tin 

518. 

1/1/2012 

1:37:59 J 

.17e-t006 cps 

1.15e6 

1.10e6 

1.05e6 

1.00e6 

9.50e5 

9.00e5-

8.50e5 

8.00e5 

T.50e5-

7.00e5 

« 6.50e5 

S 

^ e.OOeS 

I 5.50e5 

5.00e5 

4.50e5 

4.00e5 

3.50o5 

3.00«5 

2.50e5 

2.00e5 

1.50B5 

1.00e5 

5.00e4 

0.00 

Data printe d by STW 

Printin g Time: 3:08:54 PM 

Printin g Date: Wednesday, January 25, 2012 

Page 5 o f 9 

Page 41 of 70 
GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

Buste r J2930203 Batch Name: blll230b.da b 

r

SampteName, •b111230t>101' Sampte ID:'GLP10-01-01-24-037" Fie. "b111230b.wifr 

Peak Name: 'PFOA' Mass{es): '413.0/369.0 amu.413.0/219.0 amu,413.0/169.0 amu' 

Commeni. •DAL-GW-135R-0-' Annotation ~ 

5.2e6 

S0e6 

43e6 

4.6e6 

4.4e6 

4.2e6 

4j0e6 

3.6e6 

ZAet 

3.2e6 

3.0e6 

2.e«6 

2.6e6 

2.4e6 

2.2e6 

2.O06 

1.606 

1.ee6 

1.4e6 

1.206 

1.0e6 

e.0e5 

6.0e5 

4.0e5 

2.0«5 

I

Sampte Name, -ti111230b108' Sampte ID:'GLPKKI1-O1-24-O40' Fite "b111230b.wirr 

Peak Name: 'PFOA' Mass{es) '413.0/369,0 amu,413.0/219.0 amu.413,0/169.0 

CommanL 'DAL-GW-135S^>-" /^nrwtalion. -

Use Relati^ 

Int. Type: 

I SampteName''b111230b114' Sampte ID; •GLP1CMJ1-01-24-O49' nte:'b111230b.wtfr I SamptoName''b111230b111' Sampte ID 'GLP 10-01-01-24-043" Fle-"b111230b.w 

Peak Name- -FTOA" Mass(os)- "413.0/369.0 ar 

• Comment: "DAL-GW-135L-ft-" Arinotatkin " 

Sample Index: 111 

Sample Type; Unknown 

Concentration: K/A 

Calculated Cone: 176. ng/mL 

Acq. Date: 1/1/2012 

Expected Rl 

Use Relati ^ 

Int . Type: 

Height: 

Star t Time: 

End Time: 

j,413.0/219.0 amu.413.0'! 69.0 ai 

3.2e6 

3.0ee 

2£e6 

2.606 

2.4e6 

2.206 

2.0e6 

e.0o5 

e.0e5 

4.0eS 

Peak Name'"PFOA" Mass(os) "413.0/369.0 

• CommenL "DAL-GW-136S-(V" Annolation," 

Sample Index' 114 

Hodified : 

RT Window: 

Expected RT: 

Use Relativ e 

Height: 

Star t T: 

End Tin. 

Data printe d by STW 

Printin g Time: 3:08:54 PM 

Printin g Date: Wednesday, January 25, 

Page 6 o f 9 

Page 42 of 70 
GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

Buste r J2930203 Batch Name: blll230b.da b 

I SampteName. t)11i230b12r Sampte ID:'GLP10-01-01-24-052" Flo,•b11l230b.w 

I Peak Name: "PFOA" Mass(es) '413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu' 

I Comment.-DAL-GW-ISSL-O-' Annotation:-

Sample Type: Unknown 

Calculated Cone: 64.9 

le- U. 9 oiir 

7275572 counts 

l,50e*006 ops 

14.5 tnir 

15.2 15.4 15.6 

I SampteNamo:-b111230bl24" Sampte ID.'GLP10-01-01-24-05e' Fite:T>ni230b.wir 

PeakName"PFOA' Massfes) -413.0/369.0ai 

• CommanL 'DAL-CW-137S-0-" Annotation, ' 

Sample Index; 124 

Sampl e Type : Unknow n 

Calculated Cone; 0.376 ng/raL 

Acq. Date: 1/1/2012 

Acq, Tlrae: 10:47:12 AH 

Modified : les 

11,413.0/219.0 emu.413.0/169.0 amu* 

I

Sampto Name-"b111230b127" Sampte ID.'GLP10-01-01-24-08r Fie'"b11l230b.wifr 

Peak Name: "PFOA" Mass(es)' "413.0/369.0 amu,413.0/219.0 amu.413.0/169.0 amu" 

Commeni. "DAL-GW-nZL-O-" Annotation: ~ 

Sample Index: 127 

Sample Type Unknown 

Acq . Date -

0.37 1 

1/1/20 1 

ng/mL 

I

SampleName "b111230b134" Sampte ID: "GLP10-O1-O1-24^J64" Fite'"blimOb.w 

Peak Name: 'PFOA' Mass(os). "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu" 

Commeni: 'D/y.-GW-l 38R-I>' Annotation." 

