Perfluorooctanoic Acid (PFOA) 

Site Related Environmental 

Assessment Program

3M and Dyneon LLC

Decatur, Alabama 

Quarterly Status Report 

October 1, 2011 to December 31, 2011

11P-0094-v4-1

3M Company

St. Paul, Minnesota

®
Perfluorooctanoic Acid (PFOA) Site Related

Environmental Assessment Program

3M Decatur, Alabama Site

Quarterly Status Report

October 1, 2011 to December 31, 2011

Prepared for

3M Company and Dyneon LLC

By

WESTON SOLUTIONS, INC.

West Chester, Pennsylvania 19380

W.O. No. 02181.129.118.0001
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i

TABLE OF CONTENTS

Section Page

1. BACKGROUND ............................................................................................................ 1-1

2. SUMMARY OF ACTIVITIES..................................................................................... 2-1

ATTACHMENTS

Attachment Title

1 GROUNDWATER SAMPLING TECHNICAL PROGRESS REPORT

2 VEGETATIVE UPTAKE STUDY TECHNICAL PROGRESS 

REPORT
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1-1

1. BACKGROUND

In accordance with the Phase 3 Work Plan for Sampling Environmental Media

(WESTON, 2009) and the Memorandum of Understanding (MOU) (3M, 2004) with 

EPA, 3M and Dyneon LLC are undertaking a Perfluorooctanoic Acid (PFOA) SiteRelated Environmental Monitoring and Assessment Program at their Decatur, Alabama,

plant. Per the agreement between EPA and 3M, this report represents the status report of 

this effort as required by the MOU for the October 1, 2011 through December 31, 2011

time period. For brevity, and following previous convention, this report will be referred 

to as the December 31, 2011 Quarterly Status Report.
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2-1

2. SUMMARY OF ACTIVITIES

The Phase 2 Work Plan and MOU were finalized on October 25, 2004. Phase 2 of the 

monitoring program has been completed and Phase 3 commenced on November 19, 2009 

with EPA’s acceptance of the Phase 3 Work Plan. This report represents the seventh

quarterly status report under Phase 3. It covers the October 1, 2011 to December 31, 2011

timeframe and includes a description of activities completed under the Phase 3 Work 

Plan. In addition to Phase 3 MOU activities, 3M is performing other non-MOU studies 

related to PFOA to provide data for itself, the Alabama Department of Environmental 

Management (ADEM) and/or EPA Region 4. Where relevant, non-MOU data may be 

incorporated in the revised Screening Level Human Exposure Assessment. This nonMOU information will also be described and provided in these quarterly status reports.

Details on activities completed during this reporting period are as follows:

Groundwater Sampling Technical Progress

• Off-site well sampling and construction – Groundwater samples were collected in 

September 2011 from two new Phase 3 monitoring wells in the epikarst (610S) 

and limestone bedrock (610L) approximately 1 mile to the southeast of the 3M 

Decatur facility. Analysis of PFOA in the 610 well cluster groundwater samples 

has been finalized and data are provided in the Groundwater Sampling Technical 

Progress Report (Attachment 1).

• On-site groundwater – Groundwater sampling was performed in September 2011 

at 18 locations in the chemical plant area and northeast of the closed landfill at the 

Decatur site as part of routine quarterly monitoring for conventional constituents. 

This effort included the collection of samples for PFOA analysis and was 

described in the September 30, 2011 Quarterly Status Report. The September 

2011 monitoring of groundwater in the chemical plant and closed landfill area is a 

component of the Remedial Action Agreement Program being executed by 3M 

under the ADEM NPDES program and is not a MOU-related activity. Analysis of 

PFOA in these groundwater samples has been finalized and data are provided in 

the Groundwater Sampling Technical Progress Report (Attachment 1).
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2-2

Groundwater sampling was performed between December 8, 2011 and December 

14, 2011 at 27 monitoring wells in the Former Sludge Incorporation Area (FSIA). 

Two of the monitoring wells, 136R and 137R, were dry at the time of sampling 

and were not sampled. The monitoring wells CW26C and CW26L located in 

Field 6 were not sampled because liner placement activities prevented access. The 

December 2011 monitoring of groundwater in the FSIA is a component of the 

Remedial Action Agreement Program being executed by 3M under the ADEM 

NPDES program and is not a MOU-related activity.

Vegetative Uptake Study Technical Progress

• Plant Growing and Maintenance Activities – Routine monitoring of watering and 

ventilation systems and plant growth has been performed at the Athens, Alabama 

nursery site where the vegetative uptake study is being conducted. Weeding, 

thinning, and pest control activities have also continued. Composite samples of 

the turnip green crop, pre-planting soils (prepared from the archived potato soil 

blends) and post-harvest soils from the turnip greens crops were collected and 

shipped to the 3M Environmental Laboratory for PFOA analysis. Additional 

details on plant growth, maintenance and sampling activities are provided in the 

Vegetative Uptake Study Technical Progress Report (Attachment 2).

Expanded summaries of these activities, where applicable, are included as attachments to 

this status report and provide additional details on the work which has been completed. 

