GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

3M 

GLP10-01-01. Interim Report 07: Analysis of PFOA in Groundwater Samples Collected at 

the Former Sludge Incorporation Area (FSIA) located in Decatur. AL in June/July 2010 

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 

Auttior 

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 

GLP10-01-01-07 

Total Number of Pages 

60 

The testing reported herein meet the requirements of iSO/iEC 17025-2005 "General 

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

the A21A Certificate #2052.01. Testing that complies with this Intemationai Standard also 

operate in accordance with ISO 9001:2000. 

Certificate #2052.01 

Page 1 of 60 
GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

This page has been reserved for specific country requirements. 

Page 2 of 60 
GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

GLP COMPLIANCE STATEMENT 

Report Title: GLP10-01-01, Interim Report 07. Analysis of PFOA in Groundwater Samples Collected 

at the Former Sludge Incorporation Area (FSIA) at Decatur, AL in June/July 2010 

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 determined under GLPs. 

Gary Hohfenstein, Sponsor Representative Date 

QMAC/ 

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

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GLP10-01-01; Interim Report 07 

Analysis of PFOA In Groundwater Samples from Decatur, AL 

June/July 2010 

QUALITY ASSURANCE STATEMENT 

Report Title: GLP10-01-01, Interim Report 07. Analysis of PFOA in Groundwater Samples Collected 

at the Former Sludge Incorporation Area (FSIA) at Decatur, AL in June/July 2010 

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 

8/18/10-8/20/10 

Phase 

Data/Interim Report 

Date Reported to 

Testing Facility 

Management 

9/10/10 

Study Director 

9/10/10 

'^' A O-^O 

QAU RepresOTitative Date 

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GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

TABLE OF CONTENTS 

GLP Compliance statement 3 

Quality Assurance Statement 4 

Table of Contents 5 

List of Tables 6 

1 Study Infomnation 8 

2 Summary 9 

3 Introduction 10 

4 Tests 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 Results 14 

8.1 Calibration 14 

8.2 System Suitability 14 

8.3 Limit of Quantitation (LOQ) 14 

8.4 Continuing Calibration 14 

8.5 Blanks 15 

8.6 Lab Control Spikes (LCSs) 15 

8.7 Analytical Method Uncertainty 17 

8.8 Field Matrix Spikes (FMS) 18 

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GLP10-01-01; Interim Report 07 

Analysis of PFOA In Groundwater Samples from Decatur, AL 

June/July 2010 

9 Data Summary and Discussion 18 

10 Conclusion 29 

11 Data/Sample Retention 29 

12 Attachments 29 

13 Signatures 30 

LIST OF TABLES 

Table 1. Summarized PFOA Results (FSIA Groundwater, Decatur, AL, June/July 2010) 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 16 

Table 7. Field Matrix Spike Levels 18 

Table 8. DAL 130R 02 Y10 SF 20 

Table 9. DAL 130S 02 Y10 SF 20 

Table 10. DAL 130LQ2 Y10SF 20 

Table 11. DAL131RQ2 Y10SF 21 

Table 12. DAL 131SQ2 Y10SF 21 

Table 13. DAL131LQ2 Y10SF 21 

Table 14. DAL 132R 02 Y10 SF 22 

Table 15. DAL 132S 02 Y10 SF 22 

Table 16. DAL 132LQ2 Y10SF 22 

Table 17. DAL 133R 02 Y10 SF 23 

Table 18. DAL133SQ2 Y10SF 23 

Table 19. DAL 133L 02 Y10 SF 23 

Table 20. DAL 134R 02 Y10 SF 24 

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GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

Table 21. DAL134SQ2 Y10SF 24 

Table 22. DAL 134L 02 Y10 SF 24 

Table 23. DAL 135R02 Y10SF 25 

Table 24. DAL 135S02 Y10SF 25 

Table 25. DAL 135L 02 Y10 SF 25 

Table 26. DAL 136S 02 Y10 SF 26 

Table27. DAL136LQ2Y10SF 26 

Table 28. DAL 137S 02 Y10 SF 26 

Table 29. DAL 137L 02 Y10 SF 27 

Table 30. DAL 138S 02 Y10 SF 27 

Table 31. DAL 138L 02 Y10 SF 27 

Table 32. Trip Blank 28 

Table 33. Rinseate Blanks 28 

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GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

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(5),mmm.com): phone (651)-733-9860 

Susan Wolf, 3M Analyst 

Jonathan Steege; Analyst 

Study Dates 

Study Initiation: March 8, 2010 

Interim Report 07 Experimental Termination: August 12,2010 

Interim Report Completion: Date of Interim Report Signing 

Location of Arcliives 

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

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

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

Page 8 of 60 
GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

2 Summar y 

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

Sludge Incorporation Area (FSIA) in Decatur, AL, representing twenty-four different sampling locations. 

A total of one hundred twenty-four 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 at least two field matrix spike (FMS) samples for each 

location, one trip blank containing Milli-0TM water and appropriate trip blank spikes, and two equipment 

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

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

received from Weston personnel on July 6, 2010. All of the samples were prepared and analyzed for 

PFOA following 3M Environmental Laboratory Method ETS-8-044.0 and conducted under 3M project 

GLP-10-01-01-07. Many of the groundwater samples required dilution to attain PFOA concentrations 

within the range of the curve, in some instances up to 10(}-fold dilution were required. The average 

measured PFOA concentrations are summarized in Table 1. The equipment rinseates and the trip 

blank were below the lower limit of quantitation (LLOQ) of 0.247 ng/mL, indicating adequate control of 

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

groundwaters ranged over three orders of magnitude from 0.297 ng/mL to 3420 ng/mL. The analytical 

uncertainty was estimated at 100 + 41 %. 

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GLP10-01-01; Interim Report 07 

Analysis of PFOA In Groundwater Samples from Decatur, AL 

June/July 2010 

Table 1. Summarized PFOA Results (FSIA Groundwater, Decatur, AL, June/July 2010) 

Sample ID 

DAL130RQ2Y10SF 

DAL130SO2Y10SF 

DAL130LO2Y10SF 

DAL131RO2Y10SF 

DAL131SO2Y10SF 

DAL131LO2Y10SF 

DAL132RO2Y10SF 

DAL132SO2Y10SF 

DAL132LQ2Y10SF 

DAL133RO2Y10SF 

DAL133SO2Y10SF 

DAL133LO2Y10SF 

DAL134RO2Y10SF 

DAL134SO2Y10SF 

DAL134LO2Y10SF 

DAL135RO2Y10SF 

DAL135SO2Y10SF 

DAL135LO2Y10SF 

DAL136SO2Y10SF 

DAL136LO2Y10SF 

DAL137SO2Y10SF 

DAL137LO2Y10SF 

DAL138SO2Y10SF 

DAL138LO2Y10SF 

Trip Blank (Milli-0TM Water) 

Equipment rinseate blanks 

Avg. PFOA 

Concentration 

(ng/mL) 

942 

163 

86.8 

2880 [a] 

26.3 

115 

303 

1410 

464 [a] 

193 

431 

254 

1880 

7.17 [b] 

540 [a] 

3420 [a] 

17.5 

203 

119 

107 

0.665 

0.297 [b] 

187 

1.80 

< 0.247 

< 0.247 

Relative 

Percent 

Difference 

0.53% 

0.55% 

1.0% 

2.3% 

5.3% 

1.5% 

1.7% 

1.8% 

0.65% 

1.6% 

1.0% 

1.7% 

0.053% 

1,6% 

2.8% 

1.1% 

7.1% 

2.0% 

1.5% 

0.84% 

14% 

0.0% 

2.4% 

1.7% 

N/A 

N/A 

N/A; not applicable 

[a] Sampling location did not have an appropriate FMS spike level to 

sufficiently evaluate PFOA recovery. 

[b] Field matrix spike did not meet method acceptance criteria of 100% ± 30%. 

3 Introduction 

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

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

information regarding concentrations of perfluorooctanoate (PFOA) in various environmental media 

such as groundwater, soils and sediments that are associated with and near the Decatur facility. This 

analytical study was conducted to analyze ground water samples collected from various wells located 

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

regional groundwater conditions. 

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

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

groundwater sampling location included a field sample, field sample duplicate, and a minimum of two 

field spike samples. Each empty container for groundwater samplings was mari<ed with a "fill to here" 

line to produce a final sample volume of 200 mL. Containers designated for field matrix samples were 

Page 10 of 60 
GLP10-01-01; Interim Report 07 

Analysis of PFOA In Groundwater Samples from Decatur, AL 

June/July 2010 

fortified with an appropriate matrix spike solution containing PFOA prior to being sent to the field for 

sample collection. See section 8.8 of the report for field matrix spike levels. 

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

Laboratory method ETS-8-044.0 "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 samples. Tables 8-33 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. 

1 Reference Substance 

Chemical Name 

Chemical Formula 

Identifier 

Source 

Expiration Date 

Storage Conditions 

Chemical Lot Number 

TCR Number 

Physical Description 

Purity 

PFOA 

Perfluorooctanoate 

C7F15COOH 

CAS # 335-67-1 

Oakwood Products 

09/29/2012 

Frozen 

3440 

TCR07-0041 

Powder 

99.5% 

PFOA 

Perfluorooctanoate 

C7F15COOAmmonium Salt 

CAS # 335-67-1 

3M 

02/27/2017 

Frozen 

332 

TCR-123 

White Powder 

95% 

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GLP10-01-01; Interim Report 07 

Analysis of PFOA In Groundwater Samples from Decatur, AL 

June/July 2010 

6 Test System 

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

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

Solutions, Inc. personnel. Samples for this study are "real worid" environmental samples. 

Sample Description Key Code. 

string Number 

Example 

1 

2 

3 

4 

5 

string Descriptor 

DAL132RQ2Y10 SFO 

Sample Location 

Well ID 

Well Level 

Sampling Date 

Sample Type 

Example 

DAL= Decatur, Alabama 

Example: 132 

R = Residum shallow water-bearing zone 

L = Bedrock water-bearing zine 

S = Epikarst middle water-bearing zone 

02 no - 2nd Quarter, 2010 

0=primary sample 

1=duplicate sample 

LS = low spike 

MS = mid spike 

HS = lilgli spike 

7 Method Summar y 

7.1 Methods 

Analysis for all analytes was completed following 3M Environmental Laboratory method ETS-8-044.0 

"Detennination of Perfluorinated Compounds In Water by High Performance Liquid 

Chromatography/Mass Spectrometry Direct Injection Analysis". 

..TM , 

7.2 Sample Collection 

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

Environmental Laboratory. Sample bottles were returned to the laboratory at ambient conditions on July 

6,2010 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 1mL sample with 9 mLs of Milli-0 water 

(dilution 1:10). Some sampling locations were diluted 1:100 by diluting the 1:10 and additonal with Milli0 water. 

7.4 Analysi s 

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

Page 12 of 60 
GLP10-01-01; Interim Report 07 

Analysis of PFOA In Groundwater Samples from Decatur, AL 

June/July 2010 

raw data hard copies placed in the final data packet, and are briefly described below in Table 2, Table 3 

and Table 4. 

