GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

3M 

GLP10-01-02: Interim Report 23 - Analysis of PFBS. PFHS. and PFOS in Groundwater 

Samples Collected at the Off-Site 610 Wells in Decatur. AL in September 2011 

Study Title 

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

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

Site-Related Monitoring Program 

Data Requirement 

EPA TSCA Good Laboratory Practice Standards 40 CFR Part 792 

Study Director 

Jaisimha Kesari P.E., DEE 

Weston Solutions, Inc. 

1400 Weston Way 

Westchester, PA 19380 

Phone: 610-701-3761 

Author 

Susan Wolf 

3M Environmental Laboratory 

Interim Report Completion Date 

Date of signing 

Performing Laboratory 

3M Environmental Health and Safety Operations 

Environmental Laboratory 

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

St. Paul, MN 55144 

Project Identification 

GLP10-01-02-23 

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 Calibration Laboratories", in accordance with the A2LA Certificate #2052.01. 

Dj Testing that complies with this International Standard also operate In accordance with ISO 9001:2000. 

Testing Cert #2052.01 

Page 1 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

This page has been reserved for specific country requirements. 

Page 2 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

GLP COMPLIANCE STATEMENT 

Report Title: Interim Report 23 - Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Collected at the Off-Site 610 Wells in Decatur, AL in September 2011 

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

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

Site-Related Monitoring Program. 

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

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

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

4t; l( 

Gary Hohi instein, Sponsor Representative Date 

Jaisimha Kesari, P.ErrDEE, Study Director 

Page 3 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

QUALITY ASSURANCE STATEMENT 

Report Title: Interim Report 23 - Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Collected at the Off-Site 610 Wells in Decatur, AL in September 2011 

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

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

Site-Related Monitoring Program. 

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

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

laboratory management and study director. 

Inspection Dates Phase 

Date Re ported to 

Inspection Dates Phase Testing Facility 

Management 

Study Director 

10/6/11 In-Phase Sample 

Preparation 10/11/11 10/11/11 

10/17-10/18/11 Data and Report 10/31/11 10/31/11 

QAU Represellative Date 

Page 4 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

TABLE OF CONTENTS 

GLP Compliance Statement 3 

Quality Assurance Statement 4 

Table of Contents 5 

List of Tables 6 

1 Study Infomriation 7 

2 Summary 8 

3 Introduction 8 

4 Test & Control Substances 9 

5 Reference Substances 9 

6 Test System 1 

7 Method Summary 1 

7.1 Methods 1 

7.2 Sample Collection 1 

7.3 Sample Preparation 1 

7.4 Analysis 1 

8 Analytical Results 12 

8.1 Calibration 12 

8.2 System Suitability 13 

8.3 Limit of Quantitation (LOQ) 13 

8.4 Continuing Calibration 13 

8.5 Blanks 13 

8.6 Lab Control Spikes (LCSs) 13 

8.7 Analytical Method Uncertainty '.15 

8.9 Field Matrix Spikes (FMS) 15 

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Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

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9 Data Summary and Discussion 16 

10 Conclusion 19 

11 Data/Sample Retention 19 

12 Attachments 19 

13 Signatures 20 

LIST OF TABLES 

Table 1. Summarized PFBS, PFHS, and PFOS Results (Off-Site 610 Wells) 8 

Table 2. Sample Description Key Code 11 

Table 3. Instrument Parameters 12 

Table 4. Liquid Chromatography Conditions 12 

Table 5. Mass Transitions 12 

Table 6: Limit of Quantitation (LOQ) 13 

Table 7. Laboratory Control Spike Recovery 14 

Table 8. Analytical Uncertainty 15 

Table 9. Field Matrix Spike Levels 16 

Table 10. DAL GW 61 OS 110921 17 

Table 11. DAL GW 61OL 110921 17 

Table 12. Trip Blank 18 

Page 6 of 60 
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Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

1 Study Information 

Sponsor 

3M Company 

Sponsor Representative 

Gary Hohenstein 

3M EHS Operations 

3M Building 224-5W-03 

Saint Paul, MN 55144-1000 

Phone:(651)737-3570 

Study Director 

Jaisimha Kesari, P.E., DEE 

Weston Solutions, Inc. 

Westchester, PA 19380 

Phone: (610) 701-3761 

Fax: (610)701-7401 

j. kesari@westonsolutions.com 

Study Location 

Testing Facility 

3M EHS Operations 

3M Environmental Laboratory 

Building 260-5N-17 

St. Paul, MN 55144 

Study Personnel 

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

Cleston Lange, Ph.D., Principal Analytical Investigator, (clanqe(a>mmm.com): phone (651 )-733-9860 

Susan Wolf, 3M Analyst 

Chelsie Grochow, Analyst 

Kevin Eich, Analyst 

Kelly Ukes, Analyst 

Jonathan Steege, Analyst 

Study Dates 

Study Initiation: March 8, 2010 

Interim 23 Experimental Termination: October 8,2011 

Interim Report Completion: Date of Interim Report Signing 

Location of Archives 

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

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

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

Page 7 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

2 Summary 

The 3M Environmental Laboratory received groundwater samples from two different wells identified as 

the off-site 610 Wells in Decatur, AL. A total of eleven sample bottles were received at the 3M 

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

and perfluorobutane sulfonate (PFBS), and included duplicate groundwater samples from each 

sampling location. Samples also included two field matrix spike (FMS) samples for each location and 

one trip blank set containing Milli-QTM water and appropriate trip blank spikes. 

The groundwater samples and trip blanks associated with GLP10-01-02-23 were received from 

Weston personnel on October 6,2011. All of the samples were prepared and analyzed for PFBS, 

PFHS, and PFOS following 3M Environmental Laboratory Method ETS-8-044.0 and conducted under 

3M project GLP10-01-02-23. The average measured PFBS, PFHS, and PFOS concentrations are 

summarized in Table 1. The trip blank sample was below the lower limit of quantitation (LLOQ), 

indicating adequate control of sample contamination during shipping and sample collections. The 

analytical method uncertainties associated with the reported results are: PFBS + 9.3%, PFHS + 8.4% 

and PFOS+ 14%. 

Table 1. Summarized PFBS, PFHS, and PFOS Results (Off-Site 610 Wells). 

3M LIMS ID Sample Description 

PFBS 

Concentration 

(ng/mL) 

PFHS 

Concentration 

(ng/mL) 

PFOS 

Concentration 

(ng/mL) 

GLP10-01-01-023-001 DAL GW 61OS-0-110921 0.0509 0.0809 0.177 

GLP10-01-01-023-002 DALGW610S-DB-110921 0.0544 0.0855 0.128 

Average 0.0527 0.0832 0.153 

%RPD Sample/Sample Dup 6.6 5.5 32(1) 

GLP10-01-01-023-005 DAL GW 61OL-0-110921 0.243 0.250 1.35 

GLP10-01-01-023-006 DAL GW 61OL-DB-110921 0.252 0.260 1.47 

Average 0.248 0.255 1.41 

VoRPD Sample/Sample Dup 3.6 3.9 8.5 

GLP10-01-01-023-009 DAL-GW-TRIP01-1 <0.0250 <0.0250 <0.0232 

The analytical method uncertainties associated with the reported results are: PFBS ± 9.3%, PFHS ± 8.4 %, and 

PFOS ±14%. 

(1) The relative percent difference (RPD) did not meet method acceptance criteria of <20%. 

3 Introduction 

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

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

information regarding concentrations of perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate 

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

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

conducted to analyze groundwater samples collected from the off-site 610 Wells located in Decatur, AL 

for PFBS, PFHS, and PFOS in an effort to characterize regional groundwater conditions. 

Page 8 of 60 
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Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

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

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

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

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

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

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

being sent to the field for sample collection. All sample bottles included the addition of ^*02-PFBS, 

"Ca-PFHS, and "Cs-PFOS (internal standard) at a nominal concentration of 1 ng/mL. All sample 

bottles also included the addition of ^^C4-PF0S (surrogate standard) at a nominal concentration of 0.1 

ng/mL. See section 8.8 of the report for field matrix spike levels. The "C4-PFOS surrogate standard 

was inadvertently not included in the analysis of the samples. 

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

Laboratory method ETS-8-044.0 "Method of Analysis for the Determination of Perfluorinated 

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

used to aid in the data quality objectives. 