For utility and clarity of communication, each attachment has been constructed as a 

separate report on a different media and/or study area.
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ATTACHMENT 1

GROUNDWATER SAMPLING

TECHNICAL PROGRESS REPORT

OCTOBER 1, 2011 – DECEMBER 31, 2011
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Att 1-1

GROUNDWATER SAMPLING

TECHNICAL PROGRESS REPORT

3M AND DYNEON DECATUR, ALABAMA

The following subsections describe groundwater sampling activities completed during the 

fourth quarter of 2011 and summarize the results of analyses for PFOA. Analytical data 

packages for Interim Report 22 and Interim Report 23 are provided in Appendices A and

B. Full analytical data packages, including raw data, chromatograms and correspondence,

are provided in the Raw Data Appendix to this quarterly status report.

OFF-SITE ACTIVITIES

Off-site 610 Series Well Cluster Construction and Sampling

Two new Phase 3 monitoring wells located approximately 1 mile to the southeast of the 

3M Decatur facility were installed in August 2011 and sampled in September 2011 as 

described in the September 30, 2011 Quarterly Status Report. Analysis of PFOA in the 

groundwater samples from the shallow epikarst Well 610S and the limestone bedrock 

Well 610L has been finalized. Analytical results are summarized in Table 1 and shown in 

Figure 1.

ON-SITE ACTIVITIES

On-Site Chemical Plant and Closed Landfill Groundwater Sampling

Groundwater sampling was performed during the weeks of September 19 and 26, 2011 at 

18 locations in the chemical plant area and northeast of the closed landfill at the Decatur 

site as part of routine quarterly monitoring for conventional constituents. This effort 

included the collection of samples for PFOA analysis. The September 2011 monitoring of 

groundwater in the chemical plant and closed landfill area is a component of the Remedial 

Action Agreement Program being executed by 3M under the ADEM NPDES program and 

is not a MOU-related activity. Monitoring locations included 17 individual wells and the 

combined groundwater discharge from the maintenance pumping wells at the closed 

landfill prior to treatment at the on-site groundwater treatment plant. The wells sampled 

included 203L, 220R, 220L, 222R, 227R, 227L, 310R, RW312R, 317L, 324L, RW327R, 
J:\FOLDERS.0-9\3M-DECAT\Phase 3 Work Plan\4Q11 Status Report\4Q11 Status Report.doc 1/30/2012

Att 1-2

328R, 328L, 330R, 330L, RW331S, 335S and the combined landfill groundwater 

extraction wells sample GRS04. Analytical results for the chemical plant area and closed 

landfill area groundwater samples have been finalized and are summarized in Table 2 and 

shown in Figure 2.

Former Sludge Incorporation Area Monitoring Wells

3M implemented a groundwater monitoring program as part of the Former Sludge 

Incorporation Area (FSIA) capping program to establish current conditions at the site and 

to provide adequate coverage to establish current conditions and monitor future conditions

at the site. Data developed on groundwater elevations, contours and PFOA concentrations 

will be used for evaluating the effectiveness of the multi-layer cap system currently being 

installed in the Former Sludge Incorporation Area. The December 2011 monitoring is not a 

MOU-related activity but is being executed by 3M under a NPDES Remedial Action 

Agreement with ADEM. The current FSIA groundwater program includes 31 existing 

monitoring wells. Monitoring well clusters consist of three wells with one in each of the 

residuum, epikarst and limestone bedrock strata (i.e., designated 130R, 130S and 130L, 

respectively). Groundwater sampling was performed between December 8, 2011 and 

December 14, 2011 at 27 monitoring wells in the Former Sludge Incorporation Area 

(FSIA). Two of the monitoring wells, 136R and 137R, were dry at the time of sampling 

and were not sampled. The monitoring wells CW26C and CW26L located in Field 6 were 

not sampled because liner placement activities prevented access. Groundwater samples 

were submitted to the 3M Environmental Laboratory for PFOA analyses and will be 

reported in a subsequent quarterly status report.
Table 1 

Off-Site 610 Monitoring Wells Groundwater Average PFOA Concentrations

September 2011

Sample ID Well ID

Average PFOA Concentration 

(ng/mL; ppb)

DAL GW 610S 0 110921 610S 1.16

DAL GW 610L 0 110921 610L 3.66

Notes:

Average PFOA is the average of primary and duplicate sample analytical results.

Well ID suffixes:

 S = epikarst

 L = bedrock

\\Weston\natacc\FOLDERS.0‐9\3M‐DECAT\Phase 3 Work Plan\4Q11 Status Report\Attachment 1\Table 1 ‐ September 2011 610 Wells Average PFOA.xls
610L

Joe Wheeler Hwy

Beltline Rd

(Highway 20/72)

Figure 1

Off-Site Phase 3

Monitoring Well Cluster 610

Groundwater Average PFOA Concentrations

September 2011

Decatur, AL

File: Y:\3MDec\MXD\MW610_PFOA_sept2011.mxd, 11/30/2011 1:32:16 PM, ricksc

400 200 Feet 0

Legend

Monitoring Well Location

3M Facility Boundary

Notes:

Average PFOA is the average of primary and duplicate

sample analytical results in ng/mL (ppb).