Table 2. Instrument Parameters. 

instrument Name 

Analytical iUethod Foiiowed 

Analysis Date 

Liquid Chromatograph 

Guard column 

Analytical column 

Injection Volume 

Mass Spectrometer 

Ion Source 

Electrode 

Polarity 

Software 

ETSOiiie 

ETS-8-044.0 

7/8/10 

Agilent 1100 

Betasil C18 (2.1 mm X 50 mm), 5 u 

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

2or10nL 

Applied Biosystems API 4000 

TurtDO Spray 

Turtx) ion electrode 

Negative 

Analyst 1.4.2 

ETS iVIaryAnn 

ETS-8-044.0 

8/12/10 

Agilent 1200 

Betasil 018 (2.1 mm X 100 mm), 5 n 

Betasil 018 (2.1 mm X 100 mm), 5n 

10 uL 

/Applied Biosystems API 5000 

Turbo Spray 

Turbo ion electrode 

Negative 

/Analyst 1.4.2 

Table 3. Liquid Chiromatograpliy Conditions. 

step 

Number 

0 

1 

2 

3 

4 

5 

Total Time 

(min) 

0 

1.0 

14.5 

15.5 

16.5 

20.0 

Flow Rate 

(fJJmin) 

Percent A 

(2 mM ammonium acetate) 

ETS-8-044.0: Analyzed 7/8/10 

300 

300 

300 

300 

300 

300 

90.0 

90.0 

10.0 

10.0 

90.0 

90.0 

Percent B 

(MethanoO 

10.0 

10.0 

90.0 

90.0 

10.0 

10.0 

ETS-8-044.0; Analyzed 8/12/10 

0 

1 

2 

3 

4 

5 

0 

2.0 

11.5 

13.5 

13.6 

17.0 

300 

300 

300 

300 

300 

300 

97.0 

97.0 

5.0 

5.0 

97.0 

97.0 

3.0 

3.0 

95.0 

95.0 

3.0 

3,0 

Table 4. Mass Transitions. 

Analyte 

PFOA 

Mass Transition 

Q1/Q3 

413/369 

413/219 

413/169 

Dwell time was 200 or 50 msec for each 

transition. The individual transitions were 

summed to produce a "total ion chromatogram" 

(TIC), which was used for quantitation. 

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Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

8 Analytical Results 

8.1 Calibration 

Samples were analyzed against an external standard caiibration curve. Calibration standards were 

prepared by spiking known amounts of the stock solution containing the target analytes into a laboratoryMilli 0 water. A total of fifteen spiked standards ranging from 0.025 ng/mL to 100 ng/mL (nominal) were 

prepared, however, not all curve points were analyzed in both analytical runs. Low and/or high curve 

points were disabled to meet accuracy or linearity criteria. A quadratic, 1/x weighted, calibration curve of 

the peak area counts was used to fit the data for each analyte. The data were not forced through zero 

during the fitting process. Calculating the standard concentrations using the peak area confinned 

accuracy of each curve point. The calibration curve was constnjcted using the linear isomer of PFOA 

only. Since the samples were expected to contain both linear and branched isomers of PFOS, LCS and 

samples were quantitated by processing the PFOA linear and branched isomers separately and 

summing the calculated concentrations together to generate the final PFOA concentration. This was 

done to help minimize any potential analytical bias due to quantitating linear and branched isomers of 

PFOA against a predominately linear reference standard for PFOA. 

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

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

analytes. The correlation coefficient (r) was greater than 0.995 for PFOA. 

8.2 System Suitability 

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

demonstrate overall system suitability. All analytes met 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. 

8.3 Limit of Quantitation (LOQ) 

The LOO 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 LOO for all analytes can be found in Table 5. 

Table 5. Limit of Quantitation (LOQ). 

Analysis Date 

7/8/2010 

8/12/10 

PFOA 

LOQ, ng/mL 

0.247 

0.0296 

8.4 Continuing Calibration 

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

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

CCVs met method criteria of 100% ± 25% with the exception of the following: 

7/8/10 analysis: Twenty-one CCVs were analyzed during the course of the run. The ending three CVs 

had recoveries of 74.1 %, 73.1 %, and 71.0%. Reported samples bracketed by these non-compliant 

CCVS include sampling location DAL 135L and the DAL 132L HS sample. A method deviation is filed 

with the raw data. 

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GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

8.5 Blanks 

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

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

performance to detennine the LOO for each analyte. 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 and are proof of 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 40 mL of laboratory 

Milli 0 water, 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 LCS at each level 

should be within 100% ± 20% with an RSD <20%, were met foithe linear PFOA low and high-level of 

LCS samples analyzed on 7/8/10. The mid-level LCS analyzed on 7/8/10 had an average recovery of 

123%. The mid and high-level LCS samples analyzed on 8/12/10 met method acceptance criteria, while 

the low-level LCS had an average recovery of 122%. 

As the reference materials used for quantitation of PFOA is predominantly linear, and the PFOA present 

in the water samples are comprised of linear and branched isomers, additional LCS samples of linear 

and branched PFOA were prepared at three concentrations to evaluate the potential for analytical bias. 

The linear and branched LCS at both the mid and high levels analyzed on 7/8/10 did not meet method 

acceptance criteria with average recoveries of 141% and 126%, respectively. The low-level linear and 

branched LCS analyzed on 7/8/10 had an average recovery of 104%. The low, mid, and high-level 

linear and branched LCS analyzed on 8/12/10 have average recoveries of 134%, 134%, and 127%, 

respectively. Based on the recovery of the linear and branched PFOA LCS, it is the opinion of the 

laboratory that the recovery discrepency of the linear and branched isomers of PFOA indicates an 

analytical bias. Because of this bias, the method uncertainty will be adjusted to 100% ± 41%, based on 

the recovery of the linear and branched LCS with the highest average recovery. 

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

, „ „ „ . „ Calculated Concentration . . „„. , 

LCS Percent Recovery = * 100% 

Spike Concentration 

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

average LCS recovery 

Page 15 of 60 
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Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

Table 6. Laboratory Control Spilte Recovery. 

ETS-8-044.0 

Analyzed 7/8/2010 

Lab ID 

LCS-100707-1 

LCS-100707-2 

LCS-100707-3 

Average ±%RSD 

LCS-100707-4 

LCS-100707-5 

LCS-100707-6 

Average ±%RSD 

LCS-100707-7 

LCS-100707-8 

LCS-100707-9 

Average ±%RSD 

Linear PFOA 

Spiked 

Concentration 

(ng/mL) 

0.493 

0.493 

0.493 

Calculated 

Concentration 

(ng/mL) 

0.547 

0.535 

0.571 

VoRecovery 

111 

109 

116 

112% ±3.3% 

4.93 

4.93 

4.93 

6.11 

5.98 

6.03 

124 

121 

122 

123%±1.1%''' 

29.6 

29.6 

29.6 

31.6 

30.7 

30.6 

107 

104 

103 

105% ±1.8% 

ETS-8-044.0 

Analyzed 7/8/2010 

Lab ID 

LCS-100707-10 ECF 

LCS-100707-11 ECF 

LCS-100707-12 ECF 

Average ±%RSD 

LCS-100707-13 ECF 

LCS-100707-14 ECF 

LCS-100707-15 ECF 

Average ± %RSD 

LCS-100707-16 ECF 

LCS-100707-17 ECF 

LCS-100707-18 ECF 

Average ±%RSD 

Linear + Branched PFOA 

Spiked 

Concentration 

(ng/mL) 

0.497 

0.497 

0.497 

Calculated 

Concentration 

(ng/mL) 

0.536 

0.516 

0.502 

VoRecovery 

108 

104 

101 

104% ±3.3% 

4.97 

4.97 

4.97 

6.97 

7.05 

7.04 

140 

142 

142 

141% ±0.62%TM 

29.8 

29.8 

29.8 

38.6 

37.2 

37.3 

129 

125 

125 

126% ±2.1%'^' 

(1) Laboratory control sample average recovery did not meet method acceptance criteria of 100% ± 20%. 

Page 16 of 60 
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Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

Table 6 continued. Laboratory Control Splice Recovery. 

ETS-8-044.0 

Analyzed 8/12/2010 

Lab ID 

LCS-100812-1 

LCS-100812-2 

LCS-100812-3 

Average ±%RSD 

LCS-100812^ 

LCS-100812-5 

LCS-100812-6 

Average ±%RSD 

LCS-100812-7 

LCS-100812-8 

LCS-100812-9 

Average ±%RSD 

Linear PFOA 

Spiked 

Concentration 

(ng/mL) 

0.493 

0.493 

0.493 

Calculated 

Concentration 

(ng/mL) 

0.583 

0.609 

0.617 

VoRecovery 

118 

124 

125 

122% ±2.9%''' 

4.93 

4.93 

4.93 

5.46 

5.48 

5.59 

111 

111 

113 

112% ±1.3% 

29.6 

29.6 

29.6 

29.3 

29.4 

29.6 

99.0 

99.3 

100 

99.4% ±0.52% 

ETS-8-044.0 

Analyzed 8/12/2010 

Lab ID 

LCS-100812-10 ECF 

LCS-100812-11 ECF 

LCS-100812-12 ECF 

Average ±%RSD 

LCS-100812-13 ECF 

LCS-100812-14 ECF 

LCS-100812-15 ECF 

Average ±%RSD 

LCS-100812-16 ECF 

LCS-100812-17 ECF 

LCS-100812-18 ECF 

Average ±%RSD 

Urn 

Spiked 

Concentration 

(ng/mL) 

0.497 

0.497 

0.497 

iar * Branched PF 

Calculated 

Concentration 

(ng/mL) 

0.677 

0.663 

0.659 

OA 

VoRecovery 

136 

133 

133 

134%±1.4%''' 

4.97 

4.97 

4.97 

6.64 

6.64 

6.69 

134 

134 

135 

134%±0.43%''' 

29.8 

29.8 

29.8 

38.0 

38.8 

37.0 

128 

130 

124 

127% ±2.4%'^' 

(1) Laboratory control sample average recovery did not meet method acceptance criteria of 100% ± 20%. 

8.7 Analytical Method Uncertainty 

The analytical uncertainty was detennined based on the quality control data generated with the LCS 

samples (Table 6) and was used to evaluate method accuracy and precision. Due to the analytical 

high bias observed during the quantitation of the linear + branched PFOA against a calibration curve 

constmcted from the analysis of calibration standards containing linear PFOA only, an analytical 

uncertainty of 41% is applied to all sample results for this project. 

Page 17 of 60 
GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

8.8 Field Matrix Spikes (FMS) 

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

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

volume of field sample to a container spiked by the laboratory with the target analytes prior to shipping 

sample containers for sample collection. Field matrix spike recoveries within method acceptance criteria 

of 100±30% confimn that "unknown" components in the sample matrix do not significantly interfere with 

the extraction and analysis of the analytes of interest. Field matrix spike concentrations must be 50% of 

the sample concentration to be considered an appropriate field spike. Field matrix spikes are presented 

in section 9 of this report. 

Table 7. Field Matrix Spike Levels. 

Sampling Location 

136R, 137R, 137s, 137L, 138L 

130L, 131L, 132L, 133R, 134S, 134L, 136S'^* 

130R, 130S, 131S, 132R, 132S, 133S, 133L, 

135S, 135L''', 136L, 138S<^', 138R 

131R, 134R, 135R 

Trip Blank 

Spike Level 

Low 

Mid 

High 

Low 

Mid 

High 

Low 

Mid 

High 

Low 

High 

Low 

Mid 

Mid-High 

High 

PFOA, ng/mL 

0.0985 

0.985 

9.85 

0.985 

9.85 

98.6 

9.85 

98.6 

986 

98.6 

986 

0.985 

9.85 

98.6 

986 

(1) One of the spiked bottles in this sampling set was overfilled by more than 10%. The field matrix spike tme value has been 

adjusted accordingly. 