Table 1 summarizes the average PFBS, PFHS, and PFOS concentrations for the duplicate samples 

collected and the trip blank. Tables 10-12 summarize the individual sample results and the associated 

field matrix spike recoveries. All results for the quality control samples prepared and analyzed with the 

samples are reported and discussed elsewhere in 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 

Reference Substance 

PFHS 

(linear) 

r'CJPFHS 

(linear) 

Chemical Name Perfluorohexane sulfonate 

Sodium 

Perfluorohexanesulfonate 

Chemical Formula CeF-isSOa "Cs^CsFisSOsNa' 

Identifier Sodium Salt CAS#MPFC-C-0511 

Use Target Analyte Reference 

Standard Intemal Standard 

Source Wellington Wellington 

Expiration Date 03/25/2018 05/25/2014 

Storage Conditions Frozen Frozen 

Chemical Lot Number LPFHxSAMOS 092310 

TCR Number TCR08-0018 TCR11-0016 

Physical Description Crystalline Liquid 

Purity 98% 5 MQ/mL 

Page 9 of 60 
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Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Reference Substance 

PROS 

(linear) 

PFOS 

(linear + branched) 

["CJ PFOS 

(linear) 

Chemical Name Perfluorooctane sulfonate Perfluorooctane sulfonate 

Sodium 

Perfluorooctanesulfonate 

Chemical Formula CsFiySOa CsFiySOs "CeFiySOjNa" 

Identifier 

Potassium Salt 

CAS #2795-39-3 

Potassium Salt 

CAS #2795-39-3 CAS#MPFC-C-0511 

Use Field Matrix Spike 

Reference Standard 

Target Analyte Reference 

Standard Intemal Standard 

Source Wellington Wellington Wellington 

Expiration Date 10/18/2018 3/17/2014 05/25/2014 

Storage Conditions Frozen Frozen Frozen 

Chemical Lot Number LPFOSKBM06 brPFOSK0708 092310 

TCR Number TCR08-0001 TCR11-0010 TCR11-0016 

Physical Description Crystalline Liquid Liquid 

Purity 100% 99.9% 5 Mg/mL 

Reference Substance 

PFBS 

(predominantly linear) 

[1802] PFBS 

(linear) 

Chemical Name Perfluorobutane sulfonate 

[^®02]-Ammonium 

Perfluorobutanesulfonate 

Chemical Formula C4F9SO3 C4F9S['^02]0-NH4^ 

Identifier Potassium Salt NA 

Use 

Target Analyte Reference 

Standard Intemal Standard 

Source 3M RTI International 

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

Storage Conditions Frozen Frozen 

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

TCR Number TCR-121 TCR-1009,TCR-1031 

Physical Description White Powder Liquid 

Purity 96.7% >99% 

(1) Custom mixture of seven mass-latieled ("C) pertluoroail<ylcartx)xylic acids, two mass labeled ("C) 

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

Page 10 of 60 
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Analysis of PFBS, PFHS and PFOS in Groundwater 

Off-Site 610 Wells; September 2011 

6 Test System 

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

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

specific lot of test substance. 

Table 2. Sample Description Key Code. 

String Number String Descriptor Example 

Example DAL-GW- 610S-LS-110921 

1 Sample Location DAL= Decatur, Alabama 

2 Sample Type GW= Groundwater 

3 Well ID Example: DAL 610 

S = Epilarst 

L = Limestone bedrock 

4 Sampling Date 110921-September 21, 2011 

5 Sample Type 0=primary sample 

DB = duplicate sample 

LS = low spike 

HS = high spike 

7 Method Summary 

7.1 Method 

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

"Method of Analysis for the Determination of Periluorinated Compounds In Water by High Performance 

Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". 

7.2 Sample Collection 

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

Environmental Laboratory. Sample bottles associated with GLP10-01-02-23 were returned to the 

laboratory at ambient conditions on October 6, 2011. Samples were stored refrigerated at the laboratory 

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

each cooler of sample collection bottles. 

7.3 Sample Preparation 

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

analysis. 

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

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

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

being sent to the field for sample collection 

7.4 Analysis 

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

performance liquid chromatography/ tandem mass spectrometry (HPLC/MS/MS). Detailed instrument 

Page 11 of 60 
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Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

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

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

Table 3. Instrument Parameters. 

Instrument Name ETSKiri< 

Analytical Method Followed ETS-8-044.0 

Analysis Date 10/7/11 - PFBS PFOS and PFHS 

Liquid Chromatograph Agilent 1200 

Guard column Betasil 018 (4.6 mm X 100 mm), 5vi 

Analytical column Betasil 018 (4.6 mm X 100 mm), 5n 

Injection Volume 25 nL 

Mass Spectrometer Applied Biosystems API 5500 

Ion Source Turbo Spray 

Electrode Turbo ion electrode 

Polarity Negative 

Software Analyst 1.5.2 

Table 4. Liquid Chromatography Conditions. 

step Total Time Flow Rate Percent A Percent B 

Number (min) (fjUmin) (2 mM ammonium acetate) (Methanol) 

ETS-8-044.0 Analyzed 10/7/2011 

0 0 750 97.0 3.0 

1 2.0 750 97.0 3.0 

2 14.5 750 5.0 95.0 

3 15.5 750 5.0 95.0 

4 16.5 750 97.0 3.0 

5 20.0 750 97.0 3.0 

Table 5. Mass Transitions. 

Analyte 

Mass Transition 

Q1/Q3 

Reference 

Material 

Structure 

Internal Standard 

Mass Transition 

Q1/Q3 

PFBS 299/80 

Linear ("OJ-PFBS 303/84 

299/99 

PFHS 

399/80 

Linear t"CJ-PFHS 402/80 399/99 

PFOS 

499/80 

Linear & 

Branched PFOS 499/99 t'CJ-PFOS 507/80 Linear & Branched PFOS t'CJ-PFOS 507/80 

499/130 

Linear & 

Branched t'CJ-PFOS 507/80 

Dwell time was 30 msec for each transition. Tfie individual transitions were summed to produce a "total ion 

cfiromatogram" (TIC), wtiicfi was used for quantitation. 

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Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Weils; September 2011 

8 Analytical Results 

8.1 Calibration 

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

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

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

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

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

ranging from approximately 0.025 ng/mL to 25 ng/mL was prepared. Sampling location DAL GW 61 OS 

was quantitated using external calibration for PFOS due to inconsistent internal standard area counts. 

The reference standard used for the calibration standards for PFOS contained both linear and branched 

isomers. 

A quadratic, 1/x weighted, calibration curve of the standard peak area/peak area ratios was used to fit 

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

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

confirmed accuracy of each curve point. 

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

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

analytes. The con-elation coefficient (r) was greater than 0.995 for PFBS, PFHS, and PFOS. 

8.2 System Suitability 

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

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

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

met for PFBS, PFHS, and PFOS. 

8.3 Limit of Quantitation (LOQ) 

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

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

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

Table 6. Limit of Quantitation (LOQ). 

Sampling location 

PFBS 

LOQ, ng/mL 

PFHS 

LOQ, ng/mL 

PFOS 

LOQ, ng/mL 

DALGW610S-110921 0.0250 0.0250 0.0278 

DALGW610L-110921 0.0250 0.0250 0.0232 

8.4 Continuing Calibration 

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

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

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

8.5 Blanks 

Two types of blanks were prepared and analyzed with the samples: procedural blanks and trip blanks. 

Procedural blank results were reviewed and used to evaluate method performance to detemnine the 

LOQ for PFBS, PFHS, and PFOS. Trip blanks reflect the shipping and sample collection conditons the 

sample bottles and samples experience. 

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Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

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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 Milli Q water or 

synthetic groundwater to produce the desired concentration. The spiked water samples were then 

prepared and analyzed in the same manner as the samples. The method acceptance criteria, average 

of LCS at each level should be within 100% ± 20% with an RSD <20% was met for all analytes. 

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

LCS Percent Recovery = 

Calculated Concentration , 

Spike Concentration 

100% 

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

average LCS recovery 

Table 7. Laboratory Control Spike Recovery. 

ETS-8-044.0 

Intemal standard 

calibration 

Analyzed 10/711 PFBS PFHS 

Lab ID 

Spiked 

Concentration 

(ng/mL) 

Calculated 

Concentration 

(ng/mL) XRecovery 

Spiked 

Concentration 

(ng/mL) 

Calculated 

Concentration 

(ng/mL) VoRecovery 

LCS-111006-1 0.198 0.229 116 0.198 0.212 107 

LCS-111006-2 0.198 0.213 108 0.198 0.205 103 

LCS-111006-3 0.198 0.218 110 0.198 0.203 103 

Average ± %RSD 111±3.7% 104% ±2.2% 

LCS-111006-4 1.98 2.23 113 1.98 2.09 105 

LCS-111006-5 1.98 2.21 112 1.98 2.07 105 

LCS-111006-6 1.98 2.17 110 1.98 2.06 104 

Average ±%RSD 112% ±1.4% 105% ±0.55% 

LCS-111006-7 9.94 10.8 109 9.94 10.2 102 

LCS-111006-8 9.94 10.5 106 9.94 9.85 99.1 

LCS-111006-9 9.94 10.8 108 9.94 10.1 101 

Average ±%RSD 108% ±1.4% 101% ±1.5% 

Page 14 of 60 
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Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Table 7 continued. Laboratory Control Spike Recovery. 