Well ID suffixes:

 S = epikarst

 L = bedrock

ID

Average PFOA 

(ng/g; ppb) 

610S 1.16

610L 3.66
Table 2 

On-Site Well Monitoring Program Groundwater Average PFOA Concentrations

September 2011

Sample ID Well ID

Average PFOA Concentration 

(ng/mL; ppb)

DAL GW 203L 110930 203L 139

DAL GW 220R 110930 220R 29.3

DAL GW 220L 110930 220L 49.8

DAL GW 222R 110930 222R 366

DAL GW 227R 110922 227R 251

DAL GW 227L 110922 227L 144

DAL GW 310R 110928 310R 969

DAL GW 312R 110929 312R 1980

DAL GW 317L 110928 317L 0.322

DAL GW 324L 110923 324L 292

DAL GW 327R 110928 327R 661

DAL GW 328R 110927 328R 361

DAL GW 328L 110928 328L 102

DAL GW 330R 110928 330R 358

DAL GW 330L 110928 330L 376

DAL GW 331S 110929 331S 735

DAL GW 335R 110927 335R 3580 [a]

DAL GW GRS04 110930 multiple wells 3010

Notes:

Average PFOA is the average of primary and duplicate sample analytical results.

DAL GW GRS04 110930 is a composite sample from multiple extraction wells.

Well ID suffixes:

 R = residuum

 S = epikarst

 L = bedrock

[a] Sampling location 335R did not have an appropriate field matrix spike to assess PFOA accuracy.

\\Weston\natacc\FOLDERS.0‐9\3M‐DECAT\Phase 3 Work Plan\4Q11 Status Report\Attachment 1\Table 2 ‐ September 2011 CP LF GW Average PFOA.xls
331S

227R

222R

220L

203L

330R

327R

312R

310R

328L

324L

317L

Tennessee River/

Wheeler Reservoir

Chemical 

Plant

Closed

Landfill

335S

331S

227R

222R

220L

203L

330R

327R

312R

310R

328L

324L

317L

Tennessee River/

Wheeler Reservoir

Chemical 

Plant

Closed

Landfill

335S

Figure 2

Groundwater PFOA Concentrations

Chemical Plant

and Closed Landfill Area

September 2011

450 225 0 Feet

Legend:

Decatur, AL

File: Y:\3MDec\MXD\PFOA_Sept2011_Chemicalplant_closedlandfill.mxd, 11/30/2011 1:54:10 PM, ricksc

Groundwater sampling locations

Notes:

-Average PFOA concentrations based on primary and

 duplicate results in ng/mL (ppb).

-GRS04 is a composite sample from multiple extraction wells.

-[a] Sampling location 335R did not have an appropriate FMS to

 assess PFOA accuracy.

R - Residuum Well

S - Epikarst Well

L - Bedrock Well

203L 139

220R 29.3

222R 366 220L 49.8

227R 251

227L 144

GRS04 3010

310R 969

312R 1980

317L 0.322

324L 292

327R 661

328R 361

328L 102

330R 358

330L 376 331S 735

335R 3580 [a]
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APPENDIX A TO ATTACHMENT 1

GLP10-01-01 INTERIM REPORT 22

The full data package, including raw data, is provided in the Raw Data Appendix.
























































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APPENDIX B TO ATTACHMENT 1

GLP10-01-01 INTERIM REPORT 23

The full data package, including raw data, is provided in the Raw Data Appendix.
GLP10-01-01; Interim Report 23 

Analysis of PFOA in Groundwater Samples 

Off-Site 610 Wells; September 2011 

3M 

GLP10-01-01. Interim Report 23: Analysis of PFOA in Groundwater Samples Collected at 

the Off-Site 610 Wells in Decatur. AL in September 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 

GLP10-01-01-23 

Total Number of Pages 

44 

ACCREDITED 

Testing Cert #2052.01 

TTie 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 A2L.A Certificate #2052.01. Testing that complies with this International Standard also 

operate in accordance with ISO 9001:2000. 

Page 1 of 44 
GLP10-01-01; Interim Report 23 

Analysis of PFOA in Groundwater Samples 

Off-Site 610 Wells; September 2011 

This page has been reserved for specific country requirements. 

Page 2 of 44 
GLP10-01-01; Interim Report 23 

Analysis of PFOA in Groundwater Samples 

Off-Site 610 Wells; September 2011 

GLP COMPLIANCE STATEMENT 

Report Title: GLP10-01-01, Interim Report 23. Analysis of PFOA in Groundwater Samples Collected 

at the off-Site 610 Wells in Decatur, AL in September 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. 

1 

Gary Hohensiein, Spoyisor Representative Date 

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

Page 3 of 44 
GLP10-01-01; Interim Report 23 

Analysis of PFOA in Groundwater Samples 

Off-Site 610 Wells; September 2011 

QUALITY ASSURANCE STATEMENT 

Report Title: GLP10-01-01, Interim Report 23. Analysis of PFOA in Groundwater Samples Collected 

