GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

3M 

GLP10-01-01. Interim Report 19: Analysis of PFOA in Groundwater Samples Collected at 

the Off-Site BP Property in Decatur. AL in July 2011 

Study Title 

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

Site-Related Monitoring Program 

Data Requirement 

EPA TSCA Good Laboratory Practice Standards 40 CFR Part 792 

Study Director 

Jaisimha Kesari P.E., DEE 

Weston Solutions, Inc. 

1400 Weston Way 

Westchester, PA 19380 

Phone:610-701-3761 

Author 

Susan Wolf 

3M Environmental Laboratory 

Interim Report Completion Date 

Date of signing 

Performing Laboratory 

3M Environmental Health and Safety Operations 

Environmental Laboratory 

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

St Paul, MN 55144 

Project Identification 

GLP10-01-01-19 

Total Number of Pages 

52 

«i^ 

lACCREDITEDl 

Tlie 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. Testing that complies with this Intemational Standard also 

operate in accordance with ISO 9001:2000. 

Testing Cert #2052.01 

Page 1 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA In Water Samples 

Off-Site BP Property - July 2011 

This page has been reserved for specific country requirements. 

Page 2 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

GLP COMPLIANCE STATEMENT 

Report Title: GLP10-01-01, Interim Report 19. Analysis of PFOA in Groundwater Samples Collected 

at the Off-Site BP Property in Decatur, AL in July 2011 

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

Decatur Phase 3 Site-Related Monitoring Program. 

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

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

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

system and no dosing of a test system. 

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

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

% . X( 

Gary Hojfiensjein, Sponsor Representative Date 

^ 

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

Page 3 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

QUALITY ASSURANCE STATEMENT 

Report Title: GLP10-01-01, Interim Report 19. Analysis of PFOA in Groundwater Samples Collected 

at the Off-Site BP Property in Decatur, AL in July 2011 

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

Decatur Phase 3 Site-Related Monitoring Program. 

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

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

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

Inspection Dates 

8/12/11,8/15/11 

Phase 

Data / Interim Report 

Date Reported to 

Testing Facility 

Management 

8/23/11 

Study Director 

8/23/11 

^^xs~-i{ 

QAU Representative 

Page 4 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

TABLE OF CONTENTS 

GLP Compliance Statement 3 

Quality Assurance Statement 4 

Table of Contents 5 

List of Tables 6 

1 Study Information 7 

2 Summary 8 

3 Introduction 9 

4 Test & Control Substances 9 

5 Reference Substances 10 

6 Test System 10 

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 12 

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 16 

8.8 Field Matrix Spikes (FMS) 16 

Page 5 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

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 PFOA Results (BP Groundwater, Decatur, AL, July 2011) 9 

Sample Description Key Code 10 

Table 2. Instrument Parameters 11 

Table 3. Liquid Chromatography Conditions 12 

Table 4. Mass Transitions 12 

Table 5. Limit of Quantitation (LOQ) 13 

Table 6. Laboratory Control Spike Recovery 14 

Table 6 continued. Laboratory Control Spike Recovery 15 

Table 7. Analytical Method Uncertainty 16 

Table 8. Field Matrix Spike Levels 16 

Table 9. DAL GWBPMW47 110713 17 

Table 10. DALGWBPMW121 110713 17 

Table 11. Trip Blank 17 

Table 12. Rinseate Blank 18 

Page 6 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

j 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 Report 18 Experimental Termination: July 29,2011 

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 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

12 Summar y 

The 3M Environmental Laboratory received groundwater samples from two different wells located at 

the Off-Site BP Property in Decatur, AL. A total of thirteen sample bottles were received at the 3M 

Environmental Laboratory for perfluorooctanoate (PFOA) analysis and included duplicate groundwater 

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

each location, one trip blank containing Milli-QTM water and appropriate trip blank spikes, and one 

equipment rinseate. The equipment rinseate blank did not have a FMS sample prepared for the 

determination of PFOA recovery. The groundwater samples, trip blanks, and equipment rinseate blank 

were received from Weston personnel on July 18,2011. All of the samples were prepared and 

analyzed for PFOA following 3M Environmental Laboratory Method ETS-8-044.0 under 3M project 

GLP-10-01-01-19. The average measured PFOA concentrations are summarized in Table 1. The 

equipment rinseate and the trip blanks were below the lower limit of quantitation (LLOQ) of 0.0250 

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

The analytical uncertainty was estimated at 100±14%. 

Page 8 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

Table 1. Summarized PFOA Results (BP Groundwater, Decatur, AL, July 2011) 

Sample ID 

DAL GWBPMW47 110713 

DALGWBPMW121 110713 

Trip Blanks (Milli-QTM Water) 

GLP10-01-01-19 Equipment rinseate blank: 

DALGWBPMW121 

Avg. PFOA 

Concentration 

(ng/mL) 

0.351 

0.0648 

< 0.0250 

< 0.0250 

Relative 

Percent 

Difference 

2.0% 

10% 

N/A 

N/A 

N/A: not applicable 

The analytical uncertainty for PFOA was estimated at 100+14%. 

[" 3 Introduction 

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

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

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

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

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

the off-site BP property in Decatur, AL for PFOA in an effort to characterize regional groundwater 

conditions. 

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

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

groundwater sampling location included a field sample, field sample duplicate, and two field spike 

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

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

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

collection. All sample bottles included the addition of ^^Cs-PFOA (intemal standard) at a nominal 

concentration of 1 ng/mL. See section 8.8 of the report for field matrix spike levels. 

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

Laboratory method ETS-8-044.0 "Determination of Perfluorinated Compounds in Water by High 

Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". The use of an 

intemal standard was used to aid in the data quality objectives. 

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

collected, the trip blank, and equipment rinseate samples. Tables 9-12 summarize the individual 

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

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

14 Tests, Control Substances I 

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

was purely analytical in nature. 

Page 9 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

\5 Reference Substances 

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

Reference 

Substance 

Chemical Name 

Chemical Formula 

Identifier 

Use 

Source 

Expiration Date 

Storage Conditions 

Chemical Lot Number 

TOR Number 

Physical Description 

Purity 

PFOA (Linear) 

Perfluorooctanoate 

C7F15COOH 

CAS #335-67-1 

Target Analyte 

Reference Standard 

Oakwood Products 

01/17/2018 

Frozen 

3440 

TCR07-0041 

Powder 

99.1% 

PFOA 

(Unear + Branched) 

Perfluorooctanoate 

C7F15COOH 

/Ammonium Salt 

GAS #335-67-1 

LCS Reference 

Standard 

3M 

02/27/2017 

Frozen 

332 

TCR-123 

White powder 

95% 

"Cs-PFOA 

Perfluorooctanoate 

''C8HF15O2 

CAS#MPFC-C-0511 

Intemal Standard 

Wellington 

05/25/2014 

Frozen 

IVIPFC-C-0511 

TOR11-0016 

Liquid 

NA<^' 

(1) Compound is part of a custom mixture of mass-lat)eled periluorinated compounds at a concentration of 5.0 pg/mL. 

6 Test System 

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

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

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

Sample Description Key Code. 

string Number 

Example 

1 

2 

3 

4 

string Descriptor Example 

DAL GWBPMW47 0110713 

Sample Location 

Well ID 

Sampling Date 

Sample Type 

DAL= Decatur, Alabama 

Example: BPMW47 

110713-July 13,2011 

0=primary sample 

DB=duplicate sample 

LS = low spike 

MS = mid spike 

HS = high spike 

Page 10 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

\7 Method Summar y j 

7.1 Methods 

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

"Determination of Perfluorinated Compounds In Water by High Performance Liquid 

Chromatography/Mass Spectrometry Direct Injection Analysis". 

7.2 Sample Collection 

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

Environmental Laboratory. Sample bottles associated with GLP10-01-01-19 were returned to the 

laboratory at ambient conditions on July 18, 2011. Samples were stored refrigerated at the laboratory 

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

the set 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 intemal standard mix at a nominal concentration of 1 ng/mL prior to 

being sent to the field for sample collection. 

7.4 Analysi s 

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

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

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

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

and Table 4. 

Table 2. Instrument Parameters. 

Instrument Name 

Analytical Method Followed 

Analysis Date 

Liquid Chromatograph 

Guard column 

Analytical column 

Injection Volume 

Mass Spectrometer 

Ion Source 

Electrode 

Polarity 

Software 

ETSKIrk 

ETS-8-044.0 

7/28/11-7/29/11 

Agilent 1200 

Betasil C18 (4.6 mm X 100 mm), 5n 

Betasil 018 (4.6 mm X 100 mm), 5u 

25 nL 

/Applied Biosystems API 5500 

Tutbo Spray 

Turbo ion electrode 

Negative 

Analyst 1.5.2 

Page 11 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

Table 3. Liquid Chromatography Conditions. 

step 

Number 

Total Time 

(min) 

Flow Rate 

(pUmIn) 

Percent A 

(2 mM ammonium acetate) 

PercentB 

(MethanoO 

7/28/11-7/29/11 Analysis 

0 

1 

2 

3 

4 

5 

0.0 

2.0 

14.5 

15.5 

16.5 

20.0 

750 

750 

750 

750 

750 

750 

97.0 

97.0 

5.0 

5.0 

97.0 

97.0 

3.0 

3.0 

95.0 

95.0 

3.0 

3.0 

Table 4. Mass Transitions. 

Analyte 

PFOA 

Mass Transition 

Q1/Q3 

413/369 

413/219 

413/169 

Intemal standard 

fCJPFOA 

Mass Transition 

Q1/Q3 

421/376 

Dwell time was 30 msec for eacfi transition. Tfie individual transitions were summed to produce a 

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

8 Analytical Results 

8.1 Calibration 

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

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

laboratory-prepared synthetic groundw^ater 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 100 ng/mL was prepared. Sample DAL GW BPMW47 was 

quantitated using extemal calibration due to inconsistent internal standard. 

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 PFOA. 

8.2 System Suitability 

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

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

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

met for PFOA. 

Page 12 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

8.3 Limit of Quantitation (LOQ) 

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

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

blanks. The nominal LOQ for all analytes can be found in Table 5. 