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

FMS Recovery = -^^ ^-^ * 100% 

Spike Concentraton 

9 Data Summar y and Discussion 

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

locations as well as the Trip Blanks and rinseate blanks. Results and average values are rounded to 

three significant figures according to EPA rounding rules. Because of rounding, values may vary slightly 

from those listed in the raw data. 

Field matrix spike recoveries meeting the method acceptance criteria of ± 30%, demonstrate that the 

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

DAL 137L-The mid-level FMS did not meet method acceptance criteria with a recovery of 137%. 

The high-level FMS did meet method acceptance criteria with a recovery of 122%. The low-level FMS 

was not appropriate as compared to the sample concentration. 

Page 18 of 60 
GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

DAL 1348 - The mid-level FMS did not meet method acceptance criteria with a recovery of 137%. 

The high-level FMS did meet method acceptance criteria with a recovery of 101%. The low-level FMS 

was not appropriate as compared to the sample concentration. 

DAL 132L- Due to the high concentration of PFOA detected in the sample, this sampling location did 

not have an appropriate FMS spike level to sufficiently evaluate PFOA recovery. 

DAL 134L- Due to the high concentration of PFOA detected in the sample, this sampling location did 

not have an appropriate FMS spike level to sufficiently evaluate PFOA recovery. 

DAL 131R- Due to the high concentration of PFOA detected in the sample, this sampling location did 

not have an appropriate FMS spike level to sufficiently evaluate PFOA recovery. 

DAL 135R- Due to the high concentration of PFOA detected in the sample, this sampling location did 

not have an appropriate FMS spike level to sufficiently evaluate PFOA recovery. 

Trip Blanit - The low-level FMS did not meet method acceptance criteria with a recovery of 135%. 

The mid-level FMS did not meet method acceptance criteria with a recovery of 131%. 

Page 19 of 60 
GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwter Samples from Decatur, AL 

June/July 2010 

Tables. DAL 130RQ2 Y10 SF 

3MLIMSID 

GLP10-01-01-07-001 

GLP10-01-01-07-002 

GLP10-01-01-07-003 

GLP10-01-01-07-004 

GLP10-01-01-07-005 

Description 

DAL130RQ2Y10SF0 

DAL130RQ2Y10SF1 

DAL130RQ2Y10SFLS 

DAL130RQ2Y10SFMS 

DAL130RQ2Y10SFHS 

Average Concentration (ng/mL) ± %RPD 

PFOA 

Concentration 

(ng/mL) 

939 

944 

949 

1040 

1820 

VoRecovery 

NA 

NA 

NC 

NC 

88.7 

942 ng/mL ±0.53%'^' 

NA= Not Applicable 

NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. 

(1) Sampling location did not have an appropriate spike level to evaluate PFOA recovery. 

Table 9. DAL 1308 Q2 Y10 SF 

3MLIMSID 

GLP10-01-01-07-006 

GLP10-01-01-07-007 

GLP10-01-01-07-008 

GLP10-01-01-07-009 

GLP10-01-01-07-010 

Description 

DAL130SQ2Y10SF0 

DAL130SQ2Y10SF1 

DAL130SQ2Y10SFLS 

DAL130SQ2Y10SFMS 

DAL130SQ2Y10SFHS 

Average Concentration (ng/mL) ± VoRPD 

PFOA 

Concentration 

(ng/mL) 

164 

163 

179 

273 

1170 

VoRecovery 

NA 

NA 

NC 

111 

102 

163 ng/mL ±0.55% 

NA = Not Applicable 

NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. 

Table 10. DAL 130L Q2 Y10 SF 

3MLIMSID 

GLP10-01-01-07-011 

GLP10-01-01-07-012 

GLP10-01-01-07-013 

GLP10-01-01-07-014 

GLP10-01-01-07-015 

Description 

DAL130LQ2Y10SF0 

DAL130LQ2Y10SF1 

DAL130LQ2Y10SFLS 

DAL130LQ2Y10SFMS 

DAL130LQ2Y10SF 

Average Concentration (ng/mL) ± VoRPD 

PFOA 

Concentration 

(ng/mL) 

86.3 

87.2 

86.7 

535 <^' 

194 

VoRecovery 

NA 

NA 

NC 

NC 

109 

86.8 ng/mL ± 1.0% 

NA = Not Applicable 

NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. 

(1) The MS sample concentration detected was not consistent with spike level. A recovery was not calculated. 

Page 20 of 60 
GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

Table 11. DAL 131RQ2 Y10 SF 

3MLIMSID 

GLP10-01-01-07-016 

GLP10-01-01-07-017 

GLP10-01-01-07-018 

GLP10-01-01-07-019 

Description 

DAL131RQ2Y10SF0 

DAL131RQ2Y10SF1 

DAL131RQ2Y10SFLS 

DAL131RQ2Y10SFHS 

Average Concentration (ng/mL) ± VoRPD 

PFOA 

Concentration 

(ng/mL) 

2910 

2850 

2960 

3570 

VoRecovery 

NA 

NA 

NC 

NC 

2880 ng/mL ±2.3% 

NA = Not Applicable 

NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. 

Table 12. DAL 131S Q2 Y10 SF 

3MLIMSID 

GLP10-01-01-07-020 

GLP10-01-01-07-021 

GLP10-01-01-07-022 

GLP10-01-01-07-023 

GLP10-01-01-07-024 

Description 

DAL131SQ2Y10SF0 

DAL131SQ2Y10SF1 

DAL131SQ2Y10SFLS 

DAL131SQ2Y10SFMS 

DAL131SQ2Y10SFHS 

Average Concentration (ng/mL) ± VoRPD 

PFOA 

Concentration 

(ng/mL) 

27.0 

25.6 

38.1 

149 

1050 

VoRecovery 

NA 

NA 

NC 

124 

104 

26.3 ng/mL ±5.3% 

NA = Not Applicable 

NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. 

Table 13. DAL 131LQ2 Y10 SF 

3IVIUMSID 

GLP10-01-01-07-025 

GLP10-01-01-07-026 

GLP10-01-01-07-027 

GLP10-01-01-07-028 

GLP10-01-01-07-029 

Average Cone 

Description 

DAL131LQ2Y10SF0 

DAL131LQ2Y10SF1 

DAL131LQ2Y10SFLS 

DAL131LQ2Y10SFMS 

DAL131LQ2Y10SFHS 

entration (ng/mL) ± VoRPD 

PFOA 

Concentration 

(ng/mL) 

116 

114 

118 

124 

188 

115 ng/mL 

VoRecovery 

NA 

NA 

NC 

NC 

74.1 

± 1.5% 

NA = Not Applicable 

NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. 

Page 21 of 60 
GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

Table 14. DAL 132RQ2 Y10 SF 

3MUIVISID 

GLP10-01-01-07-030 

GLP10-01-01-07-031 

GLP10-01-01-07-032 

GLP10-01-01-07-033 

GLP10-01-01-07-034 

Description 

DAL132RQ2Y10SF0 

DAL132RQ2Y10SF1 

DAL132RQ2Y10SFLS 

DAL132RQ2Y10SFMS 

DAL132RQ2Y10SFHS 

Average Concentration (ng/mL) ± VoRPD 

PFOA 

Concentration 

(ng/mL) 

300 

305 

312 

409 

1250 

VoRecovery 

NA 

NA 

NC 

NC 

96.1 

303 ng/mL ±1.7% 

NA= Not Applicable 

NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. 

Table 15. DAL 132S Q2 Y10 SF 

3MLIMSID 

GLP10-01-01-07-035 

GLP10-01-01-07-036 

GLP10-01-01-07-037 

GLP10-01-01-07-038 

GLP10-01-01-07-039 

Description 

DAL132SQ2Y10SF0 

DAL132SQ2Y10SF1 

DAL132SQ2Y10SFLS 

DAL132SQ2Y10SFMS 

DAL132SQ2Y10SFHS 

Average Concentration (ng/mL) ± VoRPD 

PFOA 

Concentration 

(ng/mL) 

1430 

1400 

1390 

1450 

2250 

VoRecovery^ 

NA 

NA 

NC 

NC 

84.4 

1410 ng/mL ±1.8% 

NA = Not Applicable 

NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. 

Table 16. DAL 132LQ2 Y10 SF 

3MLIMSID 

GLP10-01-01-07-040 

GLP10-01-01-07-041 

GLP10-01-01-07-042 

GLP10-01-01-07-043 

GLP10-01-01-07-044 

Description 

DAL132LQ2Y10SF0 

DAL132LQ2Y10SF1 

DAL132LQ2Y10SFLS 

DAL132LQ2Y10SFMS 

DAL132LQ2Y10SFHS 

Average Concentration (ng/mL) ± VoRPD 

PFOA 

Concentration 

(ng/mL) 

462 

465 

474 

473 

575 

VoRecovery^ 

NA 

NA 

NC 

NC 

NC 

464 ng/mL ±0.65%^'^ 

NA = Not Applicable 

NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. 

(1) Sampling location did not have an appropriate spike level to evaluate PFOA recovery. 

Page 22 of 60 
GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

Table 17. DAL 133R Q2 Y10 SF 

3IVILIMSID 

GLP10-01-01-07-045 

GLP10-01-01-07-046 

GLP10-01-01-07-047 

GLP10-01-01-07-048 

GLP10-01-01-07-049 

Description 

DAL133RQ2Y10SF0 

DAL133RQ2Y10SF1 

DAL133RQ2Y10SFLS 

DAL133RQ2Y10SFIVIS 

DAL133RQ2Y10SFHS 

Average Concentration (ng/mL) ± VoRPD 

PFOA 

Concentration 

(ng/mL) 

192 

195 

187 

193 

273 

193 ng/mL 

VoRecovery 

NA 

NA 

NC 

NC 

80.6 

± 16% 

NA = Not Applicable 

NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. 

Table 18. DAL 133S Q2 Y10 SF 

3MLIMSID 

GLP10-01-01-07-050 

GLP10-01-01-07-051 

GLP10-01-01-07-052 

GLP10-01-01-07-053 

GLP10-01-01-07-054 

Description 

DAL133SQ2Y10SF0 

DAL133SQ2Y10SF1 

DAL133SQ2Y10SFLS 

DAL133SQ2Y10SFMS 

DAL133SQ2Y10SFHS 

Average Concentration (ng/mL) ± VoRPD 

PFOA 

Concentration 

(ng/mL) 

429 

433 

443 

536 

1320 

VoRecovery 

NA 

NA 

NC 

NC 

90.1 

431 ng/mL ± 1.0% 

NA = Not /Applicable 

NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. 

Table 19. DAL 133LQ2 Y10 SF 

3MLIMSID 

GLP10-01-01-07-055 

GLP10-01-01-07-056 

GLP10-01-01-07-057 

GLP10-01-01-07-058 

GLP10-01-01-07-059 

Description 

DAL133LQ2Y10SF0 

DAL133LQ2Y10SF1 

DAL133LQ2Y10SFLS 

DAL133LQ2Y10SFMS 

DAL133LQ2Y10SFHS 

Average Concentration (ng/mL) ± VoRPD 

PFOA 

Concentration 

(ng/mL) 

252 

256 

268 

372 

1110 

254 ng/mL 

VoRecovery 

NA 

NA 

NC 

NC 

87.1 

± 1.7% 

NA = Not Applicable 

NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. 