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

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

inspection Dates Phase 

Date Reported to 

inspection Dates Phase Testing Facility 

Management 

Study Director 

9/6/11 In-Phase Sample 

Preparation 

10/11/11 10/11/11 

10/13-10/14/11 Data and Report 10/31/11 10/31/11 

QAU Repre^ntative Date 

Page 4 of 44 
GLP10-01-01; Interim Report 23 

Analysis of PFOA in Groundwater Samples 

Off-Site 610 Wells; September 2011 

TABLE OF CONTENTS 

GLP Compliance Statement 3 

Quality Assurance Statement 4 

Table of Contents 5 

List of Tables 6 

1 Study Infonnation 7 

2 Summary 8 

3 Introduction 8 

4 Test & Control Substances 9 

5 Reference Substances 9 

6 Test System 10 

7 Method Summary 10 

7.1 Methods 10 

7.2 Sample Collection 10 

7.3 Sample Preparation 10 

7.4 Analysis 10 

8 Analytical Results 11 

8^1 Calibration 11 

8.2 System Suitability 12 

8.3 Limit of Quantitation (LOQ) 12 

8.4 Continuing Calibration 12 

8.5 Blanks 12 

8.6 Lab Control Spikes (LCSs) 12 

8.7 Analytical Method Uncertainty 13 

8.8 Field Matrix Spikes (FMS) 13 

Page 5 of 44 
GLP10-01-01; Interim Report 23 

Analysis of PFOA in Groundwater Samples 

Off-Site 610 Wells; September 2011 

9 Data Summary and Discussion 14 

10 Conclusion 16 

11 Data/Sample Retention 16 

12 Attachments 16 

13 Signatures 17 

LIST OF TABLES 

Table 1. Summarized PFOA Results (Off-Site 610 Wells, September 2011) 8 

Table 2. Sample Description Key Code 10 

Table 3. Instrument Parameters 11 

Table 4. Liquid Chromatography Conditions .11 

Tables. Mass Transitions 11 

Table 6. Limit of Quantitation (LOQ) 12 

Table 7. Laboratory Control Spike Recovery 13 

Table 8. Analytical Method Uncertainty 13 

Table 9. Field Matrix Spike Levels 14 

Table 10. DAL GW 61 OS 110921 15 

Table 11. DAL GW 61OL 110921 15 

Table 12. Trip Blank 110921 15 

Page 6 of 44 
GLP10-01-01; Interim Report 23 

Analysis of PFOA in Groundwater Samples 

Off-Site 610 Wells; September 2011 

1 Study Information 

Sponsor 

3M Company 

Sponsor Representative 

Gary Hohenstein 

3M EHS Operations 

3M Building 224-5W-03 

Saint Paul, MN 55144-1000 

Phone:(651)737-3570 

Study Director 

Jaisimha Kesari, P.E., DEE 

Weston Solutions, Inc. 

Westchester, PA 19380 

Phone: (610) 701-3761 

Fax: (610)701-7401 

j. kesari@westonsolutions.com 

Study Location 

Testing Facility 

3M EHS Operations 

3M Environmental Laboratory 

Building 260-5N-17 

St. Paul, MN 55144 

Study Personnel 

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

Cleston Lange, Ph.D., Principal Analytical Investigator, (clanqe@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 23 Experimental Termination: October 7,2011 

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 44 
GLP10-01-01; Interim Report 23 

Analysis of PFOA in Groundwater Samples 

Off-Site 610 Wells; September 2011 

2 Summary 

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

the Off-Site 610 Wells in Decatur, AL. A total of eleven 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 and one trip blank containing Milli-QTM water and appropriate trip blank spikes. The 

groundwater samples and trip blanks were received from Weston personnel on October 6, 2011. All of 

the samples were prepared and analyzed for PFOA following 3M Environmental Laboratory Method 

ETS-8-044.0 under 3M project GLP10-01-01-23. The average measured PFOA concentrations are 

summarized in Table 1. The trip blank was below the lower limit of quantitation (LLOQ) of 0.0240 

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

The analytical uncertainty was estimated at 100±12%. 

Table 1. Summarized PFOA Results (Off-Site 610 Wells, September 2011) 

3M LIMS ID Sample Description 

PFOA 

Concentration 

(ng/mL) 

GLP10-01-01-023-001 DAL GW 61OS-0-110921 1,01 

GLP10-01-01-023-002 DAL GW610S-DB-110921 1.31 

Average 1.16 

YoRPD Sample/Sample Dup 26(1) 

GLP10-01-01-023-005 DALGW610L-0-110921 3.55 

GLP10-01-01-023-006 DAL GW 61OL-DB-110921 3.76 

Average 3.66 

%RPD Sample/Sample Dup 5.7 

GLP10-01-01-023-009 DAL-GW-TRIP01-1 <0.0240 

The analytical uncertainty for PFOA was estimated at 100+12%. 

(1) The relative percent difference (RPD) did not meet method acceptance 

criteria ofs20%. 

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 

infonnation 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 Off-Site 610 wells 

located 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 marked with a "fill to here" line to 

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

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

collection. All sample bottles included the addition of "Ca-PFOA (internal standard) at a nominal 

Page 6 of 44 
GLP10-01-01; Interim Report 23 

Analysis of PFOA in Groundwater Samples 

Off-Site 610 Wells; September 2011 

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, and ^^C4-PF0A (surrogate standard) at a nominal concentration of 0.1 

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

was inadvertently not included in the analysis of the samples. 

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

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

Compounds in Water by LC/MS/MS; Direct Injection Analysis". The use of an intemal standard was 

used to aid in the data quality objectives. 

Table 1 summarizes the average PFOA concentration for the duplicate groundwater samples collected 

and the trip blank sample. Tables 10-12 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. 