Table 5. Limit of Quantitation (LOQ). 

Analysis Date 

iiim ^ 

PFOA 

LOQ, ng/mL 

0.0250 

8.4 Continuing Calibration 

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

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

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

8.5 Blanl(s 

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

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

performance to detemnine the LOQ for PFOA. Trip blanks refiect the shipping and sample collection 

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

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

and are proof of no cross contamination of samples from the equipment. 

8.6 Lab Control Spikes (LCSs) 

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

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

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

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

LCS at each level should be within 100% ± 20% with an RSD ^20%, were met for the linear PFOA LCS 

samples. 

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

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

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

The linear and branched LCS met method acceptance criteria at all levels. All LCS samples were used 

in the detemnination of method uncertainty in section 8.7. 

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

1 ^o n . r. Calculated Concentration . , .„. , 

LCS Percent Recovery = * 100% 

Spike Concentration 

LCS% RSD = "'^"^^^'^ ^^'^'^"° " "-^^ ^^P"^'^" • 100% 

average LCS recovery 

Page 13 of 52 
Table 6. Laboratory Control Spike Recovery. 

GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

ETS-8-044.0 Intemal 

standard calibration 

Analyzed 7/28/2011 

Lab ID 

LCS-110726-1 

LCS-110726-2 

LCS-110726-3 

Average ±%RSD 

LCS-110726-4 

LCS-110726-5 

LCS-110726-6 

Average ±%RSD 

LCS-110726-7 

LCS-110726-8 

LCS-110726-9 

Average ±%RSD 

Spiked 

Concentration 

(ng/mL) 

0.199 

0.199 

0.199 

Linear PFOA 

Calculated 

Concentration 

(ng/mL) 

0.210 

0.211 

0.221 

%Recovery 

106 

106 

111 

108%±2.r/o 

1.99 

1.99 

1.99 

2.03 

1.97 

2.02 

102 

98.7 

102 

101% ±1.9% 

19.9 

19.9 

19.9 

19.1 

19.3 

19.3 

96.0 

97.0 

96.8 

96.6% ±0.55% 

ETS-8-044.0 Intemal 

standard calibration 

Analyzed 7/28/2011 

Lab ID 

LCS-110726-10 ECF 

LCS-110726-11 ECF 

LCS-110726-12 ECF 

Average ±%RSD 

LCS-110726-13 ECF 

LCS-110726-14 ECF 

LCS-110726-15 ECF 

Average ±%RSD 

LCS-110726-16 ECF 

LCS-110726-17 ECF 

LCS-110726-18 ECF 

Average ±%RSD 

LIm 

Spiked 

Concentration 

(ng/mL) 

0.199 

0.199 

0.199 

iar * Branched PF 

Calculated 

Concentration 

(ng/mL) 

0.206 

0.215 

0.217 

OA 

VoRecovery 

104 

108 

109 

107%±Z5% 

1.99 

1.99 

1.99 

1.99 

2.01 

2.14 

100 

101 

107 

103% ±3.8% 

19.9 

19.9 

19.9 

20.2 

21.7 

22.7 

102 

109 

114 

108% ±5.6% 

Page 14 of 52 
Table 7 continued. Laboratory Control Spike Recovery. 

GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

ETS-8-044.0 Extemal 

standard calibration 

Analyzed 7/28/2011 

Lab ID 

LCS-110726-1 

LCS-110726-2 

LCS-110726-3 

Average ±%RSD 

LCS-110726-4 

LCS-110726-5 

LCS-110726-6 

Average ±%RSD 

LCS-110726-7 

LCS-110726-8 

LCS-110726-9 

Average ±%RSD 

Spiked 

Conceittratlon 

(ng/mL) 

0.199 

0.199 

0.199 

Linear PFOA 

Calculated 

Concentration 

(ng/mL) 

0.232 

0.231 

0.237 

VoRecovery 

117 

116 

119 

117% ±1.3% 

1.99 

1.99 

1.99 

2.20 

2.12 

2.16 

110 

107 

109 

109% ±1.4% 

19.9 

19.9 

19.9 

20.3 

20.4 

20.5 

102 

103 

103 

103% ±0.56% 

ETS-8-044.0 Extemal 

standard calibration 

Analyzed 7/28/2011 

Lab ID 

LCS-110726-10 ECF 

LCS-110726-11 ECF 

LCS-110726-12 ECF 

Average ±%RSD 

LCS-110726-13 ECF 

LCS-110726-14 ECF 

LCS-110726-15 ECF 

Average ±%RSD 

LCS-110726-16 ECF 

LCS-110726-17 ECF 

LCS-110726-18 ECF 

Average ±%RSD 

Lint 

Spiked 

Concentration 

(ng/mL) 

0.199 

0.199 

0.199 

iar* Branched PF 

Calculated 

Concentration 

(ng/mL) 

0.232 

0.227 

0.233 

OA 

VoRecovery 

117 

114 

117 

116% ±1.5% 

1.99 

1.99 

1.99 

2.09 

2.14 

2.26 

105 

108 

114 

109% ±4.2% 

19.9 

19.9 

19.9 

21.5 

22.9 

23.8 

108 

115 

120 

114% ±5.3% 

Page 15 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

8.7 Analytical Method Uncertainty 

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

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

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

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

con-esponds to a confidence level of 95%. 

Table 8. Analytical IVIethod Uncertainty. 

Analyte 

PFOA 

Method 

ETS-8-044.0 

Standard Deviation 

7.01 

IVIethod 

Uncertainty 

±14% 

8.8 Field Matrix Spikes (FMS) 

Two field matrix spikes were collected at each sampling point to verify that the analytical method is 

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

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

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

100±30% confinn 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 

MW47 

IVIW121 

Trip Blank 

Spike Level 

Low 

High 

Low 

High 

Low 

Mid 

High 

PFOA, ng/mL 

0.250 

1.00 

2.00 

20.0 

0.250 

1.00 

20.0 

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

FMS Recovery = -^ ^^* 100% 

Spike Concentraton 

\9 Data Summary and Discussion | 

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

locations as well as the Trip Blank and rinseate 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 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

Table 10. DAL GW BPMW47 110713 (1) 

3M LIMS ID 

GLP10-01-01-19-005 

GLP10-01-01-19-006 

GLP10-01-01-19-007 

GLP10-01-01-19-008 

Description 

DAL GW BPMW47 0 110713 

DAL GW BPMW47 DB 110713 

DAL GW BPMW47 LS 110713 

DAL GW BPMW47 HS 110713 

Average Concentration (ng/mL) ± VoRPD 

PFOA 

Concentration 

(ng/mL) 

0.347 

0.354 

0.638 

1.43 

VoRecovery 

NA 

NA 

115 

108 

0.351 ng/mL ± 2.0% 

NA= Not Applicable 

(1) Results generated using extemal standard calibration. 

Table 11. DAL GW BPMW121 110713 (1) 

3M LIMS ID 

GLP10-01-01-19-010 

GLP10-01-01-19-011 

GLP10-01-01-19-012 

GLP10-01-01-19-013 

Description 

DALGWBPMW121 0110713 

DALGWBPMW121 DB 110713 

DAL GW BPMW121 LS 110713 

DAL GW BPMW121 HS 110713 

Average Concentration (ng/mL) ± VoRPD 

PFOA 

Concentration 

(ng/mL) 

0.0682 

0.0614 

2.10 

20.6 

VoRecovery 

NA 

NA 

102 

103 

0.0648 ng/mL 110% 

NA = Not /Applicable 

(1) Results generated using intemal standard calibration. 

Table 11. Trip Blank (1) 

3M LIMS ID 

GLP10-01-01-19-001 

GLP10-01-01-19-002 

GLP10-01-01-19-003 

GLP10-01-01-19-004 

Description 

DAL GWTRIP1 0110713 

DAL GWTRIP1 LS110713 

DAL GWTRIP1 MS 110713 

DAL GWTRIP1HS 110713 

PFOA 

Concentration 

(ng/mL) 

<0.0250 

0.249 

0.961 

20.3 

VoRecovery 

NA 

99.6 

96.1 

102 

NA = Not Applicable 

(1) Results generated using intemal standard calibration. 

Page 17 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

Table 12. Rinseate Blank (1) 

3M LIMS ID 

GLP10-01-01-19-009 

Description 

DAL GW BPMW121 RS 110713 

PFOA 

Concentration 

(ng/mL) 

<0.0250 

VoRecovery 

NA 

NA = Not /Applicable 

(1) Results generated using intemal standard calibration. 

Page 18 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

10 Conclusion 

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

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

Laboratory method ETS-8-044.0 described herein. 

11 Data/Sample Retention 

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

to 3M Environmental Laboratory standard operating procedures. 

\12 Attachment s 

Attachment A: Protocol Amendment 19 (General Project Outline) 

Attachment B: Representative Chromatograms and Calibration Curves 

Attachment C: Analytical Method - ETS-8-044.0 

Page 19 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

13 Signatures 

P-Jzshe^ff 

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

^ 'j/^Ct/sr^a/l 

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

Gary Hohenstein, 7M Sponsor Representative 

gAMJy 

\ 

Date 

Jaisimha Kesan, Study Director 

Page 20 of 52 
GLP10-01-01; Interim Report 19 

/Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

ATTACHMENT A: PROTOCOL AMENDMENT 

Page 21 of 52 
GLP10-01-01; Interim Report 19 

/Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

Analytical Protocol: GLP10-01-01 

Amendment 19 

Study Title 

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

SIVi Decatur Phase 3 Site-Related Monitoring Program 

PROTOCOL AMENDMENT NO. 19 

Amendment Date: 

Julys, 2011 

Performing Laboratory 

3M Environmental, Health, and Safety Operations 

3M Environmental Laboratory 

Building 260-5N-17 

Maplewood, MN 55144-1000 

Laboratory Project Identification 

GLP10-01-01 

Sampling Event 

Decatur Phase 3; Off-Site BP Property 

Page 1 of 7 

Page 22 of 52 
GLP10-01-01; Interim Report 19 

/Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

Analytical Protocol: GLP10-01-01 

Amendment 19 

This amendment modifies the following portion of protocol: 

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

3M Decatur Phase 3 Site-Related Monitoring Program" 

PROTOCOL READS: 

No changes to the wording of the protocol are required. 