ETS-8-044.0 

Intemal standard 

calibration 

Analyzed 10/7/11 PFOS (linear* branched) 

Lab ID 

Spiked 

Concentration 

(ng/mL) 

Calculated 

Concentration 

(ng/mL) %Recovery 

LCS-111006-1 0.184 0.196 107 

LCS-111006-2 0.184 0.191 104 

LCS-111006-3 0.184 0.190 103 

Average ± %RSD 105% ±2.0% 

LCS-111006-4 1.84 1.93 105 

LCS-111006-5 1.84 1.90 103 

LCS-111006-6 1.84 1.96 106 

Average ±%RSD 105% ±1.5% 

LCS-111006-7 9.22 9.47 103 

LCS-111006-8 9.22 8.99 97.5 

LCS-111006-9 9.22 9.26 100 

Average ±%RSD 100% ±2.7% 

ETS-8-044.0 

External standard 

calibration 

Analyzed 10/7/11 PFOS (linear + branched) 

Lab ID 

Spiked 

Concentration 

(ng/mL) 

Calculated 

Concentration 

(ng/mL) XRecovery 

LCS-111006-1 0.184 0.174 94.6 

LCS-111006-2 0.184 0.173 94.3 

LCS-111006-3 0.184 0.173 93.8 

Average ± %RSD 94.2% ±0.43% 

LCS-111006-4 1.84 1.80 97.6 

LCS-111006-5 1.84 1.90 103 

LCS-111006-6 1.84 1.74 94.6 

Average ± %RSD 98.4% ±4.3% 

LCS-111006-7 9.22 8.66 94.0 

LCS-111006-8 9.22 8.96 97.2 

LCS-111006-9 9.22 8.81 95.6 

Average ± %RSD 95.6% ±1.7% 

8.7 Analytical Method Uncertainty 

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

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

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

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

Page 15 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

con-esponds to a confidence level of 95%. The most recent 50 data points were used to generate the 

method uncertainty values listed in Table 8. 

Table 8. Analytical Uncertainty. 

Analyte Standard Deviation Method Uncertainty 

PFBS 4.66 ±9.3% 

PFHS 4.18 ±8.4% 

PFOS 6.83 ±14% 

8.8 Field Matrix Spikes (FMS) 

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

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

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

(linear), and PFOS (linear) prior to shipping sample containers for sample collection. Field matrix spike 

recoveries within method acceptance criteria of 100±30% confirm that "unknown" components in the 

sample matrix do not significantly interfere with the extraction and analysis of the analytes of interest. 

Field matrix spike concentrations must be 50% of the sample concentration to be considered an 

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

Table 9. Field Matrix Spike Levels. 

Sampling Location Spike Level PFBS, ng/mL PFHS, ng/mL PFOS, ng/mL 

61 OS, 61 OL and Trip Blanks 

Low 0.250 0.250 0.250 61 OS, 61 OL and Trip Blanks High 1.00 1.00 1.00 

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

FMS Recovery = -^^ — * 100% 

Spike Concentraton 

9 . Data'Summary arid Discussion 

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

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

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

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

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

Page 16 of 60 
Table 10. DAL GW 61 OS 110921 

GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

PFBS PFHS PFOS 

Concentration Concentration Concentration 

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

GLP10-01-01-23-001 DAL GW 61 OS-0-110921 0.0509 NA 0.0809 NA 0.177 NA 

GLP10-01-01-23-002 DAL GW 61OS-DB-110921 0.0544 NA 0.0855 NA 0.128 NA 

GLP10-01-01-23-003 DAL GW610S-LS-110921 0.279 90.5 0.309 90.3 0.409 103 

GLP10-01-01-23-004 DAL GW 61OS-HS-110921 1.16 111 1.16 108 0.850 69.8 

Average Concentration (ng/mL) ± %RPD 0.0527 ng/mL ±6.6% 0.0832 ng/mL ±5.5% 0.153 ng/mL ± 32% 

NA = Not /Applicable 

Results for PFBS and PFHS were generated using intemal standard calibration. Results for PFOS were generated using external standard calibration. 

(1) Tfie relative percent difference (RPD) did not meet method acceptance criteria of S20%. 

Table 11. DAL GW 61 OL 110921 

PFBS PFHS PFOS 

Concentration Concentration Concentration 

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

GLP10-01-01-23-005 DAL GW 61 OL-0-110921 0.243 NA 0.250 NA 1.35 NA 

GLP10-01-01-23-006 DAL GW 61 OL-DB-110921 0.252 NA 0.260 NA 1.47 NA 

GLP10-01-01-23-007 DAL GW 61OL-LS-110921 0.495 99.0 0.493 95.2 1.54 NC 

GLP10-01-01-23-008 DAL GW 61OL-HS-110921 1.38 113 1.34 109 2.32 91.0 

Average Concentration (ng/mL) ± %RPD 0.248 ng/mL ±3.6% 0.255 nfl/mL± 3.9% 1.41 ng/mL ±8.5% 

NC=Not Calculated. The sample concentration is greater than 2x the spike level 

NA = Not Applicable 

Results for PFBS, PFHS, and PFOS were generated using intemal standard calibration. 

Page 17 of 60 
Table 12. Trip Blank 

GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

PFBS PFHS PFOS 

Concentration Concentration Concentration 

3M LIMS ID Descrrption (ng/mL) VoRecovery (ng/mL) VoRecovery (ng/mL) VoRecovery 

GLP10-01-01-23-009 DAL GWTRIP01-0-110921 <0.0250 NA <0.0250 NA <0.0232 NA 

GLP10-01-01-23-010 DAL GWTRIP01- LS-110921 0.254 102 0.248 99.2 0.215 86.0 

GLP10-01-01-23-011 DAL GWTRIP01-HS-110921 1.10 110 1.09 109 0.953 95.3 

NA= Not Applicable 

Results for PFBS, PFHS, and PFOS were generated using intemal standard calibration. 

Page 18 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

10 Conclusion 

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

accuracy and precision for PFBS, PFHS, and PFOS. 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 electronic) will be archived according 

to 3M Environmental Laboratory standard operating procedures. 

12 Attachments 

Attachment A: Protocol Amendment 23 (General Project Outline) 

Attachment B: Representative Chromatograms and Calibration Curves 

Attachment C: Analytical Method-ETS-8-044.0 

Attachment D: Method Deviation 

Page 19 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

13 Signatures 

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

4- yL/cy^^// 

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

Gary Hohenstein, Sponsor Representative Date 

Jaisimha Kesari, Study Director Date 

Page 20 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

ATTACHMENT A: PROTOCOL AMENDMENT 

Page 21 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Analytical Protocol: GLP10-01-02 

Amendment 22 

Study Title 

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

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

Decatur Phase 3 Site-Related Monitoring Program 

PROTOCOL AMENDMENT NO. 23 

Amendment Date: 

September 14, 2011 

Performing Laboratory 

3M Environmental, Health, and Safety Operations 

3M Environmental Laboratory 

Building 260-5N-17 

Maplewood, MN 55144-1000 

Laboratory Project Identification 

GLP10-01-02 

Sampling Event 

Off-Site 610 Wells 

Rage 1 of 6 

Page 22 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Analytical Protocol: GLP10-01-02 

Amendment 23 

This amendment modifies the following portion of protocol: 

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

Decatur Phase 3 Site-Related Monitoring Program" 

PROTOCOL READS: 

No changes to the wording of the protocol are required. 

AMEND TO READ: 

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

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

as part of the 3M Decatur Phase 3 Program for PFOS, PFHS and PFBS (GLP10-01-02). The anticipated 

sample collection will occur around the timeframe of the week of September 19, 2011. The groundwater 

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

GLP1,0-01-02-23 and reportedas interim report GLP10-01-02-23, (reflecting study GLP10-01-02 and 

amendment -23)., 

Reason: 

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

anticipate groundwater sample collection event for two new wells located at an off-site location. 

The GPO is three pages in length and included as attached to this amendment forni. 

Page 2 of 6 

Page 23 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Analytical Protocol: GLP10-01-02 

Amendment 23 

Amendment Approval 

Gary HoVienstei/i,.Sponsor Representative 

It 

Date 

Cleston ' ' 'Date C: Lange, Principal Analytical Investigator 

William Reagen, BHS Opns Environmental Lab Management Date 

Jaisimha Kesari P.E^ DEE, Study Director 

Page 3 of 6 

Page 24 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Analytical Protocol: GLP10-01-02 

Amendment 23 

Environmental Health & Safety Operations, Environmental Laboratory 

General Project Outline 

To: Gary. Hohenstein, 3M EHS&Opns 

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

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

Cleston Lange, 3M EHS&Opns; Environmental Lab 

Jai Kesari, Weston Solutions 

Date: September 14, 2011 

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

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

Phase 3 Site-Related Monitoring Program; GLP Interim Report 23; Off-Site 610 Wells 

1 General Project Information 

3M Sponsor Representative 

Gary Hohenstein 

3M EHS Operations 

3M Building 224-5W-03 

Saint Paul, MN 55144-1000 

Rhone: (651) 737-3570 

aahohenstein!a>mmm.com 

3M Environmental Laboratory Management 

William K.. Reagen 

3M EHS Opns, Environmental Laboratory 

260-5N-17 

Contacts 651 733-9739 

wi< reaaen@mmm.com 

Principal Analytical Investigator 

ClestonLange 

3M EHS Opns, Environmental Laboratory 

250-5N-17 

651 733-9860 

cdangeOmmm.com 

Sampling Coordinator 

Timothy Frinak 

Weston Solutions 

timothv.frinakOwestonsolutions.com 

Phone: (334)-332-S123 

Lab Request Number GLP10-01-02-23 

Six Digit Department i^umber dept #530711, Project #0022674449 

Project Schedule/Test Dates Sampling scheduled for the week of September-19,.2011 

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

Page 4 of 6 

Page 25 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Analytical Protocol: GLP10r01-02 

Amendment 23 

2 Background Information and Project Objective(s) 

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

samples collected from two sampling locatiohs for Perfluorobutanesulfonate (PFBS), 

Perfluoi-ohex'anesulfohate (PFHS), and Perfluorooctanesulfonate (PFOS) from new wells,located off-site. 