4 Test & Control Substances 

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

was purely analytical in nature. 

5 Reference Substances 

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

Reference 

Substance 

PFOA (Linear) 

PFOA 

(Linear + Branched) 

"Cg-PFOA 

Chemical Name Perfluorooctanoate Perfluorooctanoate Perfluorooctanoate 

Chemical Formula C7F15COOH C7F15COOH ^^C8HFi502 

Identifier CAS #335-67-1 CAS #95328-99-7 CAS#MPFC-C-0511 

Use 

Target Analyte 

Reference Standard 

Target Analyte 

Reference Standard Intemal Standard 

Source Oakwood Products Wellington Wellington 

Expiration Date 01/17/2018 03/17/2014 05/25/2014 

Storage Conditions Frozen Frozen Frozen 

Chemical Lot Number 3440 TPFOA0311 MPFC-C-0511 

TOR Number TCR07-0041 TCR11-0009 TCR11-0016 

Physical Description Powder Liquid Liquid 

Purity 99.1% 98.3% NA'^* 

(1) Compound is part of a custom mixture of mass-labeled perfluorinated c»mpounds at a concentration of 5.0 pg/mL. 

Page 9 of 44 
Table 2. Sample Description Key Code. 

GLP10-01-01; Interim Report 23 

Analysis of PFOA in Groundwater Samples 

Off-Site 610 Wells; September 2011 

String Number String Descriptor Example 

Example DAL-GW- 610S-LS-110921 

1 Sample Location DAL= Decatur, Alabama 

2 Sample Type GW= Groundwater 

3 Well ID Example: DAL 610 

S = Epikarst 

L - Limestone bedrock 

4 Sampling Date 110921- September 21, 2011 

5 Sample Type 0=primary sample 

DB=duplicate sample 

LS = low spike 

HS = high spike 

7 Method Summary 

7.1 Method 

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

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

Liquid Chromatography/Mass Spectrometry Direct Injeiition 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 GLP10-01-01-23 were retumed to the 

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

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

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 internal standard mix at a nominal concentration of 1 ng/mL prior to 

being sent to the field for sample collection. 

7.4 Analysis 

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

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

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

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

and Table 5. 

Page 10 of 44 
Table 3. Instrument Parameters. 

GLP10-01-01; Interim Report 23 

Analysis of PFOA in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Instrument Name ETS Kiri< 

Analytical Method Followed ETS-8-044.0 

Analysis Date 10/6/2011 

Liquid Ctiromatograpli Agilent 1200 

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

Analytical column Betasil CIS (4.6 mmX 100 mm), 5u 

Injection Volume 25 nL 

Mass Spectrometer Applied Biosystems API 5500 

Ion Source Turbo Spray 

Electrode Turbo ion electrode 

Polarity Negative 

Software Analyst 1.5.2 

Table 4. Liquid Chromatography Conditions. 

step Total Time Flow Rate PercenM PercentB 

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

10/6/2011 Analysis 

0 0.0 750 97.0 3.0 ' 

1 2.0 750 97.0 3.0 

2 14.5 750 5.0 95.0 

3 15.5 750 5.0 95.0 

4 16.5 750 97.0 3.0 

5 20.0 750 97.0 3.0 

Table 5. Mass Transitions. 

Analyte 

Mass Transition 

Q1/Q3 Intemal Standard 

Mass Transition 

Q1/Q3 

PFOA 

413/369 

413/219 t'CJ-PFOA 421/376 

413/169 

Dwell time was 30 msec for each transition. The individual transitions were summed to produce a 

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

8 Analytical Results 

8.1 Calibration 

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

were prepared by spiking known amounts of the stock solution containing PFOA (reference standard 

containing both linear and branched isomers) into a laboratory-prepared synthetic groundwater 

containing calcium and magnesium. A separate internal standard spiking solution was prepared and an 

aliquot was added at the same level to all calibration standards and laboratory control samples at a 

nominal concentration of 1 ng/mL. A calibration curve ranging from approximately 0.025 ng/mL to 25 

ng/mL was prepared. 

Page 11 of 44 
GLP10-01-01; Interim Report 23 

Analysis of PFOA in Groundwater Samples 

Off-Site 610 Wells; September 2011 

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 

confimned 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 

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

8.2 System Suitability 

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

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

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

met for PFOA. 

8.3 Limit of Quantitation (LOQ) 

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

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

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

Table 6. Limit of Quantitation (LOQ). 

Analysis Date PFOA 

ng/mL 

10/6/11 0.0240 

8.4 Continuing Calibration 

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

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

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

8.5 Blanks 

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

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

LOQ for PFOA. Trip blanks reflect the shipping and sample collection conditons the sample bottles and 

samples experience. 

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 PFOA. 

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

i^or, . o Calculated Concentration 

LCS Percent Recovery = * 100% 

Spike Concentration 

LCS% RSD = standard deviation LCS replicates . ^ 

average LCS recovery 

Page 12 of 44 
Table 7. Laboratory Control Spike Recovery. 