Page 23 of 60 
GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

Table 20. DAL 134RQ2 Y10 SF 

3MLIMSID 

GLP10-01-01-07-060 

GLP10-01-01-07-061 

GLP10-01-01-07-062 

GLP10-01-01-07-063 

Description 

DAL134RQ2Y10SF0 

DAL134RQ2Y10SF1 

DAL134RQ2Y10SFLS 

DAL134RQ2Y10SFHS 

Average Concentration (ng/mL) ± VoRPD 

PFOA 

Concentration 

(ng/mL) 

1880 

1880 

1940 

2680 

VoRecovery 

NA 

NA 

NC 

80.5 

1880 ng/mL ±0.053% 

NA = Not Applicable 

NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. 

Table 21. DAL 134S Q2 Y10 SF 

SMLIMSID 

GLP10-01-01-07-070 

GLP10-01-01-07-071 

GLP10-01-01-07-072 

GLP10-01-01-07-073 

GLP10-01-01-07-074 

Description 

DAL134SQ2Y10SF0 

DAL134SQ2Y10SF1 

DAL134SQ2Y10SFLS 

DAL134SQ2Y10SFMS 

DAL134SQ2Y10SFHS 

Average Concentration (ng/mL) ± VoRPD 

PFOA 

Concentration 

(ng/mL) 

7.11 

7.23 

8.55 

20.7 

107 

VoRecovery 

NA 

NA 

NC 

137'^' 

101 

7.17 ng/mL ±1.6% 

NA = Not /Applicable 

NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. 

(1) Field matrix spike did not meet method acceptance criteria of 100% ± 30%. 

Table 22. DAL 134LQ2 Y10 SF 

3IVILIMSID 

GLP10-01-01-07-075 

GLP10-01-01-07-076 

GLP10-01-01-07-077 

GLP10-01-01-07-078 

GLP10-01-01-07-079 

Description 

DAL134LQ2Y10SF0 

DAL134LQ2Y10SF1 

DAL134LQ2Y10SFLS 

DAL134LQ2Y10SFMS 

DAL134LQ2Y10SFHS 

Average Concentration (ng/mL) ± VoRPD 

PFOA 

Concentration 

(ng/mL) 

547 

532 

547 

530 

599 

VoRecovery 

NA 

NA 

NC 

NC 

NC 

540 ng/mL ±2.8%^' 

NA = Not Applicable 

NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. 

(1) Sampling location did not have an appropriate spike level to evaluate PFOA recoveiy. 

Page 24 of 60 
GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwter Samples from Decatur, AL 

June/July 2010 

Table 23. DAL 135R Q2 Y10 SF 

3M LIMB ID 

GLP10-01-01-07-064 

GLP10-01-01-07-065 

GLP10-01-01-07-066 

GLP10-01-01-07-067 

Description 

DAL135RQ2Y10SF0 

DAL135RQ2Y10SF1 

DAL135RQ2Y10SFLS 

DAL135RQ2Y10SFHS 

Average Concentration (ng/mL) ± VoRPD 

PFOA 

Concentration 

(ng/mL) 

3400 

3440 

3540 

4100 

VoRecovery 

NA 

NA 

NC 

NC 

3420 ng/mL ±1.1%"> 

NA = Not Applicable 

NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. 

(1) Sampling location did not have an appropriate spike level to evaluate PFOA recovery. 

Table 24. DAL 135S Q2 Y10 SF 

3IVILIMSID 

GLP10-01-01-07-080 

GLP10-01-01-07-081 

GLP10-01-01-07-082 

GLP10-01-01-07-083 

GLP10-01-01-07-084 

Description 

DAL135SQ2Y10SF0 

DAL135SQ2Y10SF1 

DAL135SQ2Y10SFLS 

DAL135SQ2Y10SFMS 

DAL135SQ2Y10SFHS 

Average Concentration (ng/mL) ± VoRPD 

PFOA 

Concentration 

(ng/mL) 

16.9 

18.2 

28.4 

NA<^' 

NA'^> 

VoRecovery 

NA 

NA 

110 

NA'^' 

NA'^' 

17.5 ng/mL ±7.1% 

NA = Not Applicable 

(1) Samples were re-analyzed on 8/12/10. Spike level was not analyzed sine the LS was the most appropriate spike level. 

Table 25. DAL 135L Q2 Y10 SF 

3MLIMSID 

GLP10-01-01-07-085 

GLP10-01-01-07-086 

GLP10-01-01-07-087 

GLP10-01-01-07-088 

GLP10-01-01-07-089 

Description 

DAL135LQ2Y10SF0 

DAL135LQ2Y10SF1 

DAL135LQ2Y10SFLS 

DAL135LQ2Y10SFMS'^' 

DAL135LQ2Y10SFHS 

Average Concentration (ng/mL) ± VoRPD 

PFOA 

Concentiration 

(ng/mL) 

201 

205 

208 

286 

1110 

VoRecovery 

NA 

NA 

NC 

NC 

91.6 

203 ng/mL ±2.0% 

NA = Not Applicable 

NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. 

(1) Sample bottle was overfilled by more than 10%. The FMS tme value was adjusted accordingly. 

Page 25 of 60 
GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

Table 26. DAL 136S Q2 Y10 SF 

3MLIIVISID 

GLP10-01-01-07-090 

GLP10-01-01-07-091 

GLP10-01-01-07-092 

GLP10-01-01-07-093 

GLP10-01-01-07-094 

Description 

DAL136SQ2Y10SF0 

DAL136SQ2Y10SF1 

DAL136SQ2Y10SFLS 

DAL136SQ2Y10SFMS 

DAL136SQ2Y10SFHS''' 

Average Concentration (ng/mL) ± VoRPD 

PFOA 

Concentration 

(ng/mL) 

118 

120 

118 

126 

195 

VoRecovery 

NA 

NA 

NC 

NC 

85.6 

119 ng/mL ±1.5% 

NA = Not Applicable 

NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. 

(1) Sample bottle was overfilled by more than 10%. The FMS tme value was adjusted accordingly. 

Table 27. DAL 136L Q2 Y10 SF 

3MLIIVISID 

GLP10-01-01-07-095 

GLP10-01-01-07-096 

GLP10-01-01-07-097 

GLP10-01-01-07-098 

GLP10-01-01-07-099 

Description 

DAL136LQ2Y10SF0 

DAL136LQ2Y10SF1 

DAL136LQ2Y10SFLS 

DAL136LQ2Y10SFMS 

DAL136LQ2Y10SFHS 

Average Concentration (ng/mL) ± VoRPD 

PFOA 

Concentration 

(ng/mL) 

107 

108 

113 

208 

1020 

VoRecovery 

NA 

NA 

NC 

102 

92.8 

107 ng/mL ±0.84% 

NA = Not Applicable 

NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. 

Table 28. DAL 137S Q2 Y10 SF 

3MLIMSID 

GLP10-01-01-07-100 

GLP10-01-01-07-101 

GLP10-01-01-07-102 

GLP10-01-01-07-103 

GLP10-01-01-07-104 

Description 

DAL137SQ2Y10SF0 

DAL137SQ2Y10SF1 

DAL137SQ2Y10SFLS 

DAL137SQ2Y10SFMS 

DAL137SQ2Y10SFHS 

Average Concentration (ng/mL) ± %RPD 

PFOA 

Concentration 

(ng/mL) 

0.658 

0.672 

0.766 

1.84 

12.1 

VoRecovery 

NA 

NA 

NC 

120 

116 

0.665 ng/mL ±14% 

NA = Not /\pplicable 

NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. 

Page 26 of 60 
GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

Table 29. DAL 137L Q2 Y10 SF 

3MLIMSID 

GLP10-01-01-07-105 

GLP10-01-01-07-106 

GLP10-01-01-07-107 

GLP10-01-01-07-108 

GLP10-01-01-07-109 

Description 

DAL137LQ2Y10SF0 

DAL137LQ2Y10SF1 

DAL137LQ2Y10SFLS 

DAL137LQ2Y10SFMS 

DAL137LQ2Y10SFHS 

Average Concentration (ng/mL) ± VoRPD 

PFOA 

Concentration 

(ng/mL) 

0.297 

0.297 

0.417 

1.65 

12.1 

VoRecovery 

NA 

NA 

NC 

137 <^' 

122 

0.297 ng/mL ±0.0% 

NA = Not Applicable 

NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. 

(1) Field matrix spike did not meet method acceptance criteria of 100% ± 30%. 

Table 30. DAL 138S Q2 Y10 SF 

3MLIMSID 

GLP10-01-01-07-110 

GLP10-01-01-07-111 

GLP10-01-01-07-112 

GLP10-01-01-07-113 

GLP10-01-01-07-114 

Average Cone 

Description 

DAL138SQ2Y10SF0 

DAL138SQ2Y10SF1 

DAL138SQ2Y10SFLS<^' 

DAL138SQ2Y10SFMS 

DAL138SQ2Y10SFHS 

entration (ng/mL) ± VoRPD 

PFOA 

Concentration 

(ng/mL) 

189 

184 

197 

291 

1080 

187 ng/mL 

VoRecovery 

NA 

NA 

NC 

106 

90.1 

± 2.4% 

NA = Not /Applicable 

NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. 

(1) Sample bottle was overfilled by more than 10%. The FMS tnje value was adjusted accordingly. 

Table 31. DAL 138L Q2 Y10 SF 

3MLIIVISID 

GLP10-01-01-07-115 

GLP10-01-01-07-116 

GLP10-01-01-07-117 

GLP10-01-01-07-118 

GLP10-01-01-07-119 

Description 

DAL138LQ2Y10SF0 

DAL138LQ2Y10SF1 

DAL138LQ2Y10SFLS 

DAL138LQ2Y10SFMS 

DAL138LQ2Y10SFHS 

Average Concentration (ng/mL) ± VoRPD 

PFOA 

Concentration 

(ng/mL) 

1.78 

1.82 

1.88 

3.03 

13.1 

VoRecovery 

NA 

NA 

NC 

125 

115 

1.80 ng/mL ±1.7% 

NA = Not Applicable 

NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. 

Page 27 of 60 
GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

Table 32. Trip Blank 

3MUIi/ISID 

GLP10-01-01-07-124 

GLP10-01-01-07-120 

GLP10-01-01-07-121 

GLP10-01-01-07-122 

GLP10-01-01-07-123 

Description 

TRIP BLANK 0 

TRIP BLANK LS 

TRIPBUANKMS 

TRIP BLANK MHS 

TRIP BLANK HS 

PFOA 

Concentration 

(ng/mL) 

<0.247 

1.33 

12.9 

115 

1210 

VoRecovery 

NA 

135'^' 

131 '^' 

117 

123 

NA = Not Applicable 

(1) Field matrix spike did not meet method acceptance criteria of 100% ± 30%. 

Table 33. Rinseate Blanks 

3MLIMSID 

GLP10-01-01-07-068 

GLP10-01-01-07-069 

Description 

DAL137LQ2Y10SFRB 

DAL131RQ2Y10SFRB 

PFOA 

Concentration 

(ng/mL) 

<0.247 

<0.247 

VoRecovery 

NA 

NA 

NA = Not /Applicable 

Page 28 of 60 
GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

10 Conclusion 

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

accuracy and precision for PFOA. Analysis was successfully completed following 3M Environmental 

Laboratory method ETS-8-044.0 described herein. 