Sample Index, 134 

Sample Typo; Unknown 

Calculated Cone: 252. ng/mL 

Acq. Date: 1/1/2012 

Data printe d by STW 

Printin g Time: 3:08:54 PM 

Printin g Date: Wednesday, January 25, 2012 

Page 7 o f 9 

Page 43 of 70 
GLPIO-01-01: Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

Buste r J2930203 Batch Name: blll230b.da b 

I

SampteName •b111230b13r Sampte ID.'GLP1CM)1-01-24-06r Flo'"b111230b.wlfr 

Peak Name: "PFOA" M3Ss(os) '413.0^69.0 amu.413.0^219.0 amu,413.0/169.0 emu" 

Commeni •DAL-GW.135S-0-" AnnoUtion,'" 

2,4e6-

2.3o6 

2.2a6-

2.1 e6-

2.0e6-

1,9e6-

1,ee6 

1.7e6 

1.6e6-

15e6-

1.4e6-

1.3e6 

1.2e6 

1.1e6-

9.0a5 

B.0e5-

7.0e5 

6.0e5-

5.0e5 

4 JUS 

3.0e5 

2.0e5-

I

SampteNamB:'b111230b140' SamptelD t 

Peak Name: TFOA" M3ss{es): "413.0/369.0 

Comment "DAL-GW-138L-0-* Annotation " 

0.505 

1/1/2012 

4 24:40 Ph 

Int. Type; 

Retention ] 

Height: 

1.20e5-

I.ISeSI.IOeS1.05o5-

1.00e5 

9.50e4-

9.00o4-

8.50e4-

8.00e4-

7.5004-

, 7.00e4-

^ 6.5004-

I 6.00o4-

= 5.50o4-

5.00e4-

4.50e4-

4.00e4-

3.50e4-

3.00o4-

2.50e4 

2.0De4-

1.50o4-

1.00e4-

5000.00-

0.00-

I

SampteName'"b111230[)14r SamptelD 'GLPIOOI-01-24-073" Fllo:"b111230b.wir 

Peak Name: 'PFOA- Mass(es) -413.0/369.03010.413.0/219.0 amu,413.0/169.0 amu" 

Comment. DAL-GW-140R-0-" Annotation- ~ 

Sample Index: 147 

2.3e6-

2.2e6 

2.186-

Modif 

RT Wli 

Use Relative RT; No 1.aoti1.eeS 

1.T06-

1 6e6 

1.5e6-

1.4e6-

I

SampteName "b111230b150' SamptelD:"! 

Peak Name' 'PFOA' Mass(os) "413.0/369.0 

CommenL "D/y.-GW-UIR-O-' Annotation."" 

Sample Index- 150 

2.35e+006 eps 

9.0e5 

6.0e5 

7.0o5-

6.0e5 

5.005-

4.0e5-

3.085-

2.0e5 

1.0e5-

Data printe d by STW 

Printin g Time: 3:08:54 PM 

Printin g Date: Wednesday, January 25, 

Page 8 o f 9 

Page 44 of 70 
GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

*** Buste r J2930203 Batch Name: blll230b.da b 

I

Sampte Name, 'bl 11230b153' Sampte IDPeak Name, 'PFOA' Mass(es)- '413.0/369.0 

Comment, 'DAL-.<3W-142R-0-" Annotation' -

Sample Index; 153 

Sample Type: Unknown 

Concentration: N/A 

Calculated Cone: 51.8 ng/mL 

Acq. Date; 1/1/2012 

Modified : 

RT Window: 

Expected RT: 

1.15e6-

I.IOee1.05e6-

I.00e6-

9.50e5-

9.00e5-

8.50o5-

8.00e5 

7.50e5-

7.00o5-

6.50e5 

6.00e5-

5.50o5 

5.00e5-

4.50e5 

4.00e5-

3.50e5-

3.00e5-

2.50e5-

2.00a5-

1.50e5 

1.00e5-

5.00*4-

0.00 

Manual 

!• 14.9 ni n 

1492423 counts 

3.02e-'O05 cps 

(

Sample Name. "b111230b160" Sampte ID, "GLP10-01-01-24-082" Fite- "b111230b w 

Peak Name: "PFOA" Mass(e5j "413.0/369.0 amii,413,0/219,0 omu.413.0/169.0 amu" 