Analyses will be conducted under the GLP requirements of EPA TSCA Good Laboratory Practice 

Standards 40 CFR 792. 

Groundwater samples will be collected by Weston Solutions personnel the week of September 19, 2011. 

The 3M Environmental Laboratory will prepare the sample bottles with all required spikes to ensure that 

results for PFBS, PFHS, and PFOS are of a known precision and accui-acy. The final report will be 

submitted to Gary Hohenstein and Jai Kesari upon completion under interim report GLP10-01-02-23. 

3 Project Schedule 

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

14, 2011. Sample bottles will be shipped in coolers ovemight to 3M Decatur fol-arrival on Friday, September 

^6,2011. Sample bottles should be stored refrigerated on-site until sample collection. 

Martin Smith \ Weston Trailer 

3M Deeatur Plant 

1400 State Docks Road 

Decatur, Alabama 35601 

4 Test Parameters 

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

Two sampling locations have been specified. See attacfiment A for a list of the sampling locations that will be 

collected for this sampling event For each sarhpling location, a total of four sample bottles will be collected 

(sample, sample duplicate, low field matrix spike, and high field matrix spike). The "fill to here" line on each 250 

mL Nalgene bottle will be 200 mL. One set of trip blanks consisting of reagent-grade water as well trip blank 

spikes will be prepared at the 3M Environmental Laboratory and sent to the sampling location with the other 

bottles. All sample bottles will include the addition of '^Oj-PFBS, '^Oz-PFHS, and '^Ca-PFOS (internal 

standard) at a nominal concentration of 1 ng/mL. All sample bottles will also include the addition of C4-PFOS 

(surrogate spike) at a nominal concentration of 0.1 ng/mL. The table below lists the matrix spike levels that will 

be prepared. 

Well No. Sample Level Spike Cone. (ng/mL) 

610S andeiOR Low 0.25 610S andeiOR High 1.0 

Trip Blank Low 0.25 Trip Blank High 1.0 

Page 5 of 6 

Page 26 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Analytical Protocol: GLP10^01-02 

Amendment 23 

Test Methods 

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

Compounds In Water by High Perfonnance Liquid Chromatography/Mass Spectrometry Direct Injection 

Analysis". Alternately, samples may be analyzed by ETS 8-154.3 "Determination of Peifluorinated Adds, 

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

Chromatography/Mass Spectrometry". 

The data quality objectives for these studies are quantitative results for the target analytes with an analytical 

accuracy of ld0±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. 

Where applicable, samples will be analyzed against an internal standard calibration curve. Each curvie point will 

contain isotopically-labeled perfluorocarboxylic acids and perfluorosulfonic acids at a nominal concentration of 1 

ng/mL. The calibration curve will be generated by taking the ratio of the standard peak area counts over the 

internal standard peak area counts to fit the data for each analyte. 

6 Reporting Requirements 

For each sampling location, the report will contain the results for the sannple, sahiple duplicate, and the field 

matrix spikes. Trip blank and trip blank spikes will be reported for the sampling event as will any 

equipment/rinseate blanks prepared in the field. Laboratory conti-ol spikes of reagent water prepared at the time 

of sample extraction will also be reported and used to evaluate the overall method accuracy and precision. 

Method blanks of reagent water prepared at the time of sample extraction will be used to deterfnine the method 

detection lihiit For those sampling locations where the field matrix spike level was not iappropriate, due to 

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

the final report. 

Page 6 of 6 

Page 27 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

ATTACHMENT B : REPRESENTATIVE SAMPLE CHROMATOGRAMS AND 

CALIBRATION CURVE(S) 

Page 28 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Result s Name: klllOOTa.rd b 

31 -

30-

29-

28-

27-

26-

25-

24-

23-

22-

21-

20-

19-

CD 18-

< 17-

16-

(0 Are 

15-

<D %. 14-

(0 

c 

< 

13-

12-

11 -

10-

9-

8-

7-

6-

5-

4-

3-

2-

1 -

0-

9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0 17.0 18.0 19.0 20.0 21.0 22.0 23.0 24.0 

Analyte Cone. / IS Cone. 

Data printed by 

Printing Time: t 

STW 

:07:41 AM 

Page 1 o f 1 

Page 29 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Result s Name: klllOOVa.rd b 

Data printe d by STW 

Printin g Time: 8:07:09 AM 

Page 1 of 1 

Page 30 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

•Kir k BB21501010 

Printin g Time: 8:01:34 AH Page 1 of 1 

Page 31 of 60 
*ETS-Kirk 

GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Result s Name: klll007a.rd b 

I

SampleNam«:-|(11IO07aO16- SampteID:'11 003-4O4' Fl«: 

Peak Name: •13C3PFHS<IS)- Mass(es); -402.000^0.000 Da* 

Cotnment: '1.0 nglmL FC aid ki Synth. Water Annotatioo;" 

Sample Index: 16 

Sample Type: Standard 

Concentiation : 0.945 ng/riL 

Calculated Cone: H/A 

Acq. Date: 10/7/2011 

Acq. Tine: 2:41:07 PM 

, AlgoElthm: Specify I 

• Percentage: SO 

. Sub. Window: l.OC 

-Split . Factor: 2 

Sample Name: Til 11007a023- Sample ID: '11 OOS-223" Fie: "kl 11007a.wlfr 

Peak Name; M3C3PFHS(IS)- Massfes): "402.000/80.000 DaComment -Method Blank^ AnrK>tation: ~ 

Sanple Index; 23 

I

Sample Name: -k11100ra024' Sample ID: -QLP10-01-02-23-001' 

Peak Name: -13C3PFHS(iS)- Massfes): "402.000/80.000 Da" 

Commeni:-DAL-GW-eiOS*-' Annotatkm;-

Sample Index: 24 

Sample Type: Unknown 

Concentration: 0,945 ng/mL 

Calculated Cone: K/A 

Acq. Date: 10/7/2011 

Acq. Tine: 5:30:04 PH 

Hoi: 

. Algol 

? Perce 

: Specify Paranetei 

Sample ID: "GLP 1 CM) 1-02-23-005* File: 

M3ss(es): "402.000/80.000 DaAnnotation: ~ 

ameCers - HQ II ] 

Nlndoi 

Poak-Split. Factor 

Report Largest Peal 

Hin . Peak Height: 

Min. Peak Width: 

Smoothing Width: 

RT Window: 

mpecl 

Height: 

Star t Ti 

End Tims 

1 RT: 

! RT: 

2.47«t005 cps 

Data printe d by STW 

Printin g Time: 8:09:10 AM 

Page 1 o f 12 

Page 32 of 60 
*ETS-Kirk 

GLP10-01-02; Interim Report 23 

/Vnalysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Result s Name: kl11007a.rdb 

Data printe d by STW 

Printin g Time: 8:09:11 AM 

Page 

Page 33 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Result s Name: klll007a.rd b 

I

Sample Name: -k111007a016' Sample ID: '11 003-40^ Fie: "hi 1 lOOTa.wifr 

Peak Name: -13C8PFOSJS(iS)- Mass(e3): "507.000/80.000 Da" 

C<imrnent;'1.0ng/mLFCs[<J In Synth. Water" Armotalion: " 

Sample Index: 16 

Sample Type: Standard 

Concentration; 0.960 ng/nL 

Acq. Date: 10/7/2011 

Acq. Tine: 2:41:07 PM 

Modified: Yes 

Ptoc. Algorithm; Specify Poiameters - MQ II I 

Noise Percentage: 50 

Baae. Sub. Hindow: 1.00 min 

Peak-Split. Factoi; 2 

Peak: Yes 

.n. Peak Height: 

. Peak 

RT HindoH: 

Expected RT: 

'idth : 0.00 

I

Sample Narrw: "V111007a024" Sample ID: "GLPItM)1-02-23-001" File: •kl11007a.wir 

Peak Name: •13C8PFOS-IS<IS)" Ma»5{«): -507.000/80.000 DaComment: "DAL-GW-6I0S-0-" Annoeatkm: "• 

Sanple Index: 24 

Sample Type: Unknown 

Concentration: 0.960 ng/mL 

Calculated Cone: N/A 

Acq. Date: 10/7/2011 

Acq. Time: 5:30:01 PM 

I

Sample Name: "kl 11007a023" Sample ID: '11 005-223" Fie: "kt 11007a.w<fr 

Peak Name: '13CaPFOS4S{tS)- Massfes): '507.000/80.000 DaComment: "Method Blank* Annotatkxi: "* 

:a9e: 

Baac. Sub. Window: 

Report Largest Pe; 

Hin. Peak Height: 

Smoothing Hldth : 

RT Window: 

RT: 

yes 

: Specify Paratoetei 

Base. Sub. Hindow; 

Peak-Split. Factoi 

Report Largest Fe; 

Min. Peak Height; 

Min. Peak Width: 

Snoothing Width: 

RT Window: 

Expected RT: 

Int . Type: 

Area: 

Height: 