11 Data/Sample Retention 

All remaining samples and associated project data (hardcopy and elecrtronic) will be archived according 

to 3M Environmental Laboratory standard operating procedures. 

12 Attachments 

Attachment A: Protocol Amendment 07 (General Project Outline) 

Attachment B: Representative Chromatograms and Calibration Curves 

Attachment C: Analytical Method 

Attachment D: Method Deviation 

Page 29 of 60 
GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

13 Signatures 

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

/ y J^^<^Poyo 

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

Id 

Gary Hohertstdh, 3M Sponsor Representative 

4Whl,i 

Date 

Jaisimha Kesari, Study Director ' / Date 

Page 30 of 60 
GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

Attachment A June/July 2010,. , „ , , ^ , „^ ^ „ ^ „ ^ 

Analytical Protocol: GLP10-01-01 

Amendment 07 

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. 07 

Amendment Date: 

June 16, 2010 

Performing Laboratory 

3M Environmental, Health, and Safety Operations 

3M Environmental Laboratory 

Building 260-5N-17 

Maplewood, MN 55144-1000 

Laboratory Project Identification 

GLP10-01-01 

Sampling Event 

Former Sludge Incorporation Area (FSIA) Groundwater 

Page 1 of 8 

Page 31 of 60 
GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

Attachment A June/Julv 2010^. , „ ^ . ^ , r,^/, ^> o> 

Analytical Protocol: GLP10-01-01 

Amendment 07 

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 RBADS: 

Section 9.2.1 : A stable isotope-labeled internal standard, [(1,2,3,4,5,6,7,8-"C8)-PFOA] will be added to each 

sample, LMS, LCS, procedural blank and calibration standard for aiding quantitation of PFOA and the 

surrc^ate. A stable isotope-labeled sumagate [(1,2,3,4-"C4)-PFOA] will also be added at a fixed level to each 

sample, LMS, LCS, procedural blank, and at variable known concentrations in calibration standards, and 

quantified to determine surrogate recoveries. 

AMEND ro KBAD: 

A stable isotope-labeled intemal standard. [{1,2,3,4.5,6,7.8-"C8)4'FOA] may be added to each sample, LMS, 

LCS, procedural blank and calibration standard for aiding quantitation of PFOA and the surrogate. A stable 

isotope-labeled sun-ogate [{1,2,3,4-^^C4)-PFOA] may also be added at a fixed level to each sample, LMS. LCS, 

procedural blank, and at variable known concentrations in calibration standards, and quantified to detennine 

surrogate recoveries. The use of intemal standards and sunnogates are only appropriate for those sampling 

locations with PFOA coricenlraflons in the low ppb range. Prior to each sampling event, if previously obtained 

PFOA data is available for the sampling points cif interest ttie data will be reviewed to determine if the use of 

intemal standards and surrogates is appropriate for the current sampling event. 

PROTOCOL RBADS: 

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 

Vtxe addition of the General Project Outiine (GPO) for the coilectidn and analysis of groundwater samples 

at Decatur, AL. and conducted as part of the 3M Decatur Phase 3 Program for PFOA (GLP10-01-01). 

The anticipated sample coiiection will occur around the timeframe of June 21. 2010. The groundwater 

samples for this sampling event will be entered into the 3M Environmental Laboratory LIMS as project 

GLP10-01-01-07 and reported as interim report GLP10-01-01-07, (reflecting study GLP10-01-01 and 

amendment -07). 

Reason: 

The reason for this amendment is to document the General Projecit 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 tiiis amendment fonn. 

Page 2 of 8 

Page 32 of 60 
GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

Attachment A June/Julv 2010^. , „ ^ , ^ . r,^^ ^ . ^> 

Analytical Protocol: GLP10-01-01 

Amendment 07 

Amendment Approval 

Gary Hohenstein, Sponsor Representative Date 

7 

Cleston C. Lange, Principal Analytical Investigator Date 

William Reagen, EHS Opjns Environmental Lab Management Date 

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

Page 3 of 8 

Page 33 of 60 
Attachment A 

GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

Analytical Protocol: GLP10-01-01 

Amendment 07 

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 

Cliffton Jacoby, 3M EHS&Opns; Environmental Lab 

Jai Kesari, Weston Solutions 

Charles Young, Weston Solutions 

Tim Frinak, Weston Solutions 

Date: June 16,2010 

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

Decatur Phase 3 Site-Related Monitoring Program; GLP Interim Report 07 - Fonmer Sludge 

Incorporation Area (FSIA) Groundwater 

1 General Project Information 

Contacts 

Lab Request Number 

Six Digit Department Number 

Project Schedule/Test Dates 

3M Sponsor Representative 

Gary Hohenstein 

3M EHS Operations 

3M Building 224-5W-03 

Saint Paul, MN 55144-1000 

Phone:(651)737-3570 

aahohensteiniammm.com 

3M Environmental Laboratory Management 

William K. Reagen 

3IVI EHS Opns, Environmental Laboratory 

260-5N-17 

651 733-9739 

wkreaaen(a!mmm.cora 

Principal Analytical Investigator 

Cleston Lange 

3M EHS Opns, Environmental Laboratory 

260-5N-17 

651 733-9860 

cclanaeOmmm.com 

Santplirig Coordinator 

Timothy Frinak 

Weston Solutions 

Tlmothv.frinak(a!westonsolutions.com 

Phone: (334).332^9123 

GLP10-01-01-07 

Dept #530711, Proiect #0022674449 

Sampling scheduled for the week of June 21, 2010 

All verbal and written correspondence will be directed to Gary Hohenstein. 

Page 4 of 8 

Page 34 of 60 
Attachment A 

GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

Analytical Protocol: GLP10-01-01 

Amendment 07 

2 Background Information and Project Objective(s) 

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

samples cx)llected 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 June 

21, 2010. 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 GLP10-01-01-07. 

3 Project Schedule 

Sample collection bottles will be prepared by 3M Environmental Laboratory for sampling Uie week of June 21, 

2010. Sample bottles will be shipped in coolers overnight to 3M Decatur for arrival on Friday, June 18, 2010. 

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 twenty-seven sampling locations have been specified. For each sampling location, a sample, sample 

duplicate and a minimum of two field matrix spikes will be collected. Table 1 indicates tiie well ID and 

corresponding field spike levels. The "fill to here" line on each 250 mL Nalgene bottle will be 200 mL. Three 

sets of trip blanks consisting of reagent-grade water, a low-level tilp 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. Two additional bottles will be prepared to be used for the preparation 

of the equipment rinseate blanks. A total of 145 sample bottles will be prepared. 

Table 1. Sampiing Locations and Field Matrix Spike levels. 

Well No. 

136R, 137R, 137S, 137L, 

138L 

130L, 131L, 132L, 133R, 

134S, 134L, 136S 

130R, 130S. 131S. 132R, 

132S, 133S, 133L, 135S. 

135L. 136L. 138S, 138R 

131R, 134R, 135R 

TripBlankSet 1,2, and3 

Sample Level 

Low 

Mid 

Hiflh 

Low 

Mid 

High 

Low 

Mid 

High 

Low 

HIph 

Low 

Mid 

Mid-High 

High 

Spike Cone. (ng/mL) 

0.1 

1.0 

10 

1 

10 

100 

10 

100 

1000 

100 

1000 

1 

10 

100 

1000 

Page 5 of 8 

Page 35 of 60 
GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

Attachment A June/July 2010 

Analytical Protocol: GLP10-01-01 

Amendment 07 

5 Tesit Methods 

Samples will be prepared and analyzed by LC/MS/MS following ETS-8-044.0 "Detennination of Perfluorinated 

Compounds In Water by High Performance Liquid Chromatography/Mass Spectrometiy Direct Injection 

Analysis". The data quality objectives for ttiese studies are quantitative results for the target analytes witfi 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. 

Alternately, samples may be analyzed by ETS 8-154.3 "Determination of Perfluorinated Acids, Alcohols, 

Amides, and Sulfonates In Water By Solid Phase Extraction and High Performance Liquid 

Chromatography/Mass Specti-omety. MeUiod ETS-8-154 has been validated for PFOA and PFOS only; 

however, specific quality control samples analyzed with the samples will be used to detennine overall method 

precision and accxinacy. 

6 Reporting Requirements 

For each sampling location, the report will contain the resufte for the sample, sample duplicate, and field matiix 

spikes. Trip blank and trip blank spikes will be reported for frie 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 matiix spike level was not appropriate, due to 

higher than expected analyte concentirations, a laboratory matrix spike may be prepared and will tie included in 

the final report 

7 Email Correspondence 

Attachment A: Sampling Bottle Request 

Page 6 of 8 

Page 36 of 60 
Attachment A 

GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

Analytical Protocol: GLP10-01-01 

Amendment 07 

Project Duration: 21 June through 2 July 2010 Date Required: 18-Jun-lO 

Ship Containers to: 

Weston Solutions, Inc. Field 

Office 

3M Decatur Plant 

1400 State Docks Road 

Decatur, Ai 35601 

256-552-6189 

Attn: Martin Smith 

Sample Media 

Groundwater 

Sample Container Requirements 

Samples 

27 

Duplicate 

Samples 

na 

Rinsate Blank 

Sets 

2 

Trip Blank Sets 

See Note 1 

Note 1: One trip blank will be required for each shipping container returned to the laboratory. It should be 

noted that ice will be required for shipments of soil / sediment samples which rrtay result in an increase in 

the number of shipping containers (and trip blanks) required. 

Note 2: Rinsate Blank Sets should be accompanied with an appropriate volume of water to accomplish the 

sampling. The volume should account for spillage during the rinsing process. 

Note 3: Please note that any bottle sets not used due to unique field conditions will be isolated and returned 

to the laboratory labeled for disposal. 

Page 7 of 8 

Page 37 of 60 
Attachment A 

GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/JulY2010 

Analytical Protocol: GLP10-01-01 

Amendment 07 

Wells Included in This Sampling 

Event: 

Well No. 