/^ENDTOREAO: 

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 PFOA (GLP10-01-01). The anticipated sample collection 

will occur around the timeframe of the week of July 11, 2011. The groundwater samples for this sampling 

event will be entered into the 3M Environmental Laboratory LIMS as project GLP10-01-01-19 and 

reported as interim report GLP10-01-01-19, (reflecting study GLP10-01-01 and amendment -19). 

Reason ; 

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

anticipate groundwater sample collection event for two existing wells located at an off-site location on the 

BP Property. 

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

Page 2 of 7 

Page 23 of 52 
GLP10-01-01; Interim Report 19 

/Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

Analytical Protocol: GLP10-01-01 

Amendment 19 

Amendment Approval 

^'H] fMlh'^'i^i/ 

2 X 

IL 

Gary Hbhenstein, Sponsor Representative 

dc 

Date 

'^//V^^>' 

Cleston C. Lange, Principal Analytical Investigator Date 

O//^/^// 

William Reagen, EHS Opns Environmental Lab Management 

kml' 

Date 

TMil 

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

Page 3 of 7 

Page 24 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

Analytical Protocol: GLP10-01-01 

Amendment 19 

Olw l 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: July 6,2011 

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

Decatur Phase 3 Site-Related Monitoring Program; GLP Interim Report 19 - Decatur Phase 

3; Off-Site BP Property 

1 General Project Information 

Contacts 

Lab Request Number 

Six Digit Department Number 

Project Schedule/Test Dates 

3iM Sponsor Representative 

Gary Hohenstein 

3M EHS Operations 

3M Building 224-5W-03 

Saint Paul, MN 55144-1000 

Phone: (651) 737-3570 

qahoheristein(a^mmm,com 

3M Environmental Laboratory Management 

William K. Reagen 

3M EHS Opns. Environmental Laboratory 

260-5N-17 

651 733-9739 

wkreaqen(S>mmm.com 

Principal Analytical Investigator 

Cleston Lange 

3M EHS Opns, Environmental Laboratory 

260-5N-17 

651 733-9860 

cclanQeSJmmm.com 

Sampling Coordinator 

Timothy Frinak 

Weston Solutions 

TimothY,ffinak(awestonsQlution5.eom 

Phone: (334).332-9123 

GLP10-01-01-19 

Dept #530711, Project #0022674449 

Sampling scheduled for the wael^ of July 11,2011 

All verbal and written correspondence will t>e directed to Gary Hotienstein and Jai Kesari. 

Page 4 of 7 

Page 25 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

Analytical Protocol: GLP10-01-O1 

Amendment 19 

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 locations for Perfluorooctanoic Acid (PFOA) from existing wells 

located on the BP property. 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 July 11, 2011. The 3M 

Environmental Laboratory will prepare the sample bottles with all required spikes to ensure that results for 

PFOA are of a known precision and accuracy. The final report will be submitted to Gary Hohenstein and 

Jai Kesari upon completion under interim report GLP10-01-01-19. 

3 Project Schedule 

Sample collection bottles will be prepared by 3M Environmental Laboratory for sampling the week of July 11, 

2011. Sample bottles will be shipped in coolers ovemight to 3M Decatur for anival on Friday, July 8, 2011. 

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

Martin Smith \ Weston Trailer 

3M Decatur Plant 

1400 State Docks Road 

Decatur, Alabama 35601 

4 Test Parameters 

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

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

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

(sample, sample duplicate, low field matrix spike, and high field matrix spike). The iill 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 ^^Cs-PFOA (intemal standard) at a nominal concentration 

of 1 ng/mL. All sample bottles will also include the addition of "C4-PFOA (sumsgate spike) at a nominal 

concentration of 0.1 ng/mL. One additional bottle will be prepared to be used for the preparation of the 

equipment rinseate blank. A 500mL bottle of laboratory reagent water will be sent with the sample bottles to be 

used to generate the rinseate blank sample. The table bebw lists the matrix spike levels that will be prepared. 

Well No. 

MW.47 

MW-121 

Trip Blank 

Sample Level 

Low 

High 

Low 

High 

Low 

Mid 

High 

Spike Cone. (ng/mL) 

0.25 

1.0 

2.0 

20 

0.25 

1.0 

20 

5 Test Methods 

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

Confipounds in Water by High Perfbnmance Liquid Chromatography/Mass Spectrometry Direct Injection 

Page 5 of 7 

Page 26 of 52 
GLP10-01-01; Interim Report 19 

/Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

Analytical Protocol: GLP10-01-01 

Amendment 19 

/^alysis". Alternately, samples may be analyzed by ETS 8-154.3 "Determination of Perfluorinated Acids, 

Alcohols, Amides, and Sulfonates In Water By Solid Phase Extractton 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 100±30%. Field matrix spikes not yielding recoveries within 100±30% will be addressed in the 

report and the final accuracy statement may be adjusted accordingly. 

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

contain isotopically-labeled perfluorocartxjxylic ackJs and perfluorosulfbnic acids at a nominal concentieition of 1 

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

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

6 Reporting Requirements 

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

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

equipment/rinseate blanks prepared in tiie fleld. Laboratory control spikes of reagent water prepared at the time 

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

Method blanks of reagent water prepared at the time of sample extraction will be used to detennine the mettiod 

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

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

tiie final report. 

Page 6 of 7 

Page 27 of 52 
GLP10-01-01; Interim Report 19 

/Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

Analytical Protocol: GLP10-01-01 

Amendment 19 

Attachment A 

Bottle request - BP Weil Sampling Week of 11 July 2011 

Young, Charles T. cbjacoby2@mmm.com, stwolf@mmm.com, clange@mmm.com 07/05/2011 01:51 PM 

^^ "Frinak, Timothy R." 

The access agreement for sampling two existing wells on the BP property is in place and it is anticipated that 

sampling will occur next week as a part of the Phase 3 effort. Analyses should be performed under GLPlO-01-01. 

The former (abandoned) wells 60IR and 601L on the BP property were close to the new locations and would best 

serve as an estimate of the appropriate spiking levels. PFOA levels were 0.107 ng/mL (5/2006) and 0.179 ng/mL 

(9/2007) in the residuum well 601R and 19.8 ng/mL (5/2006) and 11 ng/mL (9/2007) in the bedrock well 601L. The 

existing BP well MW-47 is the residuum well and MW-121 is the bedrock well. In addition to samples fi-om these 

two wells, a rinseate blank will be collected. 

Can you prepare a bottle set for shipment to Martin Smith at the Decatur facility with arrival on Monday, July 11, 

2011? 

Thanks, 

Charlie 

Charles T. Young 

Technical Director 

Weston Solutions, Inc. 

1400 Weston Way (5-2) 

West Chester, PA 19380 

(610)701-3787 

Fax (610) 701-3401 

Page 7 of 7 

Page 28 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

ATTACHMENT B: REPRESENTATIVE SAMPLE CHROMATOGRAMS AND 

CALIBRATION CURVE(S) 

Page 29 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

Results Name: kll0728a.rdb 

Data printed by STW 

Printing Time: 9:23:57 AM 

Printing Date: Thursday, August 25, 2011 

Page 1 of 1 

Page 30 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

Results Name: kll0728a.rdb 

Sample Type: 

I

San^Name:-k110728a016' Sanvto ID: "11 0O»M r Fte:'V110728a.wtir 

PMkNBme:"13C8PR3A-IS{lsr M»M««): "421.000376.000 Da" 

Comntnt "1.0 ngAnL FC «td In Synlh. Water Annotttkin: * 

Sample Index: 16 

idard 

.00 ng/mL 2^5 -

2.4e5-

23«5-

MO II I "e5 . 

2.1e5-

2JO»5-

laeS1^5 -

1.7»5-

1.6e5-

1^5 -

5 '*= • 

I 1285 

* ,.,.5 ^ 

1.0e5 

9.0e4 

8.0a4' 

7J)ft4 

6.0»4' 

5.0»4 

4.0»4' 

3J>e4' 

2.0e4' 

1.0a4 

Calculate d Cone: 

Acq. Date : 

Acq, Time : 

Modified : 

Proc . Mgoclthm : 

Hols e Percentag e 

N/A 

7/28/2011 

3:16:32 PM 

Yes 

Specif y Param 

50 

Base . Sub . Window: 1.00 n> 

Peak-Split , Fac t t : 2 

Report Largest Peak: Yes 

Min- Peak Heigfit 

Min. Peak Hidth : 

Smoothing Width : 

RT Window: 

Expected RT: 

Use Relativ e RT: 

Int . Type : 

Retentio n Time : 

0.0 0 

0.0 0 

30. 0 se c 

15.8 min 

No 

Valle y 

15.7 Bin 

Area : 1505817 counts 

Height : 

Star t Time : 

End Time: 

.52«*00S cp s 

15.6 min 

16.0 min 

0.0-

13.5 I 

I

S«mpteName:'VI10728aO2ar SanvtelD:-LCS-110726-1- Rto: 1(110728a.»ir 

P«akNaine:-13CSPPCWrlS(IS}* Uats(e«>:-421.00(V376.000Da' 

Ccntntnt 'D.2ppb LCS* Annotation: ~ 

e Type: QC 

I

S«mptoN»ma:T(110728aO2r Sampte ID: "11 00&«r File: 1(1107288. 

PMk NanM:-13C6F^^A4S<IS)- MaM(M): -421.00CV376.000 Da* 

Commwui-MrthodHartT Annotation:" 

Sample Type: 

Concentration : 

Calculate d Cone: 

Acq. Date : 

Acq. Time: 

Modified : 

Proc . Algorithm: 

Noiae Percentag e 

Base . Sub. Wlndo 

PeaK-SplIt . Fac t 

Unknown 

1.00 

K/A 

7/2B/2011 

7:08:2 8 PM 

Yes 

Specif y Pa 

50 

•: 1.00 

t : 2 

Report Largest Peak: Yes 

Min. Peak Heigh t 

Min. PeaK Midth: 

Smoothing Width: 

RT Window: 

Expecte d RT: 

Use Relativ e RT: 

Int . Type : 

Retentio n Time: 

Area : 17 

Height : 

Star t Time: 

End Time: 

0.0 0 

0.0 0 

0 

30. 0 

15. a 

No 

Valle y 

15.7 n 

Saa2 cour 

.016*005 

15.6 R 

16. 0 n 

I

SwnpieN«me:-k110728a03r Sarr«>lelD:-LCS-110726-4- Fl«: I d 10728a. 