GLP10-01-01; Interim Report 23 

Analysis of PFOA in Groundwater Samples 

Off-Site 610 Wells; September 2011 

ETS-8-044.0 

Analyzed 10/6/2011 Linear + Branched PFOA 

Lab ID 

Spiked 

Concentration 

(ng/mL) 

Calculated 

Concentration 

(ng/mL) YoRecovery 

LCS-111006-1 0.190 0.186 97.8 

LCS-111006-2 0.190 0.177 93.0 

LCS-111006-3 0.190 0.187 98.2 

Average ± %RSD 96.3% ± 3.0% 

LCS-111006-4 1.90 1.96 103 

LCS-111006-5 1.90 1.96 103 

LCS-111006-6 1.90 1.94 102 

Average ± %RSO 103% ±0.56% 

LCS-111006-7 9.52 9.66 101 

LCS-111006-8 9.52 9.44 99.1 

LCS-111006-9 9.52 9.49 99.6 

Average ±%RSD 99.9% ±0.99% 

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 Method Uncertainty. 

Analyte Method Standard Deviation 

Method 

Uncertainty 

PFOA ETS-8-044.0 6.19 ±12% 

8.8 Field Matrix Spikes (FMS) 

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

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

volume of field sample to a container spiked by the laboratory with PFOA (reference standard containing 

primarily linear PFOA) 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. 

Page 13 of 44 
GLP10-01-01; Interim Report 23 

Analysis of PFOA in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Table 9. Field Matrix Spike Levels. 

Sampling Location Spike Level PFOA, ng/mL 

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

^. .„ „ (Sample Concentration of FMS-Average Concentration: Field Sample & Field Sample Dup.) ^, .„., FMS Recovery = -^^ — * 100% Spike Concentraton 

9 . Data Summary and D/sci/ss/on i 

- - _ .iii . 

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

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

figures according to EPA rounding rules. Because of rounding, values may vary slightly from those 

listed in the raw data. 

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

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

DAL GW 61 OL 110921 - The high field matrix spike at 1 ng/mL was less than 50% of the PFOA 

concentration in the sample and would nomially not be calculated. However, since the "C4-PFOA 

surrogate (which was added to the samples) was inadvertently omitted from the analysis, the field 

matrix spike recovery was calculated and found to be 84.5%. 

Page 14 of 44 
Table 10. DAL GW 61 OS 110921 

GLP10-01-01; Interim Report 23 

Analysis of PFOA in Groundwater Samples 

Off-Site 610 Wells; September 2011 

PFOA 

Concentration 

3M LIMS ID Description (ng/mL) YoRecovery 

GLP10-01-01-23-001 DAL GW 6108-0-110921 1.01 NA 

GLP10-01-01-23-002 DAL GW610S-DB-110921 1.31 NA 

GLP1CKI1-01-23-003 DAL GW610S-LS-110921 1.32 NC 

GLP10-01-01-23-004 DALGW610S-HS-110921 2.27 111 

Average Concentration (ng/mL) ± %RPD 1.16ng/mL±26%'^^ 

NA= Not Applicable 

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

(1) The relative percent difference (RPD) did not meet method acceptance criteria of s20%. 

Table 11. DAL GW 61 OL 110921 

PFOA 

Concentration 

3MUMSID Description (ng/mL) %Recovery 

GLP10-01-01-23-005 DAL GW 61OL-0-110921 3.55 NA 

GLP10-01-01-23-006 DAL GW 61OL-DB-110921 3,76 NA 

GLP10-01-01-23-007 DAL GW 61OL-LS-110921 3.56 NC 

GLP10-01-01-23-008 DAL GW610L-HS-110921 4.50 84.5 

Average Concentration (ng/mL) ± YoRPD 3.66 ng/mL ±5.r/o 

NA= Not Applicable 

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

(1) The high field matrix spike at 1 ng/mL was less than 50% of the PFOA concentration in the sample. However, since the "Cv 

PFOA surrogate (which was added to the samples) was inadvertently omitted from the analysis, the field matrix spike 

recovery was calculated. 

Table 12. Trip Blank 110921 

PFOA 

3M LIMS ID Descrrptfon 

Concentration 

(ng/mL) YoRecovery 

GLP10-01-01-23-009 DALGWTRIP01-0-110921 <0.0240 NA 

GLP10-01-01-23-010 DAL GWTRIP01- LS-110921 0.228 91.2 

GLP10-01-01-23-011 DAL GWTRIP01-HS-110921 1.05 105 

NA = Not Applicable 

Page 15 of 44 
GLP10-01-01; Interim Report 23 

Analysis of PFOA in Groundwater Samples 

Off-Site 610 Wells; September 2011 

10 Conclusion 

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

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

Laboratory method ETS-8-044.0 described herein. 

11 Data/Sample Retention 

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

to 3M Environmental Laboratory standard operating procedures. 