CommenL •DAL-GW-143R-&." Annotation, 

Sample Index: 160 

Sample Type: Unknown 

Concentration; H/A 30*5 

Calculated Cone, 12.8 n<[/nL 

Acq, Date: 1/1/2012 

Acq, Tine; 11:26:52 PM 2,8e5 

Modified ; lea 

RT Window; 30.0 sec 2 6e5 

Expected RT: 15.0 ni n 

Use Relative RT: tlo 

2.4e5 

2.2e5 

Belqlit: 

Start Time: 14.7 ni n 

End Tine : 15.1 i=in 2.0e5 

1.4o5-

1.2e5-

1.0e5-

e.0»4-

6.0*4 • 

4.0e4-

2.0e4' 

I

Sample Name: 'bl 11230bl63' Sampte ID;"' 

Peak Name: "PFOA" Massfes) "413.0/369.0 

Comment- "DAL-GW-144 R-0-' Annotation:" 

Height: 

Start Til 

End Time 

6937525 eour 

1.3e8' 

1.286 

9.5e5 

9.0e5 

B.5e5 

B.0e5 

7.5e5 

7.0e5 

6.Se5 

6.085 

5.5e5 

5.0e5-

4.5e5 

4.0e5-

3.5e5 

3.0e5 

2.5e5 

2.0e5 

13e5 

14.6 14.6 15.0 15.2 15.4 15.6 15.8 16.0 

Data printe d by STW 

Printin g Time: 3:08:55 PM 

Printin g Date: Wednesday, January 25, 2012 

Page 9 of 9 

Page 45 of 70 
GLPIO-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

ATTACHMENT C: ANALYTICAL METHOD(S) 

Page 46 of 70 
GLPIO-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

3M Eiwironmental Laboratory 

Method 

Method of Analysis for the Determination of Perfluorinated Compounds in Water 

by LC/MS/MS; Direct Injection Analysis 

Method Number: ETS-8-044.1 

Adoption Date: 4/12/07 

Effective Date: ///f// / 

Approved By; 

William K. Reagen, Technical Director, Environnnental Laboratory Date 

ETS-8-044.1 Page 1 of 22 

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

Injection Analysis 

Page 47 of 70 
GLPIO-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

1 Scope and Application 

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

water matrices using high-perfomnance liquid chromatography tandem mass spectrometry 

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

perfluoroalkyl sulfonamides and perfluorinated alkyI acids (PFAAs) such as perfluorosulfonic 

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

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

"Detennination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In Water By Solid 

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

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

Table 1. Representative Target Analytes 

Acronym Analyte 

Chemical Abstract Services 

Registry Number (CASRN) 

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

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

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

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

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

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

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

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

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

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

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

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

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

FBSA (04 Sulfonamide Perfluorobutanesulfonamide 30334-69-1 

FOSA (08 Sulfonamide) Pefluorooctanesulfonamide 754-91-6 

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

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

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

detennination of perfluorinated compounds in water matrices when analysis batch quality 

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

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

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

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

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

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

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

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

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

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

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

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

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

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Decatur, AL - December 2011 

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 perfluorocariDoxylic acids (PFCAs) are reported as anions and corrected for 

their salt or free acid fomns. Altematively, quantitation may be perfonned by extemal 

standard calibration. 

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

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

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

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

matrix. 

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

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

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

calibration curve prepared in 1:1 synthetic groundwaterMeOH. 

3 Definitions 

3.1 Analysis Batch 

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

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

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

standards. 

3.2 Analytical Sample 

A portion of a laboratory sample prepared for analysis. 

3.3 Calibration Standard 

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

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 instmment 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. 

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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 

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

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

3.6 Field Duplicate Sample (FDS, Field Dup) 

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

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

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

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

as with laboratory procedures. 

3.7 Field Matrix Spike (FMS) 

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

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

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 

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

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

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

3.9 Internal Standard (IS) 

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

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

stanclard(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 intemal 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 detemnine 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 detemnine whether the sample matrix contributes bias to 

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

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

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

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Decatur, AL - December 2011 

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 perfomnance for a 

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

3.19 Working Standard (WS) 

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

prepare calibration standards and other required analyte solutions. 

4 Warnings and Cautions 

4.1 Health and Safety 

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

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

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

might be present. 