PeakHame:-13C8Pf=OA4S(IS)- Uatt{M): "421.000076.000 Oa" 

Commw* *2ppb LCS" Annotaflon: ~ 

Sample Index: 31 

Sample Type: QC 

0.99 3 ng/mL 

Sampl 

Conce 

Calcu 

Acq. 

Modil 

Proc . 

Base . 

PeakRe poi 

Min. 

Min. 

Smool 

RT w: 

Expec 

Use R 

Int . 

Reten 

Area : 

Heigh 

e Type : 

ntration : 

late d Cone 

)ace : 

Time: 

led : 

Algorithm 

OC 

0.993 

N/A 

7/28/2 0 

7:29:32 

Yes 

Percentage : 50 

1 

PM 

Pa 

Sub. Window: 1.00 

Split . Fac 

t Largest 

?eak Heigh 

Peak Hidt h 

lin g Width 

red RT: 

elativ e RT 

Type : 

:lo n Time : 

o r : 3 

eak : Y 

: 0 

0 

0 

30. 0 

15.8 

No 

Base To 

15.8 

1666277 

2.93e*00 . 

UU 

Ba 

Calculate d Cone: 

Acq. Date : 

Acq. Time: 

Modified : 

Proc . Algorithm: 

Nois e Percentag e 

Base . Sub. Wlndo 

Peak-Split . Fact 

N/A 

7/28/2011 

a: 3?:54 PM 

No 

Specif y Pa 

50 

-: 1.00 

3r: 2 

Rejiort Largest Peak: Yes 

Min. PeaK Heigh t 

Min. Peah Width: 

Smoothing Width: 

RT Window: 

Expecte d RT: 

Use Relativ e RT: 

Int . Type : 

Retentio n Time: 

0.0 0 

0.0 0 

0 

30. 0 

15. a 

No 

Valle y 

15.8 

Area : 1665098 cou 

Height : 

Star t Time: 

End Time: 

.706.00 5 

15. 6 p 

16.0 E 

13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0 

Data printed by STW 

Printing Time: 9:35:12 AM 

Printin g Date: Thursday, August 25, 2011 

Page 1 of 6 

Page 31 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

•ETS-Kirk Results Name: kll0728a.rdb 

I

Sample Name: "kHOTZSaOsr Samr^a ID:'LCS-11072e-r nia:-k110728a.wltr 

PaakNinM:-13C8PFOA«0S>' Maaa{aa): "421.000/376.000 Da' 

Commart: '20ppb LCS" Ajvwtatton: -

Sample Index: 34 

Sample Type: 

Concentrati< 

Calculate d Cone: 

Acq. TICM : 

Modified : 

Proc . Algor: 

Nois e Percen 

:hm: 

Base . Sub. Wlndo 

Peak-Split . 

Report Large 

-ac t 

St P 

Min. PeaK Height 

Min. Peak H: 

Smoothing U: 

RT Window: 

Expecte d RT: 

Use Relativ e 

Int . Type : 

dth : 

RT: 

Retentio n Time: 

Area : 

Height : 

Star t Time: 

End Time: 

QC 

0.993 

N/A 

7/28/2 0 

9:36:14 

No 

Specif y 

SO 

-: 1.1 

3r: 2 

ak: Ye 

0 

0 

30. 0 

15. 8 

No 

Base To 

lE. e 

1593904 c 

.51e*0O5 

15. 6 

15. 9 

1 

PM 

Pa 

1> 

OO 

nn 

Ba 

15.0 15.5 16.0 16.5 

Sampie Name: 1(110728*044" Sampla ID: 'LCS-110726-1T RIe: Vt 10728a.vi«r 

PeakNanM:-13C8Pr=OA-IS{!S)- hlaM(M):'421.000/376.000 Da' 

Comment "2ppb LCS ECF" Annotation: "* 

Sampl I 

SampleNama:'V11072e»O41- Sample ID:'LCS-110726-10- Fie:"k110728a.wHT 

Peak Name: *13C8PFOA-IS(IS}- MaM(ee): '421.0001376.000 Oa*^ 

Comment: •0.2ppb LCS ECP Annotation: -

Sample 

Sample Type : 

Concentration : 

Calculate d Cone 

Acq. Time : 

Modified : 

Proc . Algorithm: ; 

Hols e Percentage : 

Base . Sub . Mindow: 

Peak-Split . FactOJ 

Report Largest 

Min- Peak Height; 

Min. Peak Width: 

Smoothing Midth: 

RT Window: 

Expecte d RT: 

Use Relativ e RT: 

0.99 3 nc 

K/A 

7/29/201 1 

12:04:0 8 AM 

Int . Type : 

Retentio n 1 

Height : 

Va 1 le y 

»e: 15.7 

1679052 c( 

2.62et00 5 

13.5 

Sample tJame: '1c11072eaO4r Sample ID: TCS-110726-18- Fie: 1c110728a.wttr 

Peak Name: -13C8PFOMS{IS)- Matc<et): "421 .OOCVST&OOO Da* 

Comment: "20ppb LCS EC r Annotation: "" 

Sample Index : 47 

Sample Type: QC 

Concentration : 0.99 3 ng/mL 

Calculate d Cone: N/A 

rithm: Specif y Parameters - MQ II I 

Sample Type : QC 

0,994 ng/mL 2.6e5-

Acq. Date : 

Acq. Time: 

Modified : 

Proc . Algorithm: 

Hois e Percentag e 

7/:9/:oi i 

1:07:32 AM 

Yes 

Specif y Par 

50 

Base . Sub. Window: 1.00 

Peak-Split . Factor: 2 

Report Largest Peak: Yes 

Min. Peak Height 

Min. Peak Hidth : 

Smooching Width; 

RT Window: 

Expecte d RT: 

Use Relativ e RT: 

int . Type : 

Retentio n Time: 

0.0 0 

0.0 0 

0 

30. 0 s 

15. 6 ni 

No 

Valle y 

15.7 m 

Area : 162702S coun 

Height : 

Star t Time: 

End Time: 

.Ble*00S c 

15.6 HI 

15. 9 n 

ameters - MQ II I 

points 

e c 

i n 

Ls 

i n 

In 

Sub . Window: 

Min. Peak Width: 

Smoothing Width: 

RT Window: 

Expecte d RT: 

1597202 ct 

2.53e-f005 

15. 6 

15. 9 

135 14.0 14.5 15.0 15.5 16.0 16.5 

Tlnw.min 

Data printe d by STW 

Printing Time: 9:35:12 AM 

Printin g Date: Thursday, August 25, 2011 

Page 2 of 6 

Page 32 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

Results Name: kll0728a.rdb 

• San«>leName:-k110728a055- Sample ID:-OLP1CM}1-01-1»-009^ Rla:'V110728a.w(r 

I Peak Name:-13C8PFOJM3(IS>* Mate(M}: "421.000376.000 Da' 

I Commenl:"DALGWBPMVV121 RS1107ir Annotatton:" 

Sampl' 

Sample Type: Unkt 

Concentration : 1 00 

Calculate d Cone: H/A 

Acq. Date : 7/29/201 1 

Acq. Time: 4:5 9 

Modified : Y 

Proc . Algorithm: Spec 

Nois e Percentage : 

Base . Sub. Window: 

Peak-Split . Factor: 

Report Largest Peak: 

Min. Peak Height : 

Min. Peak Width: 

Smoothing Width: 

RT Window: 30 

49 AM 

, fy Pa 

50 

1.00 

2 

Yes 

0.0 0 

0.0 0 

0 

0 

Expected RT: IS. a n 

Int . Type: Valle y 

Retentio n Time: 15.8 

Area : 1562420 ct 

Height : 3,01e+00S 

I

Sampla Name:'V110728a0e9r Sample ID: "OLP1CM}1<01' 

PeakName:*13C8PFOA-IS<tS)' Man{e«>:-421.00aa7e.< 

Commei<;-DALGWBPMW12101107ir Annotation:' 

Sample Index: 69 

Sample Type: Unknown 

Concentration: 1.00 ng/mL 

Calculated Cone: H/A 

I

Sample Name:-k110728a06r Sample ID:'OLP1(M]1-O1-I»00r Fle:*k110728a. 