12 Attachments 

Attachment A: Protocol Amendment 23 (General Project Outline) 

Attachment B: Representative Chromatograms and Calibration Curves 

Attachment C: Analytical Method - ETS-8-044.0 

Attachment D: Method Deviation 

Page 16 of 44 
GLP10-01-01; Interim Report 23 

Analysis of PFOA in Groundwater Samples 

Off-Site 610 Wells; September 2011 

13 Signatures 

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

•^^^y^i^^^ ^^^^^// 

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

f6 

Gary Hoher^steiny3M Sponsor Representative Date 

Jaisimha K^ari, Study Director / Date 

Page 17 of 44 
GLP10-01-01; Interim Report 23 

Analysis of PFOA in Groundwater Samples 

Off-Site 610 Wells; September 2011 

ATTACHMENT A: PROTOCOL AMENDMENT 

Page 18 of 44 
GLP10-01-01; Interim Report 23 

Analysis of PFOA in Groundwater Samples 

Analytical ProtocomPmm''''"''''°'' 

Amendment 23 

Study Title 

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

3M Decatur Phase 3 Site-Related Monitoring Program 

PROTOCOL AMENDMENT NO. 23 

Amendment Date: 

September 14, 2011 

Performing Laboratory 

3M Environmental, Health, and Safety Operations 

SM Environmental Laboratory 

Building 260-5N-17 

Maplewood, MN 55144-1000 

Laboratory Project Identification 

GLP10-01-01 

Sampling Event 

Off-Site 610 Wells 

Page 1 of 6 

Page 19 of 44 
GLP10-01-01; Interim Report 23 

Analysis of PFOA in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Analytical Protocol: GLP10-01-01 

Amendment 23 

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 vvording of the protocol are required. 

AMEND TO READ: 

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

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

as part of the 3M Decatur Phase 3 Program for PFOA (GLP10-01-01). The anticipated sample collection 

will occur around the timeframe of the week of September 19. 2011. The groundwater samples for this 

sampling event will be entered into the 3M Environmental Laboratory LIMS as project GLP10-01-01-23 

and reported as interim report GLP 10-01-01-23, (reflecting study GLP10-01-01 and amendment -23). 

Reason: 

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

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

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

Page 2 of 6 

Page 20 of 44 
GLP10-01-01; Interim Report 23 

Analysis of PFOA in Groundwater Samples 

! Off-Site 610 Wells; September 2011 

i Analytical Protocol: GLP10-01-01 

Amendment 23 

Amendment Approval 

Gary Hohenstein, Sponsor Representative Date 

Clesto Date n C. Lange, Principal Analytical Investigator 

William Reagen, EHS Opns Envil-onmental Lab Management Date 

Jaisimha Kesan P.E., DEE, Study Director mm I Date/ 

Page 3 of 6 

Page 21 of 44 
GLP10-01-01; Interim Report 23 

Analysis of PFOA in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Analytical Protocol: GLP10-01-01 

Amendment 23 

3 M Environmental Health & Safety Operations, Environmental Laboratory 

General Project Outline 

To, 

From: 

cc: 

Date: 

Subject: 

Gary Hohenstein, 3M EHS&Opns 

Susan Wolf, 3M EHS&Opns; Environmental Lab 

William Reagen, 3M EHS&Opns; Environmental Lab 

Cleston.Lange, 3M EHS&Opns; Environmental Lab 

Jai Kesari, Weston Solutions 

Septembers, 2011 

Analysis of Perfluorooctanoic Acid (PFOA) in GroOndwater, Soil and Sediment for the 3iVl 

Decatur Phase 3 Site-Related Monitoring Prograni; GLP Interim Report 23; Off-Site 610 

Wells 

1 General Project Information 

3M Sponsor Rspresentative 

Gary Hohenstein 

3M EHS Operations 

3iVI Building 224-5W-03 

Saint Paul. MN 55144-iOOO 

Phone: (651) 737-3570 

aahohensfeinfflmmm.com 

3M Environmental Laboratory Management 

William K. Reagen 

3IVI EHS Opns, Environmental Laboratory 

260-5N-17 

651 733-9739 

Contacts wkreaaeni5)mmm.com 

Principal Analytical Investigator 

Cleston Lange ; 

3M EHS Opns, Environmental Laboratory 

260-5N-17 

651 733-9860 

colanae(S>mmni com 

Sampling Coordinator 

Timothy Frinak 

vyestpn Solutions 

Timothy .frinaktawestonsolutions.coin 

Phone: {334)-332-9123 

Lab Request Number GLP10-01-01-23 

Six Digit Department Number Dept #530711, Project #0022674449 

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

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

Page 4 of 6 

Page 22 of 44 
GLP10-01-01; Interim Report 23 

Analysis of PFOA in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Analytical Protocol: GLP10-01-01 

Amendment 23 

2 Background Information and Project Objective(s) 

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

samples collected from two sampling locations for Perfluorooctanoic Acid (PFOA) from new wells located 

off-site. Analyses will be conducted under the GLP requirements of EPA TSCA Good Laboratory Practice 

Standards 40 CFR 792. 

Groundwater samples will be collected by Weston Solutions personnelthe week of September 19, 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 GLP10-01-01-23. 

3 Project Schedule 

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

14, 2011. Sample bottles will be shipped in coolers overnight to 3M Decatur for arrival on Friday, September 

16, 2011. Sample bottles should be stoi-ed refrigerated on-site until sample collection. 

Martin Smith \ V\lest6r\ Trailer 

3M Decatur Plant 

1400 State Docks Road 

Decatur, Alabama 35601 

4 Test Parameiters 

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 "fill to here" line on each 250 

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

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

bottles. All sample bottles will include the addition of "Cg-PFQA (internal standard) at a nominal concentration 

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

concentration of 0.1 ng/mL. The table below lists the matrix spike levels that will be prepared. 