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Decatur, AL - December 2011 

The laboratory is responsible for maintaining a safe wori< environment and a cun-ent 

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 infonnation 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 0.0001 g 

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 

perforrnance 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 

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Decatur, AL - December 2011 

Magnesium Acetate - A.C.S. Reagent Grade 

Methanol - HPLC grade 

Ammonium Acetate - A.C.S. Reagent Grade 

7.2 Representative Target Analytes, ISs, and SRS s 

PFBA, Heptafluorobutyric Acid, (C4 Perfluorinated Acid) 

PFPeA, Nonafluoropentanoic Acid (C5 Perfluorinated Acid) 

PFHxA, Perfluorohexanoic Acid (Ce Perfluorinated Acid) 

PFHpA, Tridecafluoroheptanoic Acid, (C7 Perfluorinated Acid) 

PFOA, Ammonium perfluorooctanoate, (Cs Perfluorinated Acid) 

PFNA, Heptadecafluorononanoic Acid, (Cg Perfluorinated Acid) 

PFDA; Nonadecafluorodecanoic Acid (C10 Perfluorinated Acid) 

PFUnA, Perfluoroundecanoic Acid, (Cn 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-"C], "C4-isotopically labeled perfluorooctanoic acid (SRS) 

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

PFUnA [1,2-"C], "C2-isotopically labeled Perfluoroundecanoic acid (SRS) 

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

"CJPFHxA, [1,2,3,4,5,6,7,8-"C8]PFOA, [1,2,3,4,5,6,7 8,9-"C9]PFNA, [1,2 -^^CJPFDA, 

[1,2,3,4,5,6,7-"CyjPFUnA, [1,2 -"CJPFDoA, [1,2,3-^XajPFHS, [1,2,3,4,5,6,7,8-"C8]PFOS, 

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

added ([1,2,3,4,5-"C5]PFPeA, ([1,2,3,4-X4]PFHpA, and [^^OJPFBS can be used to prepare 

a stock IS solution. Altematively, 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. 

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Decatur, AL - December 2011 

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, \iL 

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

levels. 

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

percent salt, acid[ETS-4^31] and purity) and dilute to 100 mL with methanol or other 

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

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

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

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

PFOS. 

^. , , molecular weight of anion 

salt correction factor = 

moclecular weight of salt 

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

538 

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

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

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

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

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

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

volumetric flask and bring up to volume with solvent. 

Storage Conditions—Store all SSSs and wori<ing standards in accordance with laboratory 

standard operating procedure or in a refrigerator at 4°db2°C for a maximum period of 6 months 

from the date of preparation. 

7.5 Calibration Standards 

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

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

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

guideline. Note: Volumes of water or water/solvent mixtures and worthing 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. Altemately, reference materials of primarily linear isomers of 

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

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

PFOA and PFOS are required^ 

7.5.1 internal Standard (IS) and Surrogate Recovery Standard (SRS) 

For IS calibration, stable isotope intemal 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 intemal standard spiking solution. Typically the 

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

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

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Decatur, AL - December 2011 

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

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

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

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

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

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

the calibration curve, typically at 1 ng/mL. 

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

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

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

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

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

intemal standard and sun'ogate standard. 

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

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

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

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

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

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

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

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

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

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

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

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

["CJ-PFOA). The same 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, 

sun'ogate 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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Decatur, AL - December 2011 

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

Compound Name Synonym or Acronym Analytical Purpose Reference Standard 

Source 

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

Wellington Labs 

(Mix or Individual) 

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

Wellington Labs 

(Mix or Individual) 

"C2-Perfluorohexanoic acid [1,2 -"CzlPFHxA IS for PFHxA 

Wellington Labs 

(Mix or Individual) 

"C4-Perfluoroheptanoic acid [1,2,3,4-"C4]PFHpA IS for PFHpA 

Wellington Labs 

(Mix or Individual) 

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

"C4]PF0A 

Wellington Labs 

(Mix or Individual) 

"CrPerfluorononanoic acid [1,2,3,4,5,6,7,8,9-"CJPFNA IS for PFNA 

Wellington Labs 

(Mix or Individual) 

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

Wellington Labs 

(Mix or Individual) 

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

Wellington Labs 

(Mix or Individual) 

'^Ca-Perfluorododecanoic acid [l,2-"C2]PFDoA IS for PFDoA, *PFTA 

Wellington Labs 

(Mix or Individual) 

"02-Ammonium Perfluorobutane sulfonate ["OzlPFBS IS for PFBS RTI International 

(Individual) 

"Cs-Ammonium Perfluorohexane sulfonate [1,2,3-"C3]PFHS IS for PFHS 

Wellington Labs 

(Mix or Individual) 

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

PFOS[l,2,3,4 "C4], 

Wellington Labs 

(Mix or Individual) 

"Cs-Perfluorooctanesulfonamide [l,2,3,4,5,6,7,8-"C8]FOSA IS for FOSA 

Wellington Labs (mix) 

RTI International 

(Individual) 

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

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

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

C6, and C8 Wellington 

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Decatur, AL - December 2011 

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

Sample Description Concentration 

ofWS,pg/mL 

Volume of 

WS.pL 

Volume of IS 

(2pg/mL),fjL 

Concentration of 

Surrogate, pg/mL 

Volume of 

Surrogate, /d. 