130R 

130S 

130L 

131R 

13 IS 

131L 

132R 

132S 

132L 

133R 

133S 

133L 

134R 

134S 

134L 

13SR 

135S 

135L 

136R 

136$ 

136L 

137R 

137S 

i37L 

138R 

138S 

138L 

Page 8 of 8 

Page 38 of 60 
*011ie : U001104O2 

Attachment B 

GLP10-01-01; Interim Report 07 

Analysis of PFOA In Groundwater Samples from Decatur, AL 

June/July 2010 

o100708a linear.rdb {PFOA_TIC): "Quadratic" Regression ("1 / x" weighting): y = -6.42e+003 x'^2 + 1.16e+006 x + 2e+005 (r = 0.9992) 

tn 

8 

of 

< 

O.ZSI 

6.0e7-

5.5e7-

5.0e7-

4.5e7-

4.0e7-

3.5e7-

3.0e7-

2.5e7-

2.0e7-

1.5e7-

1.0e7-

5.0e6-

0.0-

/ 

• / / 

/ 

/ / / / 

/ 

/ 

/ 

,-'-'" 

/ 

• ^^ ^— 

o 

0 5 10 15 20 25 30 35 40 45 50 55 

Concentration, ng/mL 

60 65 70 75 80 85 90 95 

*Daca work-up performed by STW 

Page 1 of 1 

Printing Time: 12:09:10 PM 

Printing Date: Tuesday, September 07, 2010 

Page 39 of 60 
GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

-4yVPrinting Time: 12:05:58 PM 

Printing Date: Monday, September 13, 2010 

Page 40 of 60 

*011ie : U00110402 

I Sample Nama: •o100708a023- Sampte ID: "03 008-147-1(r File: "o100708a.wfr 

Paak Nanna: •PFOA_T)C" M8ss(o6): "413.0/369.1 amu.413.0/168.9 amu.413.0/218.8 a 

I ComfTwrtt: "5.0 ppb curv« point in MittiO Water" Annotation:" 

V0ee6 

1.06e6' 

1.0486 

1.02e6 

I.OOee 

g.80e5 

9.60e5' 

9.40e5 

9.20e5 

S.DOeSe.80e5-

e.60o5' 

e.40«5 

6J?0a5-

8.00e5 

7.BOe5 

7.60e5-

7.40e5 

7.20*5 

7.00e5' 

6.eOe5-

6.60e5 

6.40e5 

6.20e5 

e.OOeS 

5.80e5-

5.6O0S5.40e5 

S.20e5 

5.00e5 

4.B0e5 

4.60e5 

4.40e5-

4.20«5 

4.00e5 

3.80e5-

3.60e5-

3.40e5 

3.20e5 

3.OO0S 

2.80e5 

2.60eS 

Z40«5-

2.20e5 

2.00e5' 

1.60e5 

1.60e5 

1.40e5 

1.20e5 

I.OOeS 

e.00e4 

6.00e4 

4.00e4 

2.00e4-

0,00 

0.84 

A 

*Data work-up performed by STW 

Page 1 of 6 
*011ie : U00110402 

GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

I Sarnple Name: "01007083030" Sample ID: 'Solvent Blank (MilliQ Elerrwntr File: "oi00708a.wifT 

Peak Name: *PFOA_TIC Mass(es]:'413.0/369.1 aniu,413.0/168.daniu.413.0/218.8 

I Comment:"TN10-0237" Annotation:'" 

ModiCied : 

RT Window; 

Exfjcte d BT: 

*Data work-up performed by STW 

Page 2 of 6 

Printing Time: 12:05:58 PM 

Printing Date: Monday, September 13, 2010 

Page 41 of 60 
GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

Printing Time: 12:05:58 PM 

Printing Date: Monday, September 13, 2010 

Page 42 of 60 

*011ie : U00110402 

I

Sairpte Name: '01007083039- Sample ID: "LCS-100707-7' File: 'ol00708a.wtr 

Peak Name: 'PFOA_TIC Mass(e«): "413.ora69.1 amu,413.0/168.9 amu.413.0/218.8 amu" 

Comment "3(^>pb LCS" Annotation; ~ 

4.8e6 

4.7e6-

4.6a6 Hodifi i 

RT Win. 

4.5e6 

4.4a6 

4.3e6 

4.2e6 

4.1e6 

4.0a6-

3.9e6 

3.S«6 

3.7e6 

3.6e6 

3.5e6-

3.4*6-

3.3e6 

3.2s6 

3.1e6 

3.0e6-

2.9e6 

2.8e6 

2.7e6 

2.6a6-

2.5e6 

2.4e6 

2.3e6 

2.2e6 

Zle6 -

2.0e6 

1.9e6 

1.8e6 

1-7e6 

1.6a6 

1.5e6 

1.4«6 

V3e6 

1.2e6-

l.le S 

l,0a6 

e.OeS 

8.0e5 

7.0e5 

6.0e5 

S.OeS 

4.0e5 

3.0e5 

2.0e5-

I.OeS 

0.0 

*Data work-up performed by STW 

Page 3 of 6 
*011ie : U00110402 

GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

I

Sample Name: "01007083050" Sample ID: "LCS-100707-14" File: "o100708a.«Mr 

Peak Name: "PFOA.TIC Pifas$<es): "413,0/369.1 arnu,413.0/168.9 amu.413.0/218.8 amu' 

Comment: "5ppb LC"s ECF" Anno&tion:" 

*Data work-up performed by STW 

Page 4 of 6 

Printing Time: 12:05:58 PM 

Printing Date: Monday, September 13, 2010 

Page 43 of 60 
GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

Printing Time: 12:05:58 PM 

Printing Date: Monday, September 13, 2010 

Page 44 of 60 

•Ollie : U00110402 

I

Sampto Name:-olOOTOaaOTB- Sampte ID: *G1.P1(W)1^31.07-115" Fila: "o10070aa.wr 

Peak Name:'PFOA TIC Masc<ea):'413.0/369.1 aiTiu.413.Dn€8.9amu.413.(V218.8 amu' 

Comment'DAL138lQ2Y10SF(r Annotafion:" 

Sample InJsJ-.; "IS 

Simple Type; Unl-.no--iin 

Calc'ilated Cone: 1.51 ng/mL 

Acq. Date: 7/9/2010 

Arq. Time: i:5i:34 PH 

Wodifisd: 

RT Window: 

Exp«cced RT 

U3h P.^lativf 

Int. Type: 

Retention T 

Area: 

Heigfit: 

Start Tine: 

End Ti»e: 

yes 

JD.O sec 

H.6 min 

KT: No 

Manual 

ne: H. ? nin 

5Sei95 cps 

U . l min 

U . i min 

3.5*5-

3.4«5 

3.3«5 

3.2e5 

3.1 eS 

3.0e5 

2.9«5 

2.8«5 

2.7e5 

2.6«5 

2.5«5 

Z4«5 

2.3e5 

2.2e5 

2.1 «5 

2.0e5 

i.a«5 

1.7e5 

1.6e5 

I.SeS1.4e5 

1.3«5-

1.2e5 

1.1«5' 

I.OeS 

9.0a4 

8.0e4 

7.0e4 

6.0e4-

5.0e4-

4.0a4 

3.0e4-

2.0e4 

1.0e4-

0.0 

*Data work-up performed by STW 

Page 5 of 6 
GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

,il^^^ 

Printing Time: 12:05:59 PM 

Printing Date: Monday, September 13, 2010 

Page 45 of 60 

•Ollie: U00110402 

I

SatTpleName:*o10a708a117' Sample ID;'GLP1O01431.07.040' f He:'o10070ea.wir 

Peak Name:'PFOA_T[C Mass^es):'413.07369.1 amu.413.0/168.9amu,413.0/218.8 amu' 

CofT«ient'DAL132LQ2Y10SF0 (dil1:10r Annotation:~ 

Sam{;l& Indax : 117 

Sjn.pl 

Calc . 

Acq. 

Acq. 

Modi I 

RT W; 

Exp-^c 

9 TVP 

ntra t 

late d 

Pate : 

Time : 

ied : 

ndow: 

t « d R 

H/h 

5.3«6 

5.2fl6 

S.1a6 

5.0e6 

4.7e6 

4.6tt6 

4.5e6 

4.4«6 

4.3*6 

4.2B 6 

4.1«6' 

4.0e6 

3.9e6 

3.8o6-

3.7e6-

3.6e6 

3.5e6-

3.4«6 

3.3e6 

3.2*6 

3.1«6 

3.0e6 

2.9e6' 

2.Be6-

2.7*6 • 

2.6*6 

Z5e 6 

2.4*6 

2.3*6 

2.2*6 

2.1*6 

Z0e6 -

1.9*6' 

1.6*6 

1.7*6 

1.6*6 

1.5*6 

1.4*6 

1.3*6 

1.2*6 

1.1*6 

1.0*6 

9.0*5 

6.0*5 

7.0*5 

6.0*5 

5.0*5 

4.0*5 

3.0*5 

2.0*5 

1,0*5-

0.0 

*Data work-up performed by STW 

Page 6 of 6 
GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

Printing Time: 12:07:07 PM 

Printing Date: Monday, September 13, 2010 

Page 46 of 60 

^Ollie: U00110402 

• Sample Nam*:'0100708*050^ SampI* ID: TCS-l00707-14" File:'o10070aa.Mifr 

• Peak Nam*:-PFOA_TIC- Ma»«(*s):-413.0/369.1 anw,413.0n68.9amu,413.W218.8«muB Comm*nt '5ppb LCS ECP Anrwbtion: ~ 

Sddiple Type : Unknown 

Calculate d Cone : 1.11 ng/mL 

Acq. Dat« : 7/9/201 0 

Acq. Tirae : 5:03:3 2 AM 1.2 

«odi£ied : 

Proc . Algorithm : 

Nois « P«r!,-a.ita7« 

Base . 3Mb. Windc 

Peak-Split . Fac t 

Report Largest P 

Min . Peak Heiyh t 

Min . Pea k Width : 

Jmocthin g Width : 

RT Window: 

Expecte d RT: 

Use Relativ e RT: 

Irtt . Tvps: 

Borentio n Tims: 

Area : It 

Height : 

Star t Ticne: 

End Time : 

No 

IntslliOLJa n 

: 5P 

w: 1.00 

o r : ; 

eak : Mo 

: 0.0 0 

0.0 0 

3 

30. 0 s 

14. 6 n, 

He, 

7a lie- / 

11. 6 n. 

9570 i co^ n 

225?9 6 cp s 

14. 3 m 

H . 7 m 

S 6.00e5 

*Data work-up performed by STW 

Page 1 of 3 
U00110402 

GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

*Data work-up performed by STW 

Page 2 of 3 

Printing Time: 12:07:07 PM 

Printing Date: Monday, September 13, 2010 

Page 47 of 60 
GLP10-01-01; Interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

Printing Time: 12:07:07 PM 

Printing Dace: Monday, September 13, 2010 

Page 48 of 60 

U00110402 

Sarrple Name; -ol00708a11T Samp** ID: "GLPICMJI-01-07-040' File: "o 100708a-Wifr 

•

Peak Name: -PFOA_TIC- Mass{*s): MIS.O/SSS.l amu.413.0/168.9 amu,4l3.0/218.8 amu" 

CommenfD/y.132.Q2Y10SF0 (d31:10r Annotetion: ~ 

Sample Inds>r: i n 

Sa&ple Type: Unknown 

N/A 

111 . 

elliQua i 

l.DD min 

5.3*6 

5.2*6 

5.1*6 

5.0*6 

4.9*6 

4.6*6-

4.7e6 

4.6*6 

4.5*6 

4.4*6 

4.3«6 

4.2*6-

4.1*6 

4.0*6 

3.9*6 

3.e*6 

3.7*6-

3.6*6-

3.5*6-

3.4*6 

3.3*6 

3.2*6 

3.1*6 

3.0*6 

2.9*6-

2.8*6-

2.7*6-

2.6*6 

2.5*6 

2.4*6 

2.3*6 

2.2*6 

2.1*6 

2.0*6 

1.9*6-

1.8*6 

1.5*6 

1.4*6 

1,3*6 

1.2*6 

1.1*6 

1.0*6 

9.0*5 

8.0*5 

7.0*5 

6.0*5 

5.0*5 

4.0*5 

3.0*5 

2.0*5 

1.0*5 

0.0 

*Data work-up performed by STW 

Page 3 of 3 
Document rrc3:fi!i;>siyse!8brit1i«ap«Bt, for 14 days from 09/13/2010 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

3M Enviroranental Laixxratory 

Method 

Method of Analysis for the Determination of Perfluorinated Compounds in Water 

by LC/MS/MS; Direct Injection Analysis 

Method Number: ETS'8-044.0 

Adoption Date: Upon Signing 

Effective Date: Q <///7 /Q, "l 

Approved By: 

^//^/ o • > 

William K. Reagen, Laboratory Manager Date 

ETS-8-044.0 Page 1 of 11 

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

Injection Analysis Page 49 of 60 
Document twx^-t^-wmatkn^m^pmtA, for 14 days from 09/13/2010 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

1 Scope and Application 

This method is to be used to quantify Perfiuorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), 

Perfluorohexanoic Acid (PFHA), Perfluoroheptanoic Acid (PFHpA), Perfluorooctanoic Acid (PFOA), 

Perfluorononanoic Acid (PFNA), Perfluorodecanoic Acid (PFDA), Perfluoroundecanoic Acid (PFUnA), 

Perfluorododecanoic Acid (PFDoA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), 

and Perfluorooctanesulfonate (PFOS) by High Perfonnance Liquid Chromatography coupled to a tandem 

Mass Spectrometric Detector (LC/MS/MS) in clean water samples. Water samples containing heavy 

particulate may require preparation by an alternate method such as ETS-8-154 "Determination of 

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

Performance Liquid Chromatography/Mass Spectrometry". 