P«ikName:'13C8PFOA4S{(S)* Mate{e«):-421.00CV376.C0ODa' 

Comment:-DALGWTRIP1 LS11071 r AnnotaBon:-

Sample Inde?<: 57 

Sample Type : Unknown 

Calculate d Cone: 

Acq. Time: 

1.00 I 

H/A 

7/29/2011 

5:42:01 AM 

Modified: Ho 

Proc. Algorithm: Specify Pari 

Noise Percentage: SO 

Base. Sub. Window: 1.00 

Peak-Split. Factor: 2 

Rept>rt Largest Peah: Yes 

Min. Peak Height: 0.00 

Min : Widi 0.00 

Smoothing Width; 

RT Window: 

Expecte d RT: 

Height : 

Star t Tin« 

End Time: 

No 

Valle y 

le: 15.8 

1834147 coi 

3.00e'OD5 

15.6 

16.0 

I

Sample Name: 1i11072BaO16' Sample ID: 1 1 003-2&6' FUe:'k110728a.wtr 

Pea)( Name: TFQA' M«M{es): -413.000OGS.000 Da.413.000m9.000 Da ,413.000/169.000 DaCwnment: "1.0 no/mL FC ttd In Synth. VMrter" Annotation:"" 

Sample Index : 16 

Acq. Date 

Acq. Time 

Modified : 

Proc . Algorithm: 

Nois e Per 

Base . Sub 

Peak-Spl i 

Min. Peak 

Min. Peak 

Smoothing 

RT Window 

11 

9: 

29/20 

55:45 

Yes 

Specif y 

Window: 

. Fact 

rgest P 

Heigh t 

Width: 

Width: 

Expected RT: 

Use Rela c 

Int . Type 

Retentio n 

Area : 

Height : 

ve RT: 

Time: 

eak 

Ba 

15608 

Star t Time: 

End Time: 

2 . 6 

SO 

1 

AM 

1.00 

2 

Yes 

0 

0 

0 

0 . 0 

IS. a 

Ho 

se To 

IS. a 

s 

Oil 

00 

Ba, 

et00 5 c 

15.7 

15. 0 

Sample Type : 

Concentration : 

Calculate d Cone: 

Acq. Date : 

Acq. Time: 

Modified : 

Proc . Algorithm: 

Hols e Percentag e 

Base . Sub. Windc 

Peak-Split . Fa d 

Standar d 

1.00 ng/mL 

0.99 8 ng/mL 

7/28/201 1 

3:16:3 2 PM 

Yes 

Specif y Paramet e 

: SO 

*: 1.00 mlii 

o r : 2 

Re!»rt Largest Peak: Yes 

Min. Peak Helghl 

Min. Peal^ Width: 

Smoothing width : 

RT Window: 

Expected RT: 

Use Relativ e RT: 

Int . Type : 

Retentio n Time: 

Area : 16 

Height : 

Star t Time: 

End Tlm-f: 

: 0.0 0 cp s 

0.00 se c 

0 po 

30. 0 se c 

15. a Bin 

Ho 

Manual 

!I7 H counts 

2.6Set00 5 cp s 

15. 6 min 

15. 9 min 

Data printe d by STW 

Printing Time: 9:35:13 AM 

Printin g Date: Thursday, August 25, 

Page 3 of 6 

Page 33 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

Results Name: kll0728a.rdb 

|l|s.r.vleName:'V110728.02 r Sample ID: "11 OOE ^ Fte:'V110728a.^r 

1 Peak Name:'PFOA- MaM<e«):"413.O0ara69.O00D*,413.O0anig.0OODa,413.00Qn69.000Da-

• Coirment-MettiodBbnir Annotation:'' 

Sample Index : 27 

Sample Type : Unknown 14 54 

n Concentration : H/A 

Calculate d Cone: 0.00359 ng/mL 

Acq. Date : 7/28/2011 i-'" * 

1 Acq. Time: 7:08:2 8 PM 

i l-B^ 

Modified : Yes 

Proc . Algorithm: Specif y Parameters - MQ II I 

Nois e Percentage : 50 •"•*** 

Base . Sub. Window: 1.00 min 

Peak-Split . Factor: 2 1,4e4 

Report Largest Peak: Yes 

Min. Peak Height : 0.0 0 cp s 

Min. Peak Width: 0.0 0 fiec ^•^** 

Smoothing Hidth : 0 points 

RT Window: 30.0 se c Ue 4 

Expecte d RT: 15.8 min 

Use Relativ e RT: No , , ^ 

Int . Type : Manual 

Retentio n Time: 15.8 min , 1.0*4 

Area : 367B9 counts g" 

Height : 5.10e + 003 cp s ^ BOQOO 

Star t Time : 15.7 min | 

End Time: 15.0 min « 

1 8000.0 

7000.0 

6000.0 

sooao 

40oao 

3000.0 

2000.0 

1000.0 

14321 

1II iiiU^lilHitlilWttf 

13.5 14.0 14? 

iSanvleName:-kn072a.03 r Sam;4elD:-LCS-1107264- Rle:-k110728a.vi*fr 

1 Peak Name:-PFOA- hla«a(e«):-413.00aO6a.00DDa,413.0Q0i^ig.00ODa,413.00(yi6d.000Da-

• Conment -2ppb LCS' Annotation:" 

1 Sample Index : 31 

Sample Type : QC 

Concentration : 1,99 ng/mL 

Calculate d Cone: 2.0 3 ng/mL 

Acq. Date : 7/:a/:01 1 

Acq. Tine : 8:32:54 PM 5.5e5 

Moditied : Ho 

Proc . Algorithm: Specif y Parameters - KO II I 

Nois e Percentage : 50 5.0e5 

Base . Sub. Window: 1.00 min 

Peak-Split . Factor: 2 

Report Largest Peak: Yes AfinH 

Min. Peak Height : 0.0 0 cp s ^"^ ^ 

Min. Peak Width: 0.0 0 se c 

Smoothing Width: 0 points 

RT Window: 30.0 se c 4,0e5 

Expecte d RT: 15.8 min 

Use Relativ e RT: No 

Int . Type : Valle y 3-5B5 

Retentio n Tims: 15.8 min -

Area : 3727598 counts gHeight : 5.93e+005 cp s ^ ao- S 

Star t Time: 15.7 min 1 " 

End Time: 16.0 min | 

23e 5 

2.0e5 

1.5e5 

1.0e5 

5.0e4' 

j 16.16 

1 "'" 15.78 IL 1 

1 II "•«"-"llli 

I I I 17.26^ J 1 III 

• l J k '°' ^ 1 UlLl7.54 llf^W I i li III il JliL?TJ1 ...isa^Hi i Willi UMLuHMIbLdll M n 

14.S9 '"-"h 1 i|BUf ililiiUMyMPIillP ii 

5 1^.0 15.5 16.0 16.5 17.0 17.5 18.0 

Time. m(n 

15 76 

A • ° ° 13.5 14.0 14. 

1 

L -" ^ 1, 

15.0 15 3 16.0 18.5 17.0 17.5 16.0 

• Sample Name:'k110728a02r Samph ID:-LCS-110726-1- Fle:'V11072ea.vrtrr 

I Peak Name:-PFOA" Ma««(ei): "413.000069.000 D*.413.000/219.000Da.413.00Qf169.000Da-

• Comment: "0.2ppb LCS" Annotation: ~ 

Sample Index : 28 

Sample Type : QC 

Concentration : 0.199 ng/mL 70*4 

Calculate d Cone: 0.210 ng/mL 

Acq. Date : 7/28/201 1 

Acq. Time: 7:29:3 2 PM g^g ^ 

Modified : Yes 

Proc . Algorithm: Specif y Parameters - MQ II I gn ^ 

Hois e Percentage : 50 

Base . Sub. Window: 1.00 mlr, 

Peak-Split . Factor: 3 5- . 

Report Largest Peak: Yes 

Min. Peak Height : 0.0 0 cp s 

Min. Peak Width: 0.0 0 se c 

Smoothing Width: 0 points °-°** 

RT Window: 30.0 se c 

Expecte d RT: 15.8 min 

Use Relativ e RT: No *-° ^ 

Int . Type : Manual 

Retentio n Time: 15.8 min , *0 ^ 

Area : 412430 counts & 

Heigtit: 6.9eet00 4 cp s ^ 

Star t Time: 15.7 min | 3.5e4 

End Time: 16.0 min « 

3.0*4 

2.Se4 

2.0e4 

1.Se4 

1.0e4 

5000.0 

14.54 

I 

1 

i1 l 

i l13.5 14.0 14.5 

• Sample Name: •kl10728a034- Sample ID: TCS-110726.r Fle:-V110728».*tr 

1 Peak Name: TFOA- M«M(et): "413.000069.000 Da,413.00CV21S.OO0Da,413JXXVie9.000Da1 Comment; •20ppb ICS" Annotatton:* 

Sample Index : 34 

Sample Type : QC 

Concentration : 19. 9 ng/mL 

Calculate d Cone: 19. 1 ng/mL 4.Be6 

Acq. Date : 7/28/201 1 

Acq. Time: 9:36:14 PM *•" « 

Modified : No *'^ ^ 

Proc . Algorithm: Specif y Parameters - MQ II I 4Je 6 

Hois e Percentage : 50 

Base . Sub. Window: 1.00 min 4.0e6 

Peak-Split . Factor: 2 

Rei>orC Largest Peak: Yes J.eeo 

Min. Peak Height : 0.0 0 cp s -- -

Min. Peak Width: 0.0 0 se c •*'" " 

Smoothing Width: 0 points 34e 6 

RT Window: 30.0 Sec 

Expected RT: 15.B min 3.2e6 

" • • "•'•" " " ' " ' 3.< « 

Int . Type : Valle y 

Retentio n Time: 15.8 min , 2.8e6 

Area : 31707235 courits g- 2.6e6 

Height : ).92B+0Oi cp s ^ 

Star t Time: 15.7 min % 2.4e6 

End Time: 16.0 min e 

1 2.2ee 

2.0e6 

1.8e6 

1.6e6 

1.4e6 

1.2.6 

1.0e6 

B.0e5 

6.0e5 

4.0«5 

2.0e5 

13.5 14.0 145 

15.76 

L15.8I 

1 

H 16.12 

• LL 18.14 

_AX^SI..;»M>' 

i f o 15.5 16.0 16.5 17.0 it s 18.0 

15.76 

1 

15.0 155- 16. m 0 16.5 17i) 17.5 18.0 | | 

II 

Data printe d by STW 

Printing Time: 9:35:13 AM 

Printin g Date: Thursday, August 25, 2011 

Page 4 of 6 

Page 34 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

Results Name: kll0728a.rdb 

|||San^Name:1c110726a041 " Sample ID:"LCS-110726.10- Fle:"lc110728a.««r 

I Peak Name: "PFOA- M«aa<ee):"413.00(V369.000D»,413.00Cy219.000Da.413.000/169.000D»' 