Base To Base 

4.0e4 

3.ee4 

3.ee4 

3.4e4 

3.2e4 

3.0e4 

2.8e4 

2.6e4' 

2.4e4 

2.2e4 

2.0e4' 

1.4M' 

1.2e4 

1.0»4' 

eooo.o6000.0-

4000.0 

2000.0-

0.0-

I

Samfie Name: "k111007a031" Sample ID: 'GLPl 001-02-23-005" File: 

Peak Name:-l3CePF0S-lS(IS)- Mass{es); "507.000^0.000 DaCommenl; -DAL-GW-610L-*.* AnrHrtaBon; -

Saraple Index: 31 

Sample Type; Unknown 

Concentration: 0.960 ng/nL 

Calculated Cone: )1/A 

Acq. Date: 10/7/2011 

Acq. Time: 7:57:59 PM 

in: Specify Pai 

Hin . Peak Wid: 

Smoothing Hid' 

Expected RT: 

Use Relative I 

Int . Type: 

Retention Timi 

Area; 

Height: 

Start Time; 

Data printe d by STW 

Printin g Time: 8:09:11 AM 

Page 3 o f 12 

Page 34 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Result s Name: klllOOVa.rd b 

I

Sample Name: •k111007a041- Sample ID:-LCS-111006-1' File;-K111007a.wfr 

Peak Name: "13C8PFOS-«S(ISr Mass(e5); "507.000/80.000 Da' I Comment "OJfppb LCS- Annotation:-

Sample Nan>e:*k1110073035' Sample ID:'GLP10-01-02-23409' File: 

Peak Name: '13C8PFO&^S(iS}' Mass(es): '507.000/BO.OOO DaComment:-DAL-GW-TRIPOl-O- Aimolalion:-

Sample Index: 3S 

Sample Type: Unknown 

Concentration: 0.960 ng/nL 

Calculated Cone: 

Date 

.cq. Tim, 

10/7/2011 

9:22:29 PM 

Peak-Split. Factor: 

Report Largest Peak: 

Min. Peak Height: 

Base To Base 

s Type: 

0.951 

Proc. Algorithm; Specify Parameters - KQ ] 

Noise Percentage: 50 

Base. Sub. Window: l.OD min 

Peak-Split. Factor: 2 

Report Largest Peak: Yes 

Min. Peak Height: 0.00 cps 

Hin. Peak Width: 0.00 sec 

Snoothing Hldth : 0 point s 

RT * 

Expect 1 RT: 

! RT: 

16.2 

) Relati i II o 

. Type: Base To Base 

•ntio n Time: 16.1 min 

>: 518228 counts 

8.17eH 

15.9 

I

SamplsName:*k111O07aD44' Sample ID:-LCS-111006^' File:-k111i 

Peak Name: 'ISCBPFOS-ISflS)- Mass(as): -507.000m0.000 DaComment: -2ppb LCS" Annotation:" 

Sample Index: 44 

Sampl e Type ; QC 

Concentration : 0.95 1 ng/m L 

Calculated Cone: N/A 

Acq. Date: lO/B/2011 

Acq. Time: 12:32:3^ AM 

; Specify Paraneterj 

:-Spl i Facte 

iport Largest Peak; Yes 

n. Peak Height: 0.00 

~'sBk Width: 0.00 

Snoothing width: 0 

RT Window; 30.0 St 

Expected RT; 

! Relai 

Height: 

Start T: 

End Tlmi 

i RT: No 

(

Sample Name:T(111007a04r Sample ID: -LCS-111006-r File: •k111007a. 

Peak Name: -13C8PFOS-IS(iS)- Mass<es): -507.000/80.000 Da" 

Commenc "10 ppb LCS" Annotatkxt: ~ 

Sample Index: 47 

Sample Type: QC 

Concentration: 0.954 ng/mL 

Calculated Cone; H/A 

Acq. Date: 10/6/2011 

Acq. Time; 1:3S:S4 AM 

Modified: Yes 

Proc. Algorithm; Specify Parameters - MQ II I 

Noise percentage: 50 

Base. Sub. window: 1.00 min 

Snoothing Hldth : 

RT Window: 

Expected RT: 

Data printe d by STW 

Printin g Time: 8:09:11 AM 

Page 4 of 12 

Page 35 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Result s Name: klllOOVa.rd b 

Sample Name:-k111007a016- Sample ID:-11 003-4(K8- Flle:-k111007a.wtrr 

Peak Name: -ie02PFBS(IS)" Mass(es): "303.000/84.000 Da' 

CommonI:'1.0 ng/mL FC std in Synth. Water* Annotation:"" 

Sample Index: 16 

Sample Type; Standard 

Concentration: 0.975 ng/nL 

Calculated Cone: N/A 

Acq. Date: 10/7/2011 

Acq. Tine: 2:41:07 PM 

Data printe d by STW 

Printin g Time: 8:09:11 AM 

Page 5 of 12 

Page 36 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Result s Name: klllOOVa.rd b 

I

Sample Name: •l(111007a035" Sample ID: "GLP!CM)1.02-23-009' File; 

Peak Name: •1802PFBS(IS)" Mass{es): "303.000/84.000 DaComment:-DAL-GW-TRIPOI-O- Anfwlalton:-

Sample Index: 35 

Sample Type: Unknown 

Concentration: 0.975 ng/mL 

Calculated Cone: N/A 

Acq. Date: 10/7/2011 

Acq. Time: 9:22:29 PH 

:ied: No 

Proc. Algorithm : Specify Pail 

Hoise Percentage: SO 

Base. Sub. Window: 1.00 

Peak-Split. Factor: 2 

Report Largest Peak: Yes 

Hin. Peak Height: 0.00 

Min. Peak width : 0.00 

Smoothing Width: 0 

RT Window: 30.0 B* 

Expected RT: 13.7 mi 

Int . Type: 

Area: 

Height: 

Start Tine 

Base To Base 

le: 13.7 min 

1165160 counts 

Sample Name: "k111007a041" Sample ID:'LCS-111006-r File:-k111007a.wtfr 

Peak Name: '1802PFBS(IS}' Ma3s(es): '303.000/84.000 Da" 

Comment '0.2ppb LCS' Annotation: " 

Sample Index: 41 

Saraple Type: QC 

Concentration: 0.966 ng/nL 

Calculated Cone: ll/A 

Acq. Date; 10/7/2011 

Acq. Time: 11:29:15 PM 

Proc. Algorithm ; Specify Pan 

Moise Percentage: 50 

Base. Sub. Window; 1.00 

Peak-Split. Factor; 2 

Report Largest Peak: Yes 

Hin. Peak Height: 0.00 

Hin. Peak Width: 0.00 

Smoothing Width: 0 

RT Window: 30.0 st 

Expected RT: 13.7 mi 

11.5 

I

Sample Name: "kl 11007aD44' Sample ID: 'LCS-111006-4- File: -kU1007a. 

Peak Name: '1802PFBS(IS)- Ma»s(es); -303.000^84.000 DaComment *2ppb LCS- Amwtatton: " 

Sample Index: 41 

Sample Type: QC 

Concentration; 0.966 ng/nL 

Calculate d Cone: N/A 

Acq. Date: 10/8/2011 

Acq. Time: 12:32:34 AM 

Noise Percentage; 

Base. Sub. window: 

Peak-Split. Factor 

Report Largest Pea 

Hin. Peak Height: 

Min. Peak Width: 

Snoothing Width: 

RT Window: 

Expected RT: 

Sample Name: "kl 11007a04r Sample ID: "LCS-111006-r File: "kll 1007a.*«r 

Peak Name: -18D2PFBS(iS)- Mass(as): *303.00Qr84.000 DaComment '10 ppb LCS' JSjmotalion: ~ 

Sample Index; 47 

Sample Type: QC 

Concentration: 0.969 ng/raL 

Calculated Cone: t(/A 

Acq. Date: lO/B/2011 

Acq. Time: 1:35:54 AM 

Proc. Algorithm: Specify Parameteri 

Noiae Percentage: 50 

Base. Sub. window: I.00 min 

Peak-Split. Factor: 2 

: Relet I RT: 

• Type: Valley 

intlo n Time: 13.7 

l : 11S2U2 C( 

Height: 

Star t T; 

End Tim. 

Height: 

Hin. Peak Width: 

Smoothing width : 

RT Window: 

Expected RT: 

Use Relativ e RT: 

Int . Type: 

Area; 1171 

Height: 1. 

0.00 

Data printe d by STW 

Printin g Time: 8:09:11 AM 

Page 6 o f 12 

Page 37 of 60 
*ETS-Kirk 

GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Result s Name: klllOOVa.rd b 

I

Sample Name: "k111007a0l6- Sample ID: "11 003-4(W Flo: "kU1007a. 