This method is considered a performance-based method. Data is considered acceptable as long as the 

defined QC elements are satisfied. 

Sample collection is not covered under this analytical procedure. 

2 IVIethod Summar y 

Clean aqueous samples are analyzed 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 centrifuge prior to removing a sample aliquot, or filtered. 

This is a performance-based method. Method accuracy is determined for each sample set using multiple 

laboratory control spikes at multiple concentrations. This method also requires that the precision and 

accuracy for each sample be determined using field matrix spikes to verify that the method is applicable to 

each sample matrix. Sample results for spikes outside of 70% to 130%, may be flagged as such (with 

expanded accuracy statements), or will not be reported due to non-compliant quality control samples. 

Fortification levels for field matrix spikes and for laboratory matrix spikes should be at least 50% of the 

endogenous level and less than 10 times the endogenous level to be used to determine the statement of 

accuracy for analytical results. 

3 Definitions 

3.1 Calibration Standard 

A solution prepared by spiking a known volume of the Wori<ing Standard (WS) into a predetermined 

amount of ASTM Type I, HPLC grade water, or other suitable water, and analyzed according to this 

method. Calibration standards are used to calibrate the instrument response with respect to analyte 

concentration. 

3.2 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. 

3.3 Field Blank (FB)/Trip Blank 

ASTM Type 1, 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 FB is to determine if test substances or 

other interferences are present in the field environment. This sample is also referred to as a Trip Blank. 

ETS-8-044.0 Page 2 of 11 

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

Injection Analysis 

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June/July 2010 

3.4 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. 

3.5 Field Matrix Spike (FMS) 

A sample to which known quantities of the target analytes 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 should be spiked between 

approximately 50% and 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. The FMS is analyzed to ascertain if any matrix 

effects, interferences, or stability issues may complicate the interpretation of the sample analysis. 

3.6 Trip Blank Spike (Field Spike Control Sample, FSCS) 

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

target analytes are added in the laboratory prior to the shipment of the collection bottles. The FSCS is 

extracted and analyzed exactly like a study sample to help determine if the method is in control and 

whether a loss of analyte could be attributed to holding time, sample storage and/or shipment issues. A 

low and high FSCS are appropriate when expected sample concentrations are not known or may vary. At 

least one separate, un-spiked sample must be taken at the same time and place as each FMS. 

3.7 Laboratory Control Sample (LCS) 

An aliquot of control matrix to which known quantities of the target analytes are added in the laboratory at 

the time of sample extraction. At least two levels are included, one generally at the low end of the 

calibration curve and one near the mid to upper range of the curve. The LCSs are extracted and analyzed 

exactly like a laboratory sample to determine whether the method is in control. LCSs should be prepared 

each day samples are extracted. 

3.8 Laboratory Matrix Spike (LMS) 

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

in the laboratory. The LMS is analyzed exactly like a laboratory sample to detennine whether the sample 

matrix contributes bias to the analytical results. The endogenous concentrations of the analytes in the 

sample matrix must be determined in a separate aliquot and the measured values in the LMS corrected 

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

3.9 Laboratory Sample 

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

3.10 Limit of Quantitation (LOQ) 

The lower limit of quantitation (LLOQ) for a dataset is the lowest concentration that can be reliably 

quantitated within the specified limits of precision and accuracy during routine operating conditions. To 

simplify data reporting, the LLOQ is generally selected as the lowest non-zero standard in the calibration 

curve that meets method criteria. Sample LLOQs are matrix-dependent. 

The upper limit of quantitation (ULOQ) for a dataset is the highest concentration that can be reliably 

quantitated within the specified limits of precision and accuracy during routine operating conditions. The 

highest standard in the calibration curve that meets method criteria is defined as the ULOQ. 

ETS-8-044.0 Page 3 of 11 

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

Injection Analysis 

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Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

3.11 Method 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. 

3.12 Sample 

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

material. 

3.13 Stock Standard Solution (SSS) 

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

compound. 

3.14 Surrogate 

A compound similar in chemical composition and behavior to the target analyte(s), but is not normally 

found in the sample(s). A surrogate compound is typically a target analyte with at least one atom 

containing an isotopically-labeled substitution. If used, surrogate(s) are added to all samples and quality 

control samples. Surrogate(s) are added to quantitatively evaluate the entire analytical procedure 

including sample collection, preparation, and analysis. Inclusion of a sun-ogate analyte is an optional 

quality control measure and is NOT required. 

3.15 Working Standard (WS) 

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

calibration standards and other required analyte solutions. 

4 Warnings and Cautions 

4.1 Health and Safety 

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

however, each should be treated as a potential health hazard. The analyst should wear gloves, a lab 

coat, and safety glasses to prevent exposure to chemicals that might be present. 

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

regulations regarding the handling of the chemicals used in this method. A reference file of material safety 

data sheets (MSDS) should be available to all personnel involved in these analyses. 

4.2 Cautions 

The analyst must be familiar with the laboratory equipment and potential hazards including, but not limited 

to, the use of solvents, pressurized gas and solvent lines, high voltage, and vacuum systems. Refer to the 

appropriate equipment procedure or operator manual for additional infomnation 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. 

ETS-8-044.0 Page 4 of 11 

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

Injection Analysis 

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June/July 2010 

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 Equipment 

6.1 Instrumentation and Equipment 

A high performance liquid chromatograph capable of pumping up to two solvents and equipped with a 

variable volume injector capable of injecting 5-100 |JL connected to a tandem Mass Spectrometer 

(LC/MS/MS). I 

Analytical balance capable of reading to 0.0001 g 

A device to collect raw data for peak integration and quantitation 

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

Gas tight syringes, 25pL, 50pL, lOOpL, 250IJL, 500pL, lOOOpL. 

1 mL plastic HPLC autovial. 

Disposable pipettes, polypropylene or glass as appropriate 

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

6.2 Chromatographic System 

Guard Column: Prism RP, 4.6 mm x 50 mm, 5 pm 

Analytical Column: Betasil CI 8,4.6 mm x 100 mm, 5 pm 

Temperature: 10°C 

Mobile Phase (A): 2 mM Ammonium Acetate in Water 

Mobile Phase (B): Methanol 

Gradient Program: 

Time (min) 

0.0 

0.5 

11.0 

13.5 

13.6 

17.0 

%A 

97 

97 

5 

5 

97 

97 

%B 

3 

3 

95 

95 

3 

3 

Flow Rate 

(mL/min) 

1.0 

1.0 

1.0 

1.0 

1.0 

1.0 

Injection Volume: 100 pL 

Quantitation: Peak Area - quadratic curve fit, 1/x weighted. 

RunTime: ~ 17minutes. 

The previous information is intended as a guide; alternate conditions and equipment may be used 

provided that data quality objectives are met. 

ETS-8-044.0 Page 5 of 11 

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

Injection Analysis 

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June/July 2010 

6.3 MS/MS System 

6.3.1 Mode: Electrospray Negative ion, MRM mode, monitoring the following transitions: 

Analyte 

PFBA 

PFPeA 

PFHA 

PFHpA 

PFOA 

PFNA 

PFDA 

PFUnA 

PFDoA 

PFBS 

PFHS 

PFOS 

Transition Monitored 

213^169 

263^219 

313-> 269 and 313-> 119 

363 -^ 319, 363 ^ 169 and 363 ^ 119 

413 ^ 369, 413 -» 219 and 413 ^ 169 

463 -> 419, 463 -> 169 and 463 -> 219 

513 -» 469, 513 -> 219 and 513 ^ 269 

563 -^ 519, 563 -> 269 and 563 -> 219 

613 -> 569, 613 ^ 169 and 613 ^ 319 

299 -» 80 and 299 -» 99 

399 -^ 80 and 399 -> 99 

499 -^ 80, 499 ^ 99 and 499 -> 130 

Multiple transitions for monitoring the analytes is an option, as summing multiple transitions may provide 

quantitation of isomers that more closely matches NMR data and may have the added benefit of 

increased sensitivity. The use of one daughter ion is acceptable if method sensitivity is achieved, 

provided that retention time criteria are met to assure adequate specificity. 

The previous information is intended as a guide, alternate instalments and equipment may be used. 

7 Reagents and Standards 

7.1 Chemicals 

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

Methanol - HPLC grade 

Ammonium Acetate -A. C.S. Reagent Grade 

7.2 Standards 

Perfiuorobutanoic Acid (PFBA - C4 acid); Oakwood Products, Inc 

Perfluoropentanoic Acid (PFPeA - C5 acid, also known as NFPA, nonafluoropentanoic acid); Alfa Aesar 

Perfluorohexanoic Acid (PFHA-C6 acid); Oakwood Products, Inc 

Perfluoroheptanoic Acid (PFHpA - C7 acid, also known as TDHA, tridecafluoroheptanoic acid); Oakwood 

Products, Inc 

Perfluorooctanoic Acid (PFOA - C8 acid); 3M 

Perfluorononanoic Acid (PFNA-C9 acid); Oakwood Products, Inc 

Perfluorodecanoic Acid (PFDA-C10 acid); Oakwood Products, Inc 

Perfluoroundecanoic Acid (PFUnA-C11 acid); Oakwood Products, Inc 

Perfluorododecanoic Acid (PFDoA-CI 2 acid); Oakwood Products, Inc 

Perfluorobutanesulfonate (PFBS - C4 sulfonate); 3M 

Perfluorohexanesulfonate (PFHS - C6 sulfonate); 3M 

Perfluorooctanesulfonate (PFOS - C8 sulfonate); 3M 

ETS-8-044.0 Page 6 of 11 

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

Analysis 

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June/July 2010 

The previous information is intended as a guide. Reagents and standards from alternate sources may be 

used. 

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 

Note: Alternative volumes may be prepared as long as the ratios of the solvent to solute ratios are maintained. 

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, pL volumes may be spiked into volumetric flasks 

when diluting stock solutions to appropriate levels. 

100 pg/mL target analyte SSSs—Weigh out 10 mg of analytical standard (corrected for percent salt and 

purity) and dilute to 10OmL with methanol or other suitable solvent, in a 10OmL volumetric flask. Transfer to a 

125mL 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 con-ection 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 CsFiySOs'K* with purity 90% = 8.35mg CsFiySOs" (10 mg*0.90*0.9275=8.35 mg) 

5 Mg/mL (5000 ng/mL) mixed working standard^Add 0.5mL each of the 100pg/mL SSSs to a lOmL volumetric 

flask and bring up to volume with solvent. 