• Comment tl.2ppb LCS ECP Annotation; ~ 

Sample Index: 41 

Sample Type: QC 

Concentration : 0.19 9 ng/mL 

Calculate d Cone: 0.20 6 ng/mL 

Acq. Date : 7/29/201 1 55e4 

y Acq. Time: 12:04:0 8 AM 

Modified : Yes 

Proc . Algorithm: Specif y Parameters - MQ II I =•* * 

Nois e Percentage : 50 

Base . Sub. Window: 1-00 min 

Peak-Split , Factor: 2 45e4 

Report Largest Peak: Yes 

Min. Peak Height : 0.0 0 cps 

Min. Peak Width: 0.0 0 se c 

Smoothing Hidth : 0 points 4 0e4 

RT Window: 30. 0 se c 

Expecte d RT: IS. 8 min 

Use Relativ e RT: No 

3.5e4 

Int . Type : Manual 

Retentio n Time: 15.B min -

Area : 408715 counts 8 

Height : 5.57et00 4 cps ^ 3-0 ^ 

Star t Time: 15. 5 min 1 

End Time: 15. 9 min • 

~ 25e4 

3X>e4 

1 5M 

1J>e4 

5on.o 

14.56 

• 1 

15.76 

1 

i5.6ajH 

• 'V^ 

m k 174. '""^ 

^ 1 ,|/\ '^f^r'"*, jJii "-^liilL 

13.5 UJO 14.5 15.0 155 16.0 16.5 17.0 1^5 18.0 

1 Sample Name:ini0h8aO4 r Samp*BtD:"LCS-110726-1ff' t*:-k110728a.»4r 

• Peak Name: "PFOA- Mata(et):"413.00(V36d.OOODa,413.00ai'2l9AX>Da,413.00CV169.000Da" 

• C««nent-20ppb LCS ECF Annotatlon:-

Sample Indsx : 47 

Sample Type: QC 

Concentration : 19. 9 ng/mL 

Calculate d Cone: 20. 2 ng/mL 4.2e6 

Acq. Date : 7/29/201 1 

Acq. Time: 2:10:5 0 AM 4.0e6 

Modified : Yes 3 8e6 

Proc . Algorithm: Specif y Parameters - MQ II I 

Nois e Percentage : 50 3 6e6 

Base . Sub. Window: 1.00 min 

Peak-Split , Factor: 2 3.4e6 

Report Largest Peal:: Yes 

Min. Peak Height: 0.0 0 cps 3Je 6 

Min. Peak Width: 0.0 0 se c 

Smoochlhg Width: 0 points 3J>e6 

RT Window: 30. 0 se c 

Expecte d RT: 15. 8 min 2_8^ 

I'se Relativ e RT: No 

2.6e6 

Int . Type: Manual 

Retentio n Time: 15. 6 min , 24«6 

Area : 33467411 counts fr 

Height : 4.336+006 cps <. 2^ $ 

Star t Time: 15.4 min 1 

End Time: 16. 1 min | j_oe6 

1.8e6 

1.6e6 

1.4eB 

1.206 

1.0e6' 

6.0e5' 

6.0e5' 

4.0e5' 

2.0e5' 

0,0-J 

15TS 

15.S3^ 

n 

• • • 

1 3 5 14.0 14.5 15.0 15.5 16.0 165 17.0 17.5 laO 

= T^"* ' -. ! 

I Peak Name: "PFOA* Maw(ea): -413.OOCV369.000 Da.413^)00219.000 Da.413.000/169.000 Da" 

I Comment: "2ppb LCS ECP Annolatton: -

Sample Index : 41 

Sample Type : QC ,s „ 

ConcentcaCIon: 1-99 iig/mL 5.0e5 

Calculate d Cone: 1.99 ng/mL 

Acq. Date : 7/29/201 1 4.8e5 

Acq. Time: 1:07:32 AM ^^ ^ 

Modified : Yes 44^5 

Proc . Algorithm: Specif y Parameters - MQ II I 

Nois e Percentage : SO 4.2*5 

Base . Sub. Window: 1.00 mtr, 

Peak-Split . Factor: 2 ^•"•S 

Report Largest Peak: Yes 1 »«•; 

Min. Peak Height : 0.0 0 cp s " 

Min. Peak Width: 0.0 0 se e 3.6e5 

Smoothing Width: 0 points 

RT Window: 30. 0 se c 3.4e5 

Expected RT: 15.8 min ,.>_« 

Use Relativ e RT: No 3.2e5 

30e 5 

Int . Type: Manual '" ^ 

Retentio n Time: 15.7 min , 2.8e5 

Area : 3558803 counts gHeight : 5.01e»005 cp s »: 2,6*5 

Star t Time: IS. 4 min 1 

End Time: 16. 0 min | •''^ ^ 

- 2.2e5 

2.0e5 

1.6eS 

1.6e5 

1.4e5 

1.2*5 

1.0*5 

8.0e4 

6.0*4 

4.0*4 

2.0*4 

15.62... 

^ 1 

• II 

13.5 14.0 14A5 1^. M^ 0 155 16.0. 16.5 

Time min 

• Sample Name: 1(110728*055" Sample ID: ^3LP1W)1-O1-1&O09- Fle:-Ml0728a.v ^ 

I Peak Name: "PFOA- Ma*a(e>):"413.00Q'369M0Da.413.OO(V319.000Da,413.0O0/169.0OODa-

• Commert:-DALGWBPUW121RS1107ir Annotation:-

Sample Index: 55 

Sample Type: Unknown ,4 ^ 

ConcenCiation : N/A 

Calculate d Cone: '' 0 2 0*4 

Acq. Date : 7/29/201 1 

Acq. Time: 4:59:4 9 AM ,_g„4. 

Modified : Yes . g^. 

Proc . Algorithm: Specif y Parameters - MQ II I 

Nois e Percentage : 50 - ^ 

Base . Sub. Window: 1.00 min '•'• * 

Peak-Split . Factor: 2 

Reixjrt Largest Peak: Yes '-^ ^ 

Min. Peak Height : 0.0 0 cp s 

Min. Peak Width: 0.0 0 se c ^•^•4 

Smoothing Midth: 0 points 

RT Window: 30. 0 se c 1.4*4 

Expecte d RT: 15.B min 

Use Relativ e RT: Ho 1.3*4 

Int . Type: Manual 1.2*4 

Retentio n Time: 15.6 min , 

Area : 2S220 counts § 1.1*4-

Helght : 1.01e->003 cp s ^ 

Star t Time: 15.7 min 1 , (w . 

End Time: IS. 9 min | 

— 9000,0 

6000.0 

6000.0 

5000.0 

4ooao 

3000.0 

2000.0 

1000.0 

0.0 

16.16 

1 

n 

15.75 fl 'S L t 

Il 1 • ill , 

17.0 1:^.5 18.0 

18.13 

1 il 

"•so, U 

1735 \ m \ 

i6.ao . I iH I 

L J Uv°,^i>i'iiit^'^ iiwuira II 15.34 H J WLUl. 

u.m J..,,.HM WUtt 

,,,:;: ^ '"^^^ 

l i s 14.0 14.5 15.0 155 16.0 16 5 

U^iUinMlulMw 1 

lUH^fliffiF •^TTl Ifl" 

17.0 17.5 18.0 

Data printe d by STW 

Printing Time: 9:35:13 AM 

Printin g Date: Thursday, August 25, 

Page 5 of 6 

Page 35 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

Results Name: kll0728a.rdb 

• San^lBMamBrTtilO ^ 

I Peak Name: "PFOA" Hata<*e):"413.00a'369.000Da.413.00(V219.000Da.413.000n69.000Da' 

• ConwnonfDALGWTRIPI LS110713" Annotatton:"" 

Sample Index: 57 

Sample Type 

N/A 

Calculate d Cone: 

Acq. Date : 

Acq. Time: 

Modified : 

Proc . Algorithm: 

Nois e Percentag e 

Base . Sub. Wlndo 

Peak-Split . Fact 

0.24 3 

7/29/201 1 

S:4Z:0 t AM 

No 

Specif y Pa 

•: 1.00 

3r: 2 

Report Largest Peak : Yes 

Min. Peak Heigh t 

Min. Peak Width: 

Smoothing Width: 

RT Window: 

Expecte d RT: 

Use Relativ e RT: 

Int . Type : 

Retentio n Time: 

0.0 0 

0.0 0 

0 

30. 0 

16. 8 n 

No 

Valle y 

Area : 526502 cour 

Height : 

Star t Time: 

End Time: 

.tle'-OOi c 

IS. 7 n 

15. 9 I> 

ng/mL 

ameters - MQ II I 

r

Sample Name:-k110728a06g^ S«mpte|D:"GLPiaO1-O1.19O10^ Fle:-k110728a.vi4r 

Peak Name: TFOA" Masses):'413.000069.000 Da.413.000/219.000 Da .413.000/168.000 Da" 

Commeot:"DALGWBPMW1210110713- -

Sample Index : 69 

Sample Type : 

Concentration : K/A 

Calculate d Cone: 0.0682 

Acq. Date : 7/29/201 1 

Acq. Time: 9:55:1 5 AM 

Modified : Yes 

Proc . Algorithm: Specif y Par 

Hois e Percentage : 50 

Base . Sub. Window: 1.00 

Peak-Split . Factor: 2 

Report Largest PeaK: Yes 

Min. Peak Height : 0.0 0 

Min. Peak Width: 0.0 0 

Smoothing Width: 0 

ng/mL 

ktneters - MO II I 

min 

s e c 

points 

RT Window: 30. 0 se c 

Expected RT: 15-B n 

Use Relativ e RT: No 

Int . Type : Manual 

Retentio n Time: 15. 8 m 

In 

in 

Height : 2.01et00 4 cp s 

Star t Time: 15. 5 m in 

^ 

^ 

2.1*4 

2.0*4 

1.9*4 

1.8*4 

1.7*4 

1.5*4 

1.4*4 

1.3*4 

1.2*4 

Data printed by STW 

Printing Time: 9:35:13 AM 

Printin g Date: Thursday, August 25, 

Page 6 of 6 

Page 36 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

Results Name: kll0728a ext.rdb 

k110728a ext.rdb (PFOA): "Quadratic" Regression ("1 / x" weighting): y = -7.06e+003 x*2 + 1.71 e+006 x + 1.66e+004 (r = 0.9994) 

1.03e8 

1.00e8 

45 50 55 

Concentration, ng/mL 

Data printed by STW 

Printing Time: 9:35:51 AM 

Printing Date: Thursday, August 25, 2011 

Page 1 of 1 

Page 37 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

Results Name: kll0728a ext.rdb 

• SanipleMame:-k110728a0ir Sample ID:*11003-25-8" Rto:l(11O720a.wtr 

I Peak Name:'PFOA- MaM{**):-413.000r3e9.000Da.413.00(V219.0000a,413.00CV169.0000a* 

• Comment-1.DnaftnLFC ttd In Synth. Wal*r- Annotation:-

Sample Indey: 16 

• B TyF>e: Standar d 

ng/mL 

ng/mL 

Sample Type : Standar d 

Concentration : 

Calculate d Cone: 0 . 