Volume of ASTM Type 1 Water, or 

other suitable solventmL 

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 synttietic groundwater:MeOH. 

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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 collecfion containers. 

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

Sample collecfion 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 cleariy labeled to indicate its intended use as a sample, field sample duplicate, low field 

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

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

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

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

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

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

include the following infonnation: 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 locafion. 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 solufion 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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500 p.L of a 0.1 ng/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 sun-ogate recovery standard (SRS) is included in the project objectives, an appropriate volume 

of a sun-ogate standard solution is added to all the bottles prior to sampling and SPE. Typically sample bottles 

are spiked with sun-ogate 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 intemal 

standard solution is added to all the bottles prior to sampling and SPE. Typically sample bottles are spiked 

with internal standard at a final desired spike concentrafion of 1 ng/mL. 

For the trip blank, the SRS spike and IS spike is added to the bottle and then ASTM Type I water (HPLC grade 

reagent water or other suitable water may used) is added to the "fill to here" line. The bottle is capped and 

sealing tape may be placed around the outer edge of the cap. Trip blank matrix spikes are prepared by adding 

the appropriate volume of target analyte spiking solution, IS, and SRS spiking solutions and filling the bottle to 

the desired volume with the appropriate water and capping and sealing the cap. 

9 Quality Control and Data Quality Objectives 

9.1 Data Quality Objectives 

This method and required quality control samples is designed to generate data accurate to ±30% with a 

targeted LOQ of 0.025 ng/mL. Any deviations from the quality control measures spelled out below will be 

documented in the raw data and footnoted in the final report. 

9.2 Method/Procedural Blanks 

The method/procedural blank is zero point calibration standard (which includes ISs) analyzed in a regular basis 

with each analysis batch. At a minimum, method blanks are analyzed prior to instmment calibration, prior to 

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

The mean area count or area ratios when using internal standard calibration, for each analyte in the method 

blanks must be less than 50% of the area count counts or area ratios when using internal standard calibration, 

of the LOQ standard. The standard deviation of the area counts, or area ratios when using internal standard 

calibrafion, 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 perfonned 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 detemnining 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 detennine 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 fimes the endogenous concentration or 

approximately 4-10 times the LOQ concentration of each target analyte. 

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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 concentrafion near the mid-point of the calibration curve and the high lab control spikes at 

approximately 80% of the upper LOQ. For each target analyte and SRSs, the percent relative standard 

deviation (method precision) for each control spike level must be less than or equal to 20% and the average 

recovery (method accuracy) for each control spike level must be 80-120%. Sample data for target analytes 

outside of the laboratory control spike acceptance criteria will be handled as follows: 

If the average recovery of a spiking level falls outside method acceptance, but at least 67% (6 out of 9) of LCS 

samples are within 20% of their respective nominal value (33% of the QC samples, not all replicates at the 

same concentration, may be outside 20% of nominal value), the average recovery will be flagged as outside 

method acceptance criteria. All LCS samples will be control charted as per ETS-4-026. If the average 

recovery of one of the spiking levels exceeded the analytical method uncertainty as detennined by ETS-12-

012, that analytical batch uncertainty will be expanded for that particular study. 

If more than 67% of the LCS samples fail to meet method acceptance criteria, the data will not be reported. 

Calibration standards consisting of mixed branched and linear isomer PFOS/PFOA are prefen-ed. However, 

for PFOS/PFOA target analytes, if the calibration standards are comprised of predominantly linear isomers 

only, at least one level of triplicate LCSs should be prepared using PFOS/PFOA which contains a mix of linear 

and branched isomers. These LCSs will be used to demonstrate quantitative equivalency (or quantitative bias) 

of the isomeric mix when using a predominantly linear standard for calibration. The mixed linear and branched 

isomer PFOS/PFOA LCSs recoveries should fall within ± 30% of expected values. Alternatively, in lieu of 

mixed branched and linear isomer PFOS/PFOA LCSs, mixed branched and linear isomer PFOS/PFOA 

TBMSs may be applied to demonstrate method accuracy and precision. 

9.5 Field Matrix Spikes (FMSs) / Surrogate Recovery Standards (SRSs) 

FMSs are prepared for each sampling location and analyzed to detennine the matrix effect and sample holding 

time on the spike recovery of each target analyte and/or appropriate SRS. Generally, each sample location 

represents a different sample and sample matrix. 