250 ng/mL mixed working standard—Add 1.25mL of the 5 pg/mL -mixed wori<ing standard solution to a 25mL 

volumetric flask and bring up to volume with solvent. 

125 ng/mL mixed standard—^Add 625pL of the 5 pg/mL-mixed worthing standard solution to a 25mL volumetric 

flask and bring up to volume with solvent. 

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

procedure or in a refrigerator at 4°±2°C for a maximum period of 6 months from the date of preparation. 

ETS-8-044.0 Page 7 of 11 

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

Analysis 

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7.5 Calibration Standards 

Using the working standards described above, prepare calibration solutions in ASTM Type I water, HPLC water, or 

other suitable water, using the following table as a guideline. Note: Volumes of water 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. 

Concentration 

of WS, ng/mL 

125 

125 

125 

125 

250 

250 

250 

250 

5000 

5000 

5000 

Volume of WS.fd. 

10 

15 

20 

30 

20 

50 

100 

200 

25 

50 

100 

Final Volume of 

Calibration Standard (mL 

of ASTM Type 1 Water, or 

other suitable water) 

50 

50 

50 

50 

50 

50 

50 

50 

50 

50 

50 

Final Concentration of 

Calibration Standard, ng/mL 

(ppb) in ASTM Type 1 Water, 

or other suitable water 

0.025 

0.0375 

0.050 

0.075 

0,100 

0.250 

0.500 

1.00 

2.50 

5.00 

10.0 

8 Sample Handling 

8.1 Water Sample Preparation 

This method is applicable to clean 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 plastic autovial. Plastic is 

preferred over the use of glass autovials, to prevent the possibly of fluorochemical sticking to the glass. 

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

Prepare method QC samples and multiple method blanks and aliquot into labeled plastic autovials. 

Prepare at least five method blanks. 

9 Sample Analysis - LC/MS/MS 

Analyze the standard curve prior to each set of samples. The standard curve may be plotted using a linear fit, 

weighted 1/x or unweighted, or by quadratic fil (y = ax^ •<• bx -i- c), weighted 1/x or unweighted, using suitable 

software. The calibration curves may include but should not be forced through zero. The mathematical method 

used to calculate the calibration curve should be applied consistently throughout a study. Any change should be 

thoroughly documented in the raw data. 

High and/or low points may be excluded from the calibration curves to provide a better fit over the range 

appropriate to the data or because they did not meet the pre-detemnined acceptance criteria. Low-level curve 

points should also be excluded if their area counts are not at least twice that of the method and/or solvent blanks. 

The coefficient of detennination (r^) value for the calibration curve must be greater than or equal to 0.990. Each 

point in the curve must be within ±25% of the theoretical concentration with the exception of the LLOQ, which may 

ETS-8-044.0 Page 8 of 11 

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

Analysis 

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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 constaict 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. 

Continuing calibration verifications (CCV) are analyzed to verify the accuracy of the calibration curve. Analyze a 

mid-range calibration standard, one of the same standards used to construct the calibration curve, at a minimum 

after every tenth sample, not including solvent blanks, with a minimum of one per sample set. Calibration 

verification injections must be within ±25% to be considered acceptable. The calibration curve and the last passing 

CCV will then bracket acceptable samples. Multiple CCV levels may be used. 

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

curve should be further diluted and reanalyzed. 

10 Quality Control 

10.1 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. 

10.2 Method Blanks 

Method blanks must be prepared with each analysis batch. At least five method blanks must be prepared. 

Method blanks may be injected multiple times, but no more than 3 injections should be removed from a single 

method blank. At a minimum, method blanks are analyzed prior to instrument calibration, prior to the analysis of 

CCV samples, and at the end of the analytical run. 

The mean area count for each analyte in the method blanks must be less than 50% of the area count of the LOQ 

standard. The standard deviation of the area counts of these method blanks should be calculated and reported. If 

the mean area counts 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, or alternatively, the method blanks must be evaluated 

statistically to detennine outliers, or technical justification to eliminate one or more results should be made. 

10.3 Sample Replicates 

Samples duplicates are collected in the field. The relative percent difference, RPD, should be reported. RPD 

results greater than 20% will be flagged in the report, but will not be excluded from reporting. The requirement for 

replicates excludes field blanks. 

10.4 Surrogate Spikes 

Surrogate spikes are not required but may be used on project specific requirements. 

10.5 Lab Control Sample 

Triplicate lab control spikes at a minimum of two different concentrations are to be prepared with each preparation 

batch. Low lab control spikes should be prepared at concentrations in the range of five to ten times higher than the 

targeted LOQ and high lab control spikes should be prepared at concentrations near the mid-point of the curve. 

The relative standard deviation of the control spikes evaluated independently at each concentration level must be 

less than or equal to 20% and the average recovery must be 80-120%. If the above criteria are not met, the entire 

set of samples should be re-injected or re-prepared as appropriate. 

ETS-8-044.0 Page 9 of 11 

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

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10.6 Field Matrix Spikes / Lab Matrix Spikes 

Recoveries of field matrix spikes and laboratory matrix spikes are anticipated to be between 70% and 130% of the 

fortified levels. Sample results for spikes outside of 70% to 130%, may be flagged as such (with expanded 

accuracy statements), or will not be reported due to non-compliant quality control samples. 

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 detennine the statement of accuracy for analytical results. 

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

11 Data Analysis and Calculations 

Use the following equation to calculate the amount of analyte found (in ng/mL, based on peak area) using the 

standard curve (linear regression parameters) generated by an appropriate software program: 

. ,^ , ., , ,, (Peak Area-Intercept) ^_ Analyte found (ng/mL) = -^ ^-^ x DF 

DF = factor by which the final volume was diluted, if necessary. 

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

percent recovery. 

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

Analyte added (ng/mL) 

12 Method Performance 

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

Nonconfonnance to any specified parameters must be described and discussed if the Technical Manager (nonGLP study) or Study Director (GLP study) chooses to report the data. 

If criteria listed in this method performance section are not met, maintenance may be performed on the system and 

samples reanalyzed, or other actions taken as appropriate. Document all actions in the raw data. 

If data are to be reported when perfonnance criteria have not been met, the data must be footnoted on tables and 

discussed in the text of the report. 

12.1 System Suitability 

System Suitability standards are not a required component of this method. If required by protocol or by the 

technical manager, a minimum of three system suitability samples are injected at the beginning of each analytical 

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

calibration curve and are repeated injections from one autosampler vial. The system suitability injections must 

have area counts with an RSD of S5% and a retention time RSD of ^2% to be compliant. 

12.2 Quantitation 

Calibration Curve: The coefficient of detennination (r^) value for the calibration curve must be greater than or 

equal to 0.990. Each point in the curve must be within ±25% of the theoretical concentration with the exception of 

the LLOQ, which may be within ±30%. 

CCV Performance: The calibration standards that are interspersed throughout the analytical sequence are 

evaluated as continuing calibration verifications in addition to being part of the calibration curve. The accuracy 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. 

ETS-8-044.0 Page 10 of 11 

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

Analysis 

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Demonstration of Specificity: Specificity is demonstrated by chromatographic retention time (within 4% of 

standard) and the mass spectral response of unique ions. 

12.3 Sensitivity 

The targeted limit of quantitation for all analytes is 0.025 ng/mL. The LOQ for any specific analyte may vary 

depending on the evaluation of appropriate blanks and the accuracy of the low-level calibration curve points. Refer 

to Section 10 for additional details. 

12.4 Accurac y 

This method and required quality control samples are designed to generate data that are accurate to +/-30%. 

Section 10 contains additional information regarding the required accuracy of laboratory control spikes, field matrix 

spikes and laboratory matrix spikes. 

12.5 Precision 

Samples should be collected in duplicate in the field. The relative percent difference, RPD, should be reported. 

RPD results greater than 20% will be flagged in the report, but will not be excluded from reporting. The 

requirement for replicates excludes field blanks or rinse blanks. 

Section 10 contains additional infomnation regarding the required precision of laboratory control spikes. 

13 Pollution Prevention and Waste Management 

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

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

14 Records 

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

Infomnation 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 (instmment batch records, instrument acquisition 

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

15 Affected Documents 

None. 

16 Revisions 

Revision 

Number Summary of Changes 

ETS-8-044.0 Page 11 of 11 

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

Analysis 

Page 59 of 60 
3M Confidential 

GLP10-01-01; interim Report 07 

Analysis of PFOA in Groundwater Samples from Decatur, AL 

June/July 2010 

RECORD OF DEVIATION/NONCONFORMANCE 

/. Identification 

study / Project No. 

GLP10-01-01-07 

Deviation type 5 

(Check one) D 

I Date(s) of Occurrence: 

i o100708aand m100812a 

SOP D Equipment Procedure 

Protocol 0 GPO 

Document Number: 

ETS-8-044.0 

0 

D 

Method 

Other: 

//. Description (attach extra pages as needed) 

Method Requirements: 

1. LCS average recovery of 100% ± 20%. 

2. CCV recovery of 100% ± 25% analyzed every tenth sample. 

3. FMS recovery of 100% ± 30%. 

Actual procedure/process: 

(1) LCS average recovery for branched PFOA was >120%. It appears that there is an analytical 

bias when quantitating branched isomers of PFOA against a calibration curve prepared from 

linear PFOA (o100708a and ml 00812a). 

(2) Three of the ending CCVs analyzed during the o100708a run had recoveries ranging from 

71.0% to 74.1%. (0100708a). 

(3) Two locations, 137L and 134S had one FMS recovery at >130% (o100708a). 

///. Actions Taken 

(suet) as amendment issued, SOP revision, etc.) 

Corrective Action (D Yes 0 No) Reference: 

Acceptability of the nonconforming work: 

1) The linear + branched PFOA LCS when quantitated against a calibration curve prepared from 

linear PFOA have been quantitating around 15-30% higher. By quantitating the linear and 

branched isomers of PFOA separately, against a linear PFOA curve, and summing the 

resulting concentrations, appears to help reduce the recovery of the linear + branched PFOA 

by 5-15%. The method analytical uncertainty was determined based on the highest average 

recovery for the linear + branched PFOA LCS (141%). 

2) Twenty-one CCVs were analyzed during the course of the run (o100708a) with the three 

ending CCVs just outside the acceptance criteria. Reported sample results bracketed by 

these ending CCVs will be noted in the final report. 

3) The two locations with FMS recoveries outside method acceptance criteria will be footnoted 

in the final report. _ 

Actions: D Halting of Work D Client Notification D Work Recall 

IZi Other: Deviations will be noted in final report. 

D Withholding of Report 

Project Lead/PAI Approval: Sjusan Wolf 

Stu^y DTrectorTif GCPF " ~^ ^ 

Date; 

Ma/ /o 

Sponsor Approval (for GLFnprotocol deviations): NA Date: m ' 

Technical Reviewer (optional): NA Date: NA 

Laboratory Department Manager Approval: Date: 

IV. Authorization to Resume Wor k 

Wfiere tialting of work occurred, resumption of work must first be approved by Laboratory Management 

Laboratory Department Manager Approval: NA Date: NA 

Deviation No. 

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

Attachment A ETS-4-008.7 Page 1 of 1 

Documentation of Deviations and Control of Nonconforming Testinc, ^^^^ ^° °' ^°