Acq. Date : l/2 i 

Acq. Time: 3:16 

Modified : Y 

Proc . Algorithm: Spec 

Koise Percentage : 

Base . Sub. Window: 

Peak-Split . Factor : 

Report Largest Peak: 

Min. Peak Height : 

Min. Peak Hidth : 

Smoothing Width: 

.00 

967 

/201 1 

:32 PM 

e s 

i l y Pa 

50 

1.00 

2 

0.0 0 

0.0 0 

0 

Int . Type 

Retentio n 

Area : 

Height : 

Time 

Man 

1 

GS9011 

2.S5 e 

a l 

.7 ml 

005 cp 

15. 9 min 

2.6a5 

3.Se5 

2.4*5 

2J3e5 

2.2e5 

2.1*5 

2J>*5 

1.9*5 

1.8*5 

1.7e5 

1.6*5 

1.5*5 

1.4*5 

1.3*5 

1J*S 

1.1*5 

1.0*5 

9.0*4 

8.0*4 

7.0*4 

6.0*4 

5.0M 

4.0*4 

3.0»4 

2.0M 

1.0*4 

0_0 

14.55 

i K 

15 75 

B i , rNmwr' tfi»,'<. iviii,":"-;ii, •T-rrW ^ 

I

sample Name: •1<1l0728a02Er Sample ID: "LCS-110726.1' FUe:"k110728a.wWr 

Peak Name: 'PFOA' MaM(**): '413.000/369.000 Da,413.00CV219.000 Da.413JXXV169.000 Oa" 

Comment-0.2ppb LCS* Annatatk>n:~ 

Sample Index: 28 

I

Sample Name: lc11072BaO2r Sample ID: Ml 00S«9' Fie: 1(110728a.wtT 

Peak Nam*: TFOA* Masa(*a): '413.OO0ir369.OD0 Da ,413.000/219.000 Da ,413.000/169.000 Da' 

Comm»nt:"M*t>>od Blank- Annotation:-

Sample Index : 27 

Sample Type : Unknown 

Concentration : N/A 

Calculate d Cone: 0.00606 ng/mL 

Acq. Date : 7/2B/2011 

Acq. Time: 

Modified : 

Proc . Algorithm 

Hois e Percentag i 

Base . Sub. Windi 

Peak-Split . Fa d 

7:0B:28 PM 

Yes 

Specif y Pa 

: 50 

J: 1.00 

o i : 2 

Report Largest Peak: Yes 

Min. Peak Heighl 

Min. Peak Width 

Smoothing Midth 

RT Window: 

Use Relativ e RT 

int . Type : 

Retentio n Time: 

Area : 

Height : 

Star t Time: 

End Time: 

0.0 0 

0 

30. 0 

15.7 D 

N* 

Manual 

15.8 

26963 cou 

<.92e-00 3 

15. 9 n 

1.7e4 

1.6*4 

1.5e4 

1.4«4 

1.3*4 

1.2*4 

1.1*4 

1.0e4 

90oao 

8000.0 

7000.0 

6000.0 

5000:0-

4000.0 

3000.0 

2000.0 

1000.0 

1434 

14.32 

ini. .iiiii.iiiJUiiuyfiiu 

15.76 

1 

14.8S '=-'^, i°^|Hi | 

MidiP ^iwff*!**, ..'T.'-.r .'•;';.•... 

16.16 

,8.,2 . 

Il i n"r£l iu|U|||P^ 

'rrPl' TM 

[

Sample Name: "Vl 10728*031' Sample ID: t.CS-110726-4" F»e: 'V11072Sa.wl^ 

Peak Name: 'PFOA' Mau(es): -413.000i'369.000 Da,413.000/219.000 Da,41 S.OOVI69.000 DaComment: '2ppb LCS' 

Sample Type: 

Concentration : 

Calculate d Cone 

Acq. Time: 

Modified: 

Proc . Algorithir 

OC 

0.199 ng/mL 

: 0.232 ng/mL 

7/28/201 1 

7:29:3 2 PM 

Yes 

: Specif y Paramete 

Base . Sub. Window: 

Peak-Split . Factor: 

Report Largest Peek: 

Smoothing llidt h 

RT Hindow: 

Elxpecced RT: 

L'se Relative RT 

Retention Tine: 

Area: 

Height : 

Star t Time: 

15.8 

I1Z159 c< 

7.00e+004 

Sample Index : 31 

Sample Type : OC 

Concentration : 1.99 

Calculate d Cone: 2.20 

Acq. Date : 7/28/201 1 

Acq. Time: 8:33:51 PM 

Modified : No 

Proc . Algorithm: Specif y Pa 

Nois e Percentage : 50 

Base . Sub. Window: 1.00 

Peak-Split . Factor: 2 

Rei>ort Largest Peak: Yea 

Min. Peah Height : O.OC 

Min. Peak Width: O.OC 

Smoothing Width: 0 

RT Window: 30. 0 

Expecte d RT: 15.7 

Use Relativ e RT: Ho 

Inc . Type : Valle y 

Retentio n Time: 15.8 

Area : 3727598 cou 

Height : S.93e+005 

ng/mL 

ng/mL 

ramet e 

min 

n is 

cps 

Data printe d by STW 

Printing Time: 9:37:04 AM 

Printin g Date: Thursday, August 25, 

Page 1 of 3 

Page 38 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

Results Name: kll0728a ext.rdb 

I

Sample Name: ini0728a041- Sampla ID: TCS-110726-10- Fie: M10728a.wttr 

Peak Name: TFOA' Maas(e«): "413.OOCV369.000 Da.413.000/219.000 Da,413.000/169.000 Da* 

Comment: *0.2ppb LCS ECF" Annotation; ~ 

Sample Inde:(: 11 

Sample Type : QC 

Concentration : 0.199 ng/mL 

Calculate d Cone: 0.232 ng/mL 

Acq. Date : 7/29/201 1 

Acq. Time: 12:01:0 8 AM 

I

San«)leNam*:-V110728a034- Sample ID:'LCS-110726-r FUe: •V110728a.vi4fr 

Peak Name: 'PFOA' Ma«*(*«): '413.000/369.000 Da,413.000/219.000 Da,413.00(V169.000 Da' 

Comnwnt '20ppb LCS" Annotation:" 

Concentr a ion : 

Calculate d Cone: 

Acq. Date 

Acq. Ti M 

Modified : 

Proc . Alg 

Nois e Pe r 

Base . Sub 

Peak-SplI 

rithm : 

entag e 

Wlndoi 

. Facto 

19. 9 

20. 3 

7/28/2 0 

9:36:1 1 

Ho 

Specif y 

1 

PM 

Pa 

: 1.00 

c : 2 

Report Largest Peak: Yes 

Min. Peak 

Min. Peak 

Smoothing 

RT Window 

Heigh t 

Hidth : 

Hidth : 

Expecte d RT: 

Use Rela t 

Int . Type 

Retentio n 

Area : 

Height : 

ve RT: 

Time: 

0 

0 

0 

30. 0 

15.7 

Ho 

Valle y 

15.8 

31707235 

Star t Time: 

End Time: 

.92etOO 

15.7 

15. 0 

00 

01) 

ng/mL 

cameters - MQ 

min 

? e c 

points 

min 

c p s 

nln 

15.0 15.5 16.0 1&5 17.0 

I

SanvlaName:'VI10728aO4r Sampla ID:'LCS-1l072S>ir Fle:-kll0728a.wtr 

Peak Nam*; 'PFOA' Mac*(es): '413.000/369.000 Oa,413.00(V219.000 Da,413JX)IV169.00D Da" 

Comment '2ppb LCS ECP AnnotaOon: ~ 

5.5*4 

Modified : 

Proc . Algorithm 

Hols e Percenta g 

y e s 

Specif y Pa 

: 50 

Base . Sub. Hindow: 1.00 

Peak-Split . Factor: 2 

Report Largest Peak: Yes 

Kin . Peak Heigh 

Min. Peak Width 

Smoothing Width 

RT Window: 

Expected RT: 

Use Relativ e RT 

Int . Type : 

Retentio n Time: 

Area : 

: 0.0 0 

0.0 0 

0 

30. 0 

15.7 D 

Ho 

Manual 

15.B D 

12501 cou 

13.5 14.0 

I

Sampl*Name:•k110728a04r SamplelD:-LCS-110726-16" Fl*; 1(110728a.wir 

Peak Name: TFOA" Mass(e«): '413.00CV369.000 Da.413.000/219.000 Da,413.000/169.000 Da' 

Commant: "ZCfipb LCS ECP Annotatnn: ~ 

Sample Index : Sample 

Sample Type: 

Calculate d Cone: 

Acq. Date : 

Acq. Time: 

Modified : 

Proc . Algorithm: 

Hols e Percentag e 

H 

QC 

1.99 

2.09 

7/29/201 1 

1:07:32 AM 

Ves 

Specif y Pa r 

50 

Base . Sub. Window: 1.00 

Peak-Split . Fact 

Report Largest P 

Min. Pe=k Height 

Min. Peak Width: 

Smoothing Width: 

RT Hindow: 

Expecte d RT: 

l'se Relativ e RT: 

Int . Type: 

Retentio n Time: 

r : 2 

a k : Yes 

0.0 0 

0.0 0 

30. 0 s 

15. 7 m 

No 

Manual 

15.7 n 

Area : 3556538 coun 

Height : 

Star t Time: 

End Time: 

.01e*005 e 

15.4 n 

15. 9 m 

ig/mL 

ig/mL 

min 

s e e 

.n 

.n 

ps 

.n 

in 

irrple Type; 

Concentration : 

Calculate d Cone 

Acq. Date : 

Acq. Time: 

Modi lied : 