Peak Name: "PFBS" Mass(B5): "asg.OOWSO.OOO Da.299.000«9.000 Da' 

Comment "1.0 ng/mL FC Std in Synth. Watei* Annotatkx>: ~ 

Sample Index: 16 

Type: Standard 

Calculat 0.982 

Proc. Algorithm: Specify I 

Noise Percentage: 50 

Base. Sub. Window: l.Dt 

Peak-Split. Factor: 1 

Report Largest Peak: Ye: 

Hin . Peak Height; 0.( 

Hin . Peak Width: 0.( 

Smoothing Width: 0 

RT Window: 30.0 

11.5 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 

(

Sample Name: "kl 11007a023" Sample ID: "11 005-223- Fie: "kl 11007a.wtir 

Peak Name: "PFBS" Uassfes): "299.00^80.000 Da ,299.000/99.000 Da* 

Comment "Method Blank" Annotation: 

Sample Index: 23 

Sanple Type: Unknown 

l i f ied : 

i Cone: 

No 

Proc. Algoritlun: Specify i 

Noise Percentage: 50 

Base. Sub. Window: l.OC 

Peak-Split. Factor: 2 

Report Largest Peak: Yes 

Htn. Peak Height: O.C 

Hin . Peak width : O.C 

Smoothing Width: 0 

RT Window: 30.0 

Expected RT: 

! Roll • RT: No 

12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 

I

Sample Name: •kl110073024- Sample ID: *GLP10-01-02-23-001" File: 1(1110073. 

Peak Name: -PFBS- Mass<es): "299.000/80.000 Da.299.000/99.000 Da" 

Comment -DAL-GW-610S-0-- Anrwtation: -

sample Index: 24 

Sample Type: Unknown 

Concentration' 

Calculated Coi 

Acq. Time: 

N / A 

Base. Sub. Window: l. ( 

Peak-Split, Factor: 2 

Report Largest Peak: Ye 

Min . Peak Height: 0. 

Hin . Peak Hldth : 0. 

Smoothing Width: 0 

RT Window: 30.0 

) Relatl i 

detention 1 

Mea; 

ioight : 

! RT: No 

Base To Base 

I

Sample Name: 1(1110073031" Sample ID: "GLPHW)1-02-23-005' File:-k111007a.wtfr 

Peak Nama: "PFBS" Massfes): -299.000/80.000 Da,299.000/99.000 DaComment "DAL-GW-610L-ft-' Annotation: ~ 

Sample Index: 31 

0.243 

10/7/2011 

7:57:59 I 

Proc. Algorithm: Specify i 

Noise Percentage: 50 

Sub. Window: l.OC 

t-SplH Fact 

Report Largest Peak: Yei 

Kin. Peak Height: O.C 

Hin. Peak Width: O.C 

Snoothing Hldth: 0 

RT Window: 30.0 

Expected RT: 13.7 

> Relat i RT; 

387052 counts 

5.64e<-004 cps 

13.5 min 

14.0 min 

Data printe d by STW 

Printin g Time: 8:09:11 AM 

Page V o f 12 

Page 38 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Result s Name: klllOOVa.rd b 

I

SamploName:"k111007a041- Samp(olD:'LCS-111C 

Peak Name: "PFBS" Mass(es): -299.OOIV80.000 Da,2' I Comment "0.2ppb LCS" Annotatton: 

Sample Name: "kllI007a035' Sample ID: -i 

Peak Name: 'PFBS* Mass(es); -299.000«0.0< 

Comment:-OAL-GW-TRIPOI-O" AnnolaBon:-

Sample Index: 35 

Sanple Type: Unknown 

Calculated Cone: < 0 

Acq. Date: 10/7/2011 

Acq. Time: 9:22:29 PM 

Modit: No 

: Height: 

RT Hindow: 

Expected RT: 

Use Relative 1 

) Type: QC 

0.198 ng/mL 

0.229 ng/mL 

10/7/2011 

11:29:15 PM 

lilied: 

ic. Algorithm: : 

SB Percentage: 

RT Hindow: 

Expected RT: 

Use Relative I 

5.8e4 

5.6e4 

5.4»4 

5.2e4 

5.0e4 

4.8e4 

4.6e4 

4/4e4 

4.2e4 

3/4e4-

32e4 

3.0e4' 

2.&e4' 

2.6e4-

2AtA2.2e4-

2.0e4' 

12e4-

1.0*4' 

8000.0 

6000.0-

4000.0-

2000.0-

13.0 13J 14.0 14.5 15.0 15.5 16.0 

I

Samp(eN3me:-V111007a044- Sampts ID: "I 

Peak Name: -pFBS" Mai*(es): •299.000/80.0< 

Comment •2ppb LCS" Annotalioo:"" 

Sample Index: 44 

Sample Type: QC 

Concentration: 1.98 n< 

Calculated Cone: 2.23 nt 

Base. Sub. window: 

Peak-Split. Factor: 

Report Largest Peak: 

Min. Peak Height: 

Start Time: 

5.5Ba-^005 cps 

S.4e5' 

5.2e5' 

5.0e5-

4.ee5-

4.6e5-

4.4e5-

4.2e5-

4.0e5-

3.8e5-

3,6e5-

3,4e5-

3.2e5-

3.0e5-

2.8eS2.eeS2.4e5-

2.2e5' 

2.0e5 

1.8e5-

8.0e4 

6.0e4 

4.0e4 

2.0»4 

I

Sample Name: "kl l 1007304r Sample ID: 'LCS-111 

Peak Name: "PFBS- Mass(es): -299.000/80.000 Da.2i 

Comment:-10 ppb LC^- Annotation: "" 

Sample Index: 47 

Sample Type: QC 

Concentration: 9.94 ng/nL 

Calculated Cone; 10.B ng/raL 

Acq. Date: 10/8/2011 

Acq. Time: 1:3S:54 AH 

Modified; No 

Proc, Algorithm; Specify Parameters - MQ 1 

Noise Percentage: 50 

Min. Peak width ; 

Smoothing Width: 

RT Window: 

Expected RT: 

End Time: 

Data printe d by STW 

Printin g Time: 8:09:11 AM 

Page 8 of 12 

Page 39 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Result s Name: klllOOVa.rd b 

(

Sample Name: "kl 11007a016" Sample ID: "11 003-W-d' Flo: "kl 11007a,wi(r 

Peak Name: "PFHS- Massfes): -399.000/99.000 Da.399.000^0.000 Da* 

Commenl: '1.0 ng/mL FC std in Synlh.Waler- Annolation; "* 

Sample Index: 16 

Sample Type: Standard 

Concentration: 1.00 ng/mL 

Calculated Cone: 0.998 ng/mL 

Acq. Date: 10/7/2011 

Acq. Tine: 2:41:07 PH 

Base. Sub. Windoi 

Peak-Split. Facti 

Report Largi 

Min. Peak Heighi 

Min. Peak width 

Smoothing Width 

Peat 

16.0 16.5 17.0 17.5 

[

Sample Name: "kl 110073023" Sample ID: "11 005-223- Fie: 'kl 11007a.*«r 

Peak N3me: 'PFHS" M3ss{es): "399.000/99.000 Da.399.000/80.000 DaComment 'Method Btsnk- Annotatnn; ~ 

2100-

2000-

1900 

1800 

1700 

1600 

1500 

1400' 

Noise Per< :age: 

Sub. Windoi 

Report Largi 

Min. Peak Height 

Min. Peak Width: 

Smoothing Width: 

RT Hindow: 

Expected RT: 

Area: 

Height: 

Peal 

1200 

1100 

1000-

(

Sample Name: *k111007a024' Sample ID: -GLP1041'02-: 

Peak Name: -pFHS- Mass(*s): -399.000/99.000 Da,399.0C 

Comment: "DAL-GW-610S-0-' Annotation;" 

Sample Index; 24 

Sample Type: Unknown 

Nois< 

Base. Sub. Hindow 

Peak-Split. Facto: 

Report Largi 

Hin. Peak Heigh' 

Hin. Peak Width 

Snoothing Width 

RT Window: 

)e09 

Peak: 

! Reli ; RT: 

(

Sample Name: 1(1110078031- Sample ID: -GLPKM)1-02-23-005" File: •k111007a.wifr 

Peak Name: "PFHS" Mass(es); "399.000/99.000 Da,399.000/80.000 DaComment "OAL-GWAeiOL-O-- Annotation: ~ 

Sample Index; 31 

0.250 

10/7/2011 

7:57:59 PM 

Peak-Split. Facte 

Report Largest Pe 

Hin. Peak Height: 

Hin. Peak Width; 

Smoothing width : 

RT Window: 

Expected RT; 

Use Relative RT: 

13.0 13,5 14.0 14,5 15,0 15.5 16.0 16.5 17.0 17.5 

Data printe d by STW 

Printin g Time: 8:09:11 AM 

Page 9 of 12 

Page 40 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Result s Name: klllOOVa.rd b 

I

Sample Name:-k111007B03S' Sample ID: "GLP 1041-02-23-009' File:-k1110073.wir 

Peak Name: "PFHS' Massfos); '399.000/99.000 Da.399.000^0.000 Da' 

Commenl: 'DAL-GW-TRIPOI-O' Annolation: -

Sample Index; 35 

Sample Type: Unknown 

Acq . Date : 

Acq . Time : 

Modified: 

ichm; Specify I 

lloise Percentage: 50 

Base. Sub. Window: 1. Of 

Peak-Split. Factor; 1 

Report Largest Peak: Ye: 

Min. Peak Height: 0.( 

Min. Peak Width: 0.( 

Smoothing Width: 0 

RT Hindow: 30.0 

Expected RT: 15.2 

Use Relative RT: No 

imetecs - KQ I 

Height: 

Valley 

15.2 min 

1891 counts 

l,03e+002 cps 

I

SamplB Name: 1(1110073044' Sample ID: 'LCS-111006-4' File:*k11l007a.Mr 

Peak Name: "PFHS' Massfes): -399.000/99,000 Da,399.000/80.000 DaComment: -2ppb LCS- Annotation:" 

Sample Type: QC 

Concentration: 1.98 ng/mL 

Calculated Cone: 2.09 ng/mL 

Acq . Date ; lO/S/201 1 

I

Sample Name: ^kll I007a041' Sample ID: 'I 

Peak Name: "PFHS' Mass{es): '399.000/99.0{ 

Comment "0.2ppb LCS' Annotation: " 

Sample Index: 41 

Sampl e Type : QC 

Concentration ; 0.19 8 ng / 

Base. Sub. Window: 

Peafc-SplIt. Factor: 

Report Largest Peak: 

8.40e*0O4 cps 

.0 14.5 15.0 15.5 16.0 18.5 17.0 17.5 

(

Sample Name: -kl 11007304r S3mple ID: -

Peak Nama: 'PFHS' Mass(es): "399.000/99. 