FMSs are QC samples to which known quantities of appropriate target analytes are added to the sample bottle 

in the laboratory before the bottles are sent to the field. Typically a low and a high target analyte FMS are 

prepared for each sampling location. The sample and field duplicate sample may contain appropriate SRSs in 

lieu of target analyte low field matrix spike and target analyte high field matrix spike samples. 

Field matrix spike method acceptance criteria are recoveries within ±30% of the expected value. If FMS 

recovery (target analyte or SRS spike) is outside of ±30% of the expected value or could not be assessed 

because the FMS (target analyte) was spiked at an inappropriate level, the sample result is reported as follows: 

1. ) If target analyte FMS recovery could not be assessed because the FMS's were at an inappropriate level, 

then Laboratory Matrix Spikes (LMS) may be substituted. If LMS recoveries are within ±30% the data are 

reportable and flagged to indicate that the FMS spikes levels were inappropriate. 

2. ) If multiple target analyte FMS's were prepared on a sample and the closest FMS level to the reported 

sample meets the ±30% acceptance criteria but additional FMS's are outside the ±30% 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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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 (sun-ogate 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 tme values. 

The average of the sample and the field duplicate should be used to calculate the recovery. 

10 Procedures 

10.1 Water Sample Preparation 

This method is applicable to water samples. Samples containing heavy particulate may not be suitable for 

analysis by this method. Samples containing suspended particulate should be centrifuge prior to removing a 

sample aliquot, or filtered. 

• Thoroughly mix sample before removing an aliquot and placing in a labeled autovial. 

• Dilute sample, if necessary, with ASTM Type I water, HPLC water, other suitable water, or solvent 

(methanol). 

• Lab control spikes are prepared for each analysis batch to detemnine method accuracy and precision. 

LCSs should be prepared at three levels in triplicate for each target analyte and at a minimum of two 

levels in triplicate for appropriate SRSs. Low lab control spikes should be prepared at a concentrafion 

in the range of approximately four to ten times higher than the targeted lower LOQ, the mid lab control 

spikes should be prepared at a concentration near the mid-point of the calibration curve and the high 

lab control spikes at approximately 80% of the upper LOQ. For IS quantitation, stable isotope intemal 

standards of each target analyte or appropriate sun-ogate ISs should be spiked at the same level as the 

samples being analyzed, in all LCSs. 

• If LCSs are being prepared using synthetic groundwater, allow the LCSs samples to equilibrate for a 

minimum of 4 hours before aliquoting for analysis or diluting with solvent (methanol). 

11 Sample Analysis - LC/MS/MS 

11.1 Instrument Setup 

Note: In this example, an Applied Biosystems Sciex API 4000 (API 5000 or API 5500) Tandem Mass 

Spectrometer (LC/MS/MS) is used. Other brands/models of LC/MS/MS instmments 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 illustrafive purposes only. Equivalent perfonnance 

may be achieved using apparatus and materials other than those specified here, but demonstration of 

equivalent perfonnance 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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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 Quatemary Pump 

Agilent Vacuum Degasser 

Agilent Autosampler 

Agilent Column Oven 

Note: One or more C18 HPLC analytical columns (2.1 mm x 100 mm, 5|xm or 2.1 mm x50 mm, 5|xm) maybe 

attached on-line after the purge valve and before the sample injection port to retard and separate any residue 

contaminants that may be in the mobile phase and/or HPLC system. 

HPLC Column: Betasil C18,4.6mm x 100mm, 5nm (ThemnoElectron Corporafion) 

Column Temperature: 35°C 

Injection Volume: 5|JL 

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 

(ftUmin) 

Percent A 

(2 mM ammonium 

acetate) 

PercentB 

(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 instmment 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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Table 4 Suggested IVIRiVI Transitions for Target Analytes, Surrogates, and internal Standards 

Analyte 

Analyte Description Mass Transition 

Ql (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 (CIO Acid) Target 513 469,269,219 