Proc . Algorithm 

Hois e Percentag e 

Base . Sub. Hlndc 

Peak-Split - Faci 

19. 9 

7/29/201 1 

3:10:50 AM 

Yes 

Specif y Pa 

: SO 

w: t.OO 

o r : 2 

Re|>ort Largest Peak: Yes 

Min. Peak Helghi 

Min. Peak Width 

Smoothing Width 

RT Window: 

Expected RT: 

irse Relativ e RT 

Int . Type : 

Retentio n Time: 

0.0 0 

0.0 0 

0 

30. 0 

ng/mL 

ng/mL 

amet e 

c p s 

ee 

15.7 min 

Ho 

Manual 

15.6 min 

4.2*6 

4.0*6 

3.8*6 

3.6*6-

3.4*6-

3.2*6 

3.0*6-

2.6*6-

2.6*6 

2.4*6-

2.2*6 

2.0*6 

1.6*6 

1.6*6-

1.4*6-

1.2*6-

1.0*6-

8.0*5-

ao*5 

4.0*5-

2.0*5-

0.0-

17.0 17.5 

Data printe d by STW 

Printing Time: 9:37:04 AM 

Printin g Date: Thursday, August 25, 2011 

Page 2 of 3 

Page 39 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA In Water Samples 

Off-Site BP Property - July 2011 

Results Name: kll0728a ext.rdb 

• SarnJle Name: Td 10728*061' Sample ID: "OLP1(«1-01-1W)06" Fll*;Tc110728a.yi«r 

• P*akNBnM:-PFOA' Ma%«<e*):'413.000/369.000 Oa,413.000/219.000Da,413.00Q/169.000Da-

• Comm«nt-DALGWBPMW4701107ir Annotatten;-

Sample Inde*-.: 61 

Sample Type : Uriknown 

0-317 

7/29/201 1 

7:06;3 5 AM 

ng/mL 

Algorithm: Specif y Parai 

Sub. Window 

Peak- p u t 

Report Largi 

Min. Peak Height : 

Min. Peak Width: 

• thin g Width: 

RT Mini 

Use Rela' 

Data printed by STW 

Printing Time: 9:37:04 AM 

Printing Date: Thursday, August 25, 2011 

Page 3 of 3 

Page 40 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

ATTACHMENT C: ANALYTICAL METHOD(S) 

Page 41 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

3M Environmental Laboratory 

Method 

Method of Analysis for the Determination of Perfluorinated Compounds in Water 

by LC/MS/MS; Direct Injection Analysis 

Method Number: ETS-8-044.0 

Adoption Date: Upon Signing 

Effective Date: Q U I n fc>~) 

Approved By: 

^//^/o y 

William K. Reagen, Laboratory IVIanager 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 42 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

1 Scope and Application 

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

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

PerfluorononanoicAcid (PFNA), Perfluorodecanoic Acid (PFDA), PerfluoroundecanoicAcid (PFUnA), 

PerfluorododecanoicAcid (PFDoA), Perfiuorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), 

and Perfiuorooctanesulfonate (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 "Detemnination of 

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

Performance Liquid Chromatography/Mass Spectrometry". 

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

defined QC elements are satisfied. 

Sample collection is not covered under this analytical procedure. 

2 IVIethod Summar y 

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

particulate may not be suitable for analysis by this method. Samples containing suspended particulate 

should be centrifuge prior to removing a sample aliquot, or filtered. 

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

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

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

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

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

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

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

accuracy for analytical results. 

3 Definitions 

3.1 Calibration Standard 

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

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

method. Calibration standards are used to calibrate the instmment 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 determine if test substances or 

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

ETS-8-044.0 Page 2 of 11 

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

Injection Analysis 

Page 43 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

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 detennine 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 determine 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. 

ETS-8-044.0 Page 3 of 11 

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

Injection Analysis 

Page 44 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

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, sun'ogate(s) are added to all samples and quality 

control samples. Sun'ogate(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 detennined; 

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

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

The laboratory is responsible for maintaining a safe wori< environment and a cun^ent awareness of local 

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

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

4.2 Cautions 

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

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

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

conditions of analysis by njnning method blanks. 

ETS-8-044.0 Page 4 of 11 

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

Injection Analysis 

Page 45 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

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 ^lL 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, 25ijL, SOpL, lOOpL, 250|JL, 500|JL, 1000|JL. 

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 |jm 

Analytical Column: Betasil CI8,4.6 mm x 100 mm, 5 |jnn 

Temperature: 10°C 

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

Mobile Phase (B): Methanol 

Gradient Program: 

Time (min) 

0.0 

0.5 

11.0 

13.5 

13.6 

17.0 

%A 

97 

97 

5 

5 

97 

97 

%B 

3 

3 

95 

95 

3 

3 

Flow Rate 

(mL/min) 

1.0 

1.0 

1.0 

1.0 

1.0 

1.0 

Injection Volume: 100 |JL. 

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

Run Time: ~ 17 minutes. 

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

provided that data quality objectives are met. 

ETS-8-044.0 Page 5 of 11 

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

Injection Analysis 

Page 46 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

6.3 MS/MS System 

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

Analyte 

PFBA 

PFPeA 

PFHA 

PFHpA 

PFOA 

PFNA 

PFDA 

PFUnA 

PFDoA 

PFBS 

PFHS 

PFOS 

Transition Monitored 

213^169 

263^219 

313 ^269 and 313 ^119 

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

413 ^ 369, 413 ^ . 219 and 413 -^ 169 

463 -^ 419, 463 -^ 169 and 463 ^219 

513 -» 469, 513 ^ 219 and 513 ^ 269 

563 -» 519, 563 ^ 269 and 563 -^219 

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

299 ^ 80 and 299 ^ 99 

399 -* 80 and 399 -> 99 

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

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

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

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

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

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

7 Reagents and Standards 

7.1 Chemicals 

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

Methanol - HPLC grade 

Ammonium Acetate - A.C.S. Reagent Grade 

7.2 Standards 

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

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

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

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

Products, Inc 

Perfluorooctanoic Acid (PFOA - C8 acid); 3M 

PerfluorononanoicAcid (PFNA-C9 acid); Oakwood Products, Inc 

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

PerfluoroundecanoicAcid (PFUnA-C11 acid); Oakwood Products, Inc 

PerfluorododecanoicAcid (PFDoA-C12 acid); Oakwood Products, Inc 

Perfiuorobutanesulfonate (PFBS - C4 sulfonate); 3M 

Perfluorohexanesulfonate (PFHS - C6 sulfonate); 3M 

Perfiuorooctanesulfonate (PFOS - C8 sulfonate); 3M 

ETS-8-044.0 Page 6 of 11 

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

Analysis 

Page 47 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

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, |JL volumes may be spiked into volumetric flasks 

when diluting stock solutions to appropriate levels. 

100 (jg/mL target analyte SSSs—^Weigh out 10 mg of analytical standard (corrected for percent salt 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 connection is given below for PFOS. 

,. X- r 1 molecular weight of anion 

salt correction factor = 

moclecular weight of salt 

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

538 

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

5 Mg/mL (5000 ng/mL) mixed working standard—Add 0.5mL each of the lOOpg/mL SSSs to a 10mL volumetric 

flask and bring up to volume with solvent. 

250 ng/mL mixed working standard—Add 1.25mL of the 5 [jg/mL -mixed worthing standard solution to a 25mL 

volumetric flask and bring up to volume with solvent. 

125 ng/mL mixed standard—Add 625|JL of the 5 |jg/mL-mixed worthing 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. 

ETS-8-044.0 Page 7 of 11 

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

Analysis 

Page 48 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

7.5 Calibration Standards 

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

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

be adjusted to meet the data quality objectives addressed in the general project outline. Calibration levels other 

than those listed below can be prepared as needed. 

Concentration 

of WS, ng/mL 

125 

125 

125 

125 

250 

250 

250 

250 

5000 

5000 

5000 

Volume of WS,M L 

10 

15 

20 

30 

20 

50 

100 

200 

25 

50 

100 

Final Volume of 

Calibration Standard (mL 

of ASTM Type 1 Water, or 

other suitable water) 

50 

50 

50 

50 

50 

50 

50 

50 

50 

50 

50 

Final Concentration of 

Calibration Standard, ng/mL 

(ppb) in ASTM Type 1 Water, 

or other suitable water 

0.025 

0.0375 

0.050 

0.075 

0.100 

0.250 

0.500 

1.00 

2.50 

5.00 

10.0 

8 Sample Handling 

8.1 Water Sample Preparation 

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

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

sample aliquot, or filtered. 

Thoroughly mix sample before removing an aliquot and placing in a labeled plastic autovial. Plastic is 

prefen-ed 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-detemnined acceptance criteria. Low-level curve 

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

The coefficient of 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 

ETS-8-044.0 Page 8 of 11 

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

Analysis 

Page 49 of 52 
GLP10-01-01; Interim Report 19 

Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

be within ±30%. Justification for exclusion of calibration curve points will be noted in the raw data. A minimum of 6 

points will be used to construct the calibration curve. 

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

curve (if necessary) and reanalyze. 

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

10.3 Sample Replicates 

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

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

replicates excludes field blanks. 

10.4 Surrogate Spikes 

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

10.5 Lab Control Sample 

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

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

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

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

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

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

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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: 

Analyte found (ng/mL) = (Peak Area - Intercept) ^ ^ ^ 

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. 

_ Total analyte found (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. 

Nonconfomnance 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 perfomnance 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 perfomnance criteria have not been met, the data must be footnoted on tables and 

discussed in the text of the report. 

12.1 System Suitability 

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

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

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

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

have area counts with an RSD of <5% and a retention time RSD of <2% to be compliant. 

12.2 Quantitation 

Calibration Curve: The coefficient of detemnination (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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Analysis of PFOA in Water Samples 

Off-Site BP Property - July 2011 

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 infomnation regarding the required precision of laboratory control spikes. 

13 Pollution Prevention and Waste Management 

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

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

14 Records 

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

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

sample and standard prep sheets/records, instrument mn log (instalment batch records, instrument acquisition 

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

15 Affected Documents 

None. 

16 Revisions 

Revision 

Number Summary of Changes 

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