Comment '10 ppb LCS' Annotation;"" 

Sample Index; 47 

Acq. Time; 12:32 :34 

Modified: No 

Proc. Algorithm: Specify Pari 

IJoise Percentage: 50 

Base. Sub. Window; 1.00 

Peak-Split. Factor: 1 

Report Largest Peak: Yes 

Min. Peak Width: 0.00 

Snoothing Width: 0 

Use Reli 

Int. Tyi 

Area: 

Height: 

i RT: 

! RT: 

15. 2 

Ho 

7.5e5 

7.0e5-

6.5e5 

6.0e5 

5.5e5-

in: Specify Parameter; 

Peak-Split. Factor 

Report Largest peal 

Kin. Peak Height: 

Kin. Peak Width: 

Smoothing Itidth: 

RT Window: 

Expected RT: 

3.4e6 

3.2e6 

3.0e6-

2.6e6-

2.6e6-

2.406 

2.2e6 

2.0e6-

1.ee6-

1.6«6-

1.4e6-

1.2e6 

1.0e6-

B.0e5-

6.0e5-

4.0eS15.5 16.0 

Data printe d by STW 

Printin g Time: 8:09:11 AM 

Page 10 o f 12 

Page 41 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Result s Name: klllOOVa.rd b 

(

Sample Name: -kil l 0078016- Sample ID: '11 003-4O-8- Fie: Td 11007a,¥rtr 

Peak Name: -PFOS- Mass{es): -499.000/99.000 Da ,499.000/80.000 D3.499,000/130.000 03" 

Commenl; "1,0 ng/mL FC Btd in Synth, Watei* Annolation: ~ 

Sample Index: 16 

Base, Sub. Hindow: 

Peak-Split. Factoi 

Report Largest Pe* 

Min. Peak Height; 

Min. Peak Width; 

Smoothing width; 

RT Window: 

: Specify Pataneteri 

RT; 

15.5 16.0 16.5 17.0 17.5 18.0 

(

Sample Name: *kl 11007a023" Sample ID: *11 005-223" Fie: 'kl 11007a,wtfr 

Peak Name: "PFOS" Mass(es): "499.000«9.000 Da.499.000/80,000 Da.499,000/130,000 Oa" 

Comment "Method Blank* Annotation: 

Sample Index; 23 

Sample Type: Unknown 

Concentration: ll/A 

10/7/2011 

5:08:55 PM 

Manual 

16.1 min 

18131 counts 

!.05e*003 cps 

14.0 14.5 15.0 

I

Sample Name: -kl 11007a024- Sample ID: "GLP 10-01-02-2 

Peak Name: -f>FOS- Mass(es): "499.000/99.000 Da,499.00i 

Comment: "DAL-GW-eiOSO-' Annotatton: "• 

sample Index: 24 

Sanple Type: Unknown 

I

Sam^Je Name: "kl 11007a03r Sample ID: 'GLP 1 (Kll-02-23005" File: "kl 11007a,wir 

Peak Name: "PFOS" Mass{es): -499.000^9.000 Da.499.000^1.000 Da,499.000/130.000 DaComment "DAL-GW-610L-(X.* Annotation:"* 

Sample Index: 31 

: Specify Parametei 

Sub. I Indow: 

. Faci 

Report Largest f i 

Min. Peak Height: 

Min. Peak Width: 

Smoothing width : 

RT Window: 

Expected RT: 

: Relat 1 RT: 

Calculated Coi 

Acq. Date: 

Acq. T i ne: 

Smoothing Widt 

RT Window; 

Area: 1131387 counts 

Height: 1.0Ee-^005 cps 

Star t Time: 15.6 min 

End Time; 16.3 min 

I.OSeS1.00e5-

9.50e4-

9.00e4' 

B.50e4-

8.00e4-

7.50*4-

7.00e4-

6.50*4-

6,00e4-

14.0 14.5 15.0 15.5 16.0 16.5 17.0 17. 

Data printe d by STW 

Printin g Time: 8:09:11 AM 

Page 11 o f 12 

Page 42 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Result s Name: klll007a.rd b 

I

SampleN3me:T(111007a035" Sample ID:-GLP10-01-02-23«l9" File:'kni0073.wifr 

Peak Name: -PFOS- Mass(es): -499.000/99.000 Da,499.000/80.000 D3,499.000/130.000 D3-

Comment:-DAL-GW-TRIPOl-0- Annolation;-

llfl i 

algorithm: Specify Paramett 

rcentage; 

Base. Sub. Window: 

Peak-Split. Factor 

Report Largest Pea 

Hin. Peak Height: 

Min. Peak Width: 

RT Window; 

Expected RT; 

Use Relative RT: 

Start Time: 

..55e+003 cps 

14.5 15,0 17.5 18.0 

I

SampteName:1il11007a041" SampteID: "LCS-II 1006-r File:-k111007a. 

Peak Name: TFOS- Ma$s(e$}: '499.000/99.000 Da.499.000/80.000 Da,499.000/130.000 Da* 

Comment -0.2ppb LCS- Annotatkin; ~ 

Sanple Index: 41 

Sample Type: OC 

Concentration; 0. 1B4 ng/mL 

Calculated Cone: 0.196 ng/mL 

Acq. Date; 10/7/2011 

Acq. Time; 11:29:15 PM 

Modified: fes 

Proc. Algorithm: Specify Parameters - MQ II I 

Woise Percentage: 50 

t-Split 

;epor 

Facti 

Peak: 

Min. Peak Height: O.l 

Min. Peak Width: O.C 

Smoothing Width: 3 

RT Window; 30.0 

Expected RT: 16.2 

Height: 

Start Ti 

14,0 14.5 15.5 16.0 16.5 17.0 17.5 18.0 18,5 

I

Sample Name: "kl 11007a044" Sample ID: "LCS-11100fr4" File: "kl l 1007a.w«r 

Peak Name: 'PFDS' Mass(as}: "499.000/99.000 Da,499.000/80.000 Da.499.000/130.000 DaCommenl: '2ppb LCS' Annotation: " 

Sample Index: 44 

Sample Type; QC 

Concentration: 1.84 ng/raL 

Calculated Cone; 1.93 ng/nL 

Acq. Date: 

Acq. Tine: 

1.7B5 

12:32:34 J 

•. Sub. 1 

L-SplH Faci 

Report Lacg' 

Min. Peak Height 

Min. Peak Width: 

Smoothing width; 

RT Window 

Peal 

peel 1 RT: 

• Relati' 

Start Tine; 

I

Sample Name: 1(111007304r Sample ID: "LCS-111006-r File: "kl 11O07a.wtr 

Peak Name; -PFOS" Mass(es): -499,000/99.000 Da,499.000/80.000 Da,499.000/130.000 DaComment '10 ppb LCS- Annotatiofi: ~ 

Sample Index; 47 

Sample Type: QC 

Concentration: 5.22 ng/mL 

Calculated Cone: 9.47 ng/nL 

Acq. Date: 10/8/2011 

Acq. Tine: 1:35:54 AM 

thn; Specify Pat 

Report Largest Pef 

Min. Peak Height; 

Min. Peak Width: 

Smoothing width; 

RT Window: 

Expected RT: 

Height: 

Start Time: 

End Time: 

17.5 18.0 15.5 16.0 16.5 17.0 17.5 18.0 18.5 

Data printe d by STW 

Printin g Time: 8:09: 

Page 12 o f 12 

Page 43 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS In Groundwater Samples 

Off-Site 610 Wells; September 2011 

Result s Name: kl11007a-ext.rd b 

kl 11007a-ext.rdb (PFOS): "Quadratic" Regression ("1 / x" weighting): y = -151 9.03e-f005 x + 4.85e-t-003 (r = 0.9997) 

10.0 11.0 12.0 13.0 14.0 15.0 

Concentration, ng/mL 

17.0 18.0 20.0 21.0 22.0 23.0 

Data printe d by 

Printin g Time: 

Page 1 o f 1 

8:11:48 AM 

Page 44 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Results Name: kll1007a-ext.rdb 