PFUnA (C11 Acid) Target 563 519.269,219 

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

PFTA (013 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-"C4IPFBA IS for PFBA 217 172 

r 1,2,3,4,5-"CslPFPeA IS for PFPeA 268 223 

fl,2-"C2lPFHxA IS for PFHxA 315 270 

[1,2,3,4- "CilPFHpA IS for PFHpA 367 322 

[l,2,3,4,5,6,7,8-"C8lPFOA IS for PFOA 421 376 

[1,2,3,4,5,6,7,8,9-"CIPFNA IS for PFNA 472 427 

[1,2,3,4,5,6 -"CfilPFDA IS for PFDA 519 474 

[1,2,3,4,5,6,7-"ClPFUnA IS for PFUnA 570 525 

fl,2-"C2lPFDoA IS for PFDoA and PFTA 615 570 

["O2IPFBS IS for PFBS 303 84 

[l,2,3-"C3lPFHS IS for PFHS 402 80 

[1,2,3,4- "C4IPFOS IS for PFOS 503 80 

[l,2,3,4,5,6,7,8-"C8lFOSA IS for FOSA 507 80 

[l,2,3,4-"C4lPFOA Surrogate (C4-C8 Acids) 417 372 

[1,2,3,4-"C4IPFOS Surrogate(Sulfonates, FOSA) 503 80 

[l,2-"C2lPFUnA 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 fime 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. Quantitafion may be perfonned 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 calibrafion 

does not meet calibration acceptance criteria, extemal calibration can be applied. See Table 1 for 

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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 = ax^ + bx + c), weighted 1/x or 

unweighted, using suitable software. The mathematical method used to calculate the calibrafion 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 rafio 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 detemnination (r^) value for the calibration curve must be greater than or equal to 0.990 (or a con-elation 

coefficient (r) of 0.995). Each point in the curve must be within ±25% of the theoretical concentration with the 

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 verificafions (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 mn, prior 

to the analysis of the calibration curve. Typically these samples are at a concentration near the mid-level of the 

calibrafion 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 intemal standard calibration, with a target RSD 

of S5% and a target retention time RSD of 22%. 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 fime 

period. Ultimately, any effects on these parameters for the System Suitability samples will also be evident on 

all standards and QC samples analyzed as part of the analysis batch. Any effect of system suitability is 

incorporated within QC acceptance criteria. 

11.5 Sample Analysis and 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 -100\A.) of each standard, analytical sample and blank into the instrument 

(unless an on-instrument sample dilution is desired). 

Samples containing analytes that are quantitated above the concentration of the highest standard in the curve 

should be further diluted and reanalyzed. 

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

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12 Data Analysis and Calculations 

The chromatography analysis software will typically calculate the amount of target analyte in the sample 

extracts using the established calibration curve. 

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

LCS Concentration (—) 

LCS% recovery = S^^^ * 100% 

Spike Concentration (—^) 

mL 

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

LMS Concentration (-^) - Concentration of Sample (-^^) 

LMS % recovery = ^ * 100% 

Spike Concentration (-^^) 

mL 

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

the percent recovery. 

Recove _ analyte found (ng/mL) - Average analyte found in sample (ng/mL) ^ 

Analyte added (ng/mL) 

13 Analysis Batch Method Performance Criteria 

Any method performance parameters that are not achieved must be considered in the evaluation of the data. 

Nonconfonnance to any specified parameters must be described and discussed in the final report if the 

Technical Manager (non-GLP study) or Study Director (GLP study) chooses to report the data. 

If criteria listed in this method perfomnance section are not met, maintenance may be peri'ormed 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 perfomnance 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 S2%. 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 njn 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 (r^) value for the calibrafion 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 Perfomriance: 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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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 

IVIethod/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 instmment calibration, prior 

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

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 

fiagged 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 detennined 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 detennined with control charted historical 

analysis batch LCS data for the method and reported with each analysis batch. ^ Uncertainty detenninations 

^ Method uncertainty based on INTERNATIONAL ANSASO/IED STANDARD 17025 reference (GUM, Guide to the Expression of 

Uncertainty in Measurement). Method application demonstrated in ETS-12-012, citing references: a.) EURACHEM/CITAC Guide, 

"Quantifying Uncertainty in Analytical Measurement," Second Edition; Editors: S.L.R. Ellison, M. Rosslein, and A. Williams. 

b.)Georgian, Thomas, "Estimation of Laboratory Analytical Uncertainty Using Laboratory Control Samples," Environmental Testing & 

ETS-8-044.1 Page 20 of 22 

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

Analysis 

Page 66 of 70 
GLPIO-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

are based on INTERNATIONAL ANS/ISO/IED STANDARD 17025 reference (GUM, Guide to the Expression 

of Uncertainty in Measurement) and described in ETS-12-012. At least thirty data points are required for 

detemnining analytical method uncertainty. The method uncertainty is defined as 2x the standard deviation of 

the percent recoveries of the pooled lab control spikes. While all LCS data points are control charted, only the 

most recent fifty data points are used for detemnining the method uncertainty. 

When less than thirty LCS data points have been generated for a given analyte, the analysis batch LCSs are 

used to detennine the data uncertainty. If FMSs meet the ±30% recovery criteria at a level appropriate to the 

endogenous level, and the LCS meet the ±20% recovery criteria, then the uncertainty of the data is detennined 

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 prefen-ed. 

Quantitation is perfonned by integrating the linear and branched isomers together. Alternately, the linear and 

branched isomers can be integrated separately, applying the appropriate tme 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. Altematively, 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 calibrafion curve that is comparable 

regardless of whether the calibration curve was generated using predominantly linear isomers of PFOS/PFOA 

or linear plus branched isomers of PFOS/PFOA. 

14 Pollution Prevention and Waste Management 

Waste generated when performing this method will be disposed of appropriately. The original samples will be 

archived at the 3M Environmental Laboratory in accordance with intemal procedures. 

Analysis, November/December 2000. c.)Taylor, B.N. and CE. Kuyatt, NIST Technical Note 1297, 1994 Edition: "Guidelines for 

Evaluating and Expressing the Uncertainty of NIST Measurement Resuhs."d.)Adams, T.M., "A2LA Guide for the Estimation of 

Measurement Uncertainty in Testing", July 2002. 

ETS-8-044.1 Page 21 of 22 

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

Analysis 

Page 67 of 70 
GLPIO-01-01; Interim Report 24. 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

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, instalment 

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

calculations. 

16 Affected Documents 

None. 

17 Revisions 

Revision 

Number Summarv of Changes 

1 Section 1. included the use of internal standard calibration by this method. 

Section 2. included the use of internal standard calibration by this method. Included the 

use of a solvent/water mixture when analyzing for PFUnA, PFDoA, PFTrDA, and FOSA. . 

Section 3. Added definitions for internal standard, surrogate internal standard, and 

surrogate recovery standard. 

Section 6. Removed the details regarding the instrument parameters to section 10 of the 

method. 

Section 7. Updated reference standards to include intemal standards and surrogates. 

Changed concentration levels for working standards and included the use of internal 

standards and surrogates. 

Section 8. inserted a new section on sample bottle preparation. 

Section 9 Quality Control. This section was previously section 10 in ETS-8-044.0. Updated 

QC criteria to be consistent with method ETS-8-154.4. 

Section 10 Procedures. This section was previously section 8 (Sample l-landiing) 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 h/iethod 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 PFO/VPFOS. 

Section 14 Pollution Prevention. This section was previously section 13 in ETS-8-044.0. 

Section 15 Records. This section was previously section 14 in ETS-8-044.0. ' '. • • 

Section 16 Affected Documents. This section was previously section 15 in ETS-8-044.0. 

Section 17 Revisions. This section was previously section 16 in ETS-8-044.0. 

ETS-8-044.1 Page 22 of 22 

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

Analysis 

Page 68 of 70 
GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

ATTACHMENT D: DEVIATION(S) 

Page 69 of 70 
GLP10-01-01; Interim Report 24 

Analysis of PFOA in Groundwater 

Decatur, AL - December 2011 

RECORD OF DEVIATION/NONCONFORMANCE 

/, Identification 

study / Project No. 

GLP10-01-01-24 

Date(s) of Occurrence: 

12/30/11 (b111230b) 

Document Number: 

ETS-8-044.1 

Deviation type • SOP 

(Check one) • Protocol 

• Equipment Procedure 0 Method 

• GPO • Other: 

//. Description (attach extra pages as needed) 

Method Requirements: 

1. FMS recoveries within 100% ± 30%. 

2. RPD values <20%. 

Actual procedure/process: 

1, DAL GW 134R FMS recovery was 62.8%. 

2. DALGW137SRPDwas21%. 

/// . Actions Taken (such as amendment issued, SOP revision, etc.) 

Corrective Action (• Yes 0 No) Reference: 

Acceptability of the nonconforming work: 

1. The non-compliant FMS will be fiagged in the final report. The method uncertainty will be expanded for PFOA to 

±37forDALGW134R. 

2. The non-compliant RPD for DAL GW 137S will be noted in the final report. 

Actions: • Halting of Work • Client Notification • Work Recall • Withholding of Report 

IZI Other: Deviations will be noted in final report. 

Project Lead/PAI Approval: Susan^Wolf 

Study Director (if GLP): 

Sponsor Approval (for GLP protocol deviations): NA Date: MA 

Technical Reviewer (optional): NA Date: NA 

Laboratory Departnnent Manager Approval: Date: 

IV. Authorization to Resume Work 

Where halting of work occurred, resumption of work must first be approved by Laboratory Management 

Laboratory Department IVIanager Approval: NA Date: N A 

Deviation No. 

(assigned by Study Director or Team Leader at the end of study or project) 

ETS-4-008.7 

Documentation of Deviations and Control of Nonconforming Testing Page 70 of 70