I

SampteName:-V1110078016* Sample 10:"11 OOi^M* Fla:Tel 11007a.wifr 

P«ak Name: "PFOS- Masstas): '499.000/99.000 Da ,499.000/80.000 Da,499.000/130.000 Da' 

Comment: -1.0 ngtmL FC std In Synth. Water" Annolation: -

A l l gori 

ttolsi 

Base. Sub. Window: 

Report Largest Pe; 

Min. Pealt Height: 

Min. Peal^ Widi 

: Specify Pataneter: 

.dth: 

RT Window: 

Expected RT: 

Use Relative 1 

Int . Type: 

Height: 

e.98e»004 cps 

1S.0 15.5 16.0 16.5 17.0 17.5 18.0 

I

Sample Name: "Kll 1007aD23- Sample ID: -11 005-223' Fle:-k111007a.war 

Peak Name: *PFOS' Masafas): '499.000/99.000 Da,499.000W).000 Da.499.000/130.000 Da* 

Comment -Method Blank- Annolation: ~ 

Smootlilng width ; 

RT Window: 

Use Relative RT; 

I

Sample Name: *k111007a024' Sample ID: -GLP10-01-02-23-00r File:' 

Peak Name: -PFOS' lulaas(as): '499.000/99.000 Da.499.000;80.000 Da,4< 

Comment:-DAL-GW-eiOS-O-- AnnotaUon:" 

Sample Index: 24 

Sample Type: Unknown 

I

Sample Name: "kl 11007aD4r Sample ID: -LCS-11 lOO&V File: -kl 11007a.wtr 

Peak Name: -PFOS' MaS3(as): -499.000/99.000 Da,499.000/80.000 Da.499.000/130.000 Da' 

CommenL -0.2ppb LCS- Annotation:"" 

N / A 

Calculated Cone: 

Acq. Tine : 

177 

Proc. Algorithm: Specify Pararaetc 

tloiae Percentage: 90 

Base. Sub. Window: 1.00 min 

Peak-Split. Factor: 3 

Report Largest Peak; Yea 

Kin . Peak Height: 0.00 cps 

Hin . Peak Width: 0.00 sec 

Snoothing Width: 0 pc 

RT Window: 30.0 sec 

Expected RT; IS.9 min 

Calculated Cone; 0.174 nt 

Acq. Date: 10/7/2011 

Acq. Tine: 11:29:15 PM 

Modified: Mo 

Proc. Algorithm : Specify Parao 

Noise Percentage: 90 

Base. Sub. Window: 1.00 n 

Expected RT: 15.9 mli 

Use Belatlv e RT: Mo 

Int . Type: Base To Base 

Retent " " ' " 

Area; 

Height: 

1.ee4 

1.7&4 

1.6e4' 

1.504 

1.4e4 

1.3e4 

1.2e4 

^ 9000.0 

8000.0 

13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0 

Data printe d by STW 

Printin g Time: 8:13:08 AM 

Page 1 o f 2 

Page 45 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Results Name: klllOOTa-ext.rdb 

Data printe d by STW 

Printin g Time: 8:13:09 AM 

Page 2 of 2 

Page 46 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

ATTACHMENT C: ANALYTICAL METHOD(S) 

Page 47 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

3IVI Environmental Labomtory 

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 y- j 

Approved By: 

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 48 of 60 
GLP10-01-02; Interim Report 23 

Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 

Off-Site 610 Wells; September 2011 

1 Scope and Application 

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

PerfluorohexanoicAcid (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 Performance 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 "Detennination 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 Method Summary 

Clean aqueous samples are analyzed by direct injection using LC/MS/MS. Samples containing heavy 

particulate may not tie 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 verity 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 Working Standard (WS) into a predetermined 

amount of ASTM Type 1, 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 I, HPLC grade water, or other suitable water, placed in a sample container in the laboratory 

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

preservation and all analytical procedures. The purpose of the FB is to detemnine if test substances or 

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

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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 detemriine 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 detemnine whether the sample 

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

sample matrix must be detemnined in a separate aliquot and the measured values in the LMS con-ected 

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. 

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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 detemnine 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 nomnally 

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 woric environment and a cun-ent awareness of local 

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

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

4.2 Cautions 

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

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

appropriate equipment procedure or operator manual for additional 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 interf'erences under 

conditions of analysis by running method blanks. 

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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 pL 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, 250pL, 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) %A % B 

Flow Rate 

(mL/min) 

0.0 97 3 1.0 

0.5 97 3 1.0 

11.0 5 95 1.0 

13.5 5 95 1.0 

13.6 97 3 1.0 

17.0 97 3 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. 

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6.3 MS/MS System 

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

Analyte Transition Monitored 

PFBA 213^ 169 

PFPeA 263^219 

PFHA 313^269 and 313 ^119 

PFHpA 363 ^ 319, 363 ^ 169 and 363 ^ 119 

PFOA 413 ^ 369, 413 ^ 219 and 413 ^ 169 

PFNA 463 ^ 419, 463 ^ 169 and 463 ^219 

PFDA 513 -> 469, 513 219 and 513 ^ 269 

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

PFDoA 613 ^. 569, 613 ^ 169 and 613 ^ 319 

PFBS 299 ^ 80 and 299 ^ 99 

PFHS 399 80 and 399 99 

PFOS 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 infomnation is intended as a guide, alternate instruments 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 

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

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

PerfluorohexanoicAcid (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 - CIO acid); Oakwood Products, Inc 

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

Perfluorododecanoic Acid (PFDoA - C12 acid); Oakwood Products, Inc 

Perfluorobutanesulfonate (PFBS - C4 sulfonate); 3M 

Perfluorohexanesulfonate (PFHS - C6 sulfonate); 3M 

Perfluorooctanesulfonate (PFOS - C8 sulfonate); 3M 

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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 Mg/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 correction is given below for PFOS. 

^. , ^ molecular weight of anion 

salt correction factor = 

moclecular weight of salt 

4QQ PFOS (K+)salt correction factor = — = 0.9275 

538 

10 mg CSFITSO/K* with purity 90% = 8.35mg CsFiySOs" (10 mg*0.90*0.9275=8.35 mg) 

5 |jg/mL (5000 ng/mL) mixed working standard—^Add 0.5mL each of the lOOpg/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 wori<ing standard solution to a 25mL volumetric 

flask and bring up to volume with solvent. 

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

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

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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 Volume of WS, fiL 

Final Volume of 

Calibration Standard (mL 

ofASTiVI Type 1 Water, or 

other suitable water) 

Final Concentration of 

Calibration Standard, ng/mL 

(ppb) in ASTM Type 1 Water, 

or other suitable water 

125 10 50 0.025 

125 15 50 0.0375 

125 20 50 0.050 

125 30 50 0.075 

250 20 50 0.100 

250 50 50 0.250 

250 100 50 0.500 

250 200 50 1.00 

5000 25 50 2.50 

5000 50 50 5.00 

5000 100 50 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 + 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-determined 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 

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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 construct the calibration curve. 

If the calibration curve does not meet acceptance criteria, perform routine maintenance or prepare a new standard 

curve (if necessary) and reanalyze. 

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 constmct 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 instmment 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 detemnine 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 

Sun"ogate 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. 

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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 determine 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: 

A . X r / , .. (Peak Area - Intercept) _ _ 

Analyte found (ng/mL) = -^^ — x DF 

Slope 

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. 

Recovery - ^"^^'y*® ^^^"^^ (ng/mL) - Average analyte found in sample (ng/mL) ^ 

Analyte added (ng/mL) 

12 Method Performance 

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

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

If criteria listed in this method perfonnance section are not met, maintenance may be perfomned 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 

mn 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 S2% to be compliant. 

12.2 Quantitation 

Calibration Curve: The coefficient of determination (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. 

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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 Accuracy 

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

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

13 Pollution Prevention and Waste Management 

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

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

14 Records 

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

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

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

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ATTACHMENT D: DEVIATION(S) 

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RECORD OF DEVIATION/NONCONFORMANCE 

/. Identification 

study / Project No. 

GLP10-01-02-23 

Date(s) of Occurrence: 

11/7/2011-k111007a-ext 

Document Number: 

ETS-8-044.0 

Deviation type • SOP • Equipment Procedure 0 Method 

(Ctieci< one) • Protocol • GPO • Other: 

/ / . Description (attacli extra pages as needed) 

Method Requirements: 

1. RPD within ±20% (section 10.3). 

Actual procedure/process: 

1. Sampling location DAL-GW-61 OS had an RPD of 32% for PFOS. 

///. Actions Taken 

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

Corrective Action (• Yes 0 No) Reference: 

Acceptability of the nonconforming work: 

1. The PFOS RPD for sampling location DAL-GW-61 OS will be flagged in the final report. 

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

IZi Other: Deviations will be noted in final report. 

Project Lead/PAI Approval: 

Study Director (if GLP): 

Sponsor Approval (for GLP protocol deviations): NA 

Date: 

Date: 

Date 

Technical Reviewer (optional): NA Date 

Laboratory ^epartnnent Manager Approval: Date: 

''^ IV. Authorization to Resume Work 

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

Laboratory Department Manager Approval: NA Date: NA 

Deviation No. 

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

ETS-4-008.7 Page 1 of 1 

Documentation of Deviations and Control of Nonconforming Testing °