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

61 OS andei.OR Low 0.25 61 OS andei.OR High 1,0 

Trip Blank Low 0.25 Trip Blank Hiqh 1.0 

Page 5 of 6 

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

Analysis of PFOA in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Analytical Protocol: GLP10-01-01 

Amendment 23 

5 Test Methods 

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

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

Analysis". Alternately, samples may be analyzed by ETS 8-154.3 "Detemnination of Perfluorinated Acids, 

Alcohols, Amides, and Sulfonates In Water By Solid Phase Extraction and High Perfomnance 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 ajsplicable, samples will be analyzed against an internal standard calibration curve.. Each curve point will 

contain isotopicallyTlabeled peffluorocarboxylic acids and perfluorosulfonic acids at a nominal concentration of 1 

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

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

6 Reporting Requirements 

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

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

equipment/rinseate blanks prepared in the field; Laboratory 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 deterhiine the method 

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

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

the final report. 

Page 6 of 6 

Page 24 of 44 
GLP10-01-01; Interim Report 23 

Analysis of PFOA in Groundwater Samples 

Off-Site 610 Wells; September 2011 

ATTACHMENT B: REPRESENTATIVE SAMPLE CHROMATOGRAMS AND 

CALIBRATION CURVE(S) 

Page 25 of 44 
Results Name: kiiioo6a.]GatP10-01-01; Interim Report23 

Analysis of PFOA in Groundwater Samples 

Off-Site 510 Wells; September 2011 

Proc. Algf 

Nols?. pare 

Base. Sub. 

Smoothing Wle 

RT Window: 

Expected RT: 

.306+005 cpa 

I

SatT^jl* N»im: •k11100e«0ie" Sirrpl' ID; "11 003-4(M- Rto: "kl 

P«k Nirr*: •13C8PFOA-IS(IS)" Misif.i): -421.000078.000 Di" 

Cotmwnt: "1.0 no/mL FC ild In Synth. VJattf Annotation;" 

1.25*5 

1.20*5 

1.15*5 

1.10*5 

1.05*5 

1.00*5 

9.50*4 

8.00*4 

6.50*4 

8.00*4 

7.50*4 

4 6.50*4 

I 6.00*4 

5.50*4 

5.00M 

4.50*4 

4.00*4 

3.50*4 

3.00M 

2.50*4 

2.00M 

1.50*4-

1.00*4 

5000.00 

0.00 

14.8 15.0 15.1 15.2 15.3 15,4 15.5 16.2 16.3 16.4 16.6 16.7 18.8 

I

SimpI* Nam*:'k111006a023' Sair^lD : 

P*ak Nam*: 'l3C8PFOA-IS(IS}- Mau(«s): 

ComrTwnt: 'Method Bbnk" Annotatton; *" 

Sample Index: 23 

I

San ^ Nam*:'kll 1006*024" SarrpI* ID:-GLP10-O1-O1-23-OO1' 

Psak Nam*: '13C8PFOArtS(tS)' MaM(**): '421.000/376.000 Da' 

Comm*nt: "DAL-GVMl 0S-O-" Annotatton: " 

Sample Index; 24 

iiii: Specify ParaniBtc 

.35e*O05 cpa 

14.8 15.0 15.1 15.2 15.3 15.4 15.5 

Data printe d by STW 

Printin g Time: 3:23:58 PM 

15.6 15.7 15.8 16.2 16.3 16.4 16.5 16.6 16.7 16.8 

Page 1 of 4 
Results Name I 

I

Sampl*Nim*:-k111O06«D35 - Sanv>l* ID:'GLP1(K)l-01-23-00S- Fk ; 

P*ak Nam*: "ISCSPFOAr^SOS)' Ma»s(*«); •421.000/376.000 DaComment : -DAL-GW-TRIPOI-O- Annotation: " 

Sampl e Index : 3 5 

Sampl e Type : Unknow n 

1.0 0 

Acq . Da t 

.thin g Width : 

i Relative Rl : 

15.0 min 

I

Sanvt * Nam*:'k1110063041 * Sampt* ID:'LCS-111006-1 ' Fil«:'k11100ea.v>ifr 

P*ak Nam*: •13C8PFOA-l3(l3)' MaM<*»): '421.000378.00 0 Da ' 

Convnant: '0.2pp b LCS ' Annotation: " 

Sampl e Index : 4 1 

L t . Factor : 

< Height : 

kiiioo6a.J36PiO-01-01; Interim Report23 

Analysis of PFOA in Groundwater Samples 

Off-Site 610 Wells; September 2011 

S.S 16.0 

T1m*.m» i 

I

SampI* Name : 'k111006a044 ' Sampl* ID: 'LCS-11100&4 ' Fl * 

Pas k Nam*: '13C8PFOMS(IS) ' Mass(«s): *421.000/376.000 Da* 

Comment: "2ppb LCS ' Arnotalion; " 

Saiqile Index: AA 

RT Windcw : 

I

Sanpl*Nam*:'kni006a04 r Sampl*ID:-LCS-111006- r Rle: 

Peak Name : •13C«PFOA^S0S>• Mass(es); "421.000376.00 0 Da ' 

Comment: "10 pp b LCS ' Annotation: ~ 

Snmple Index: 47 

Snmple Type: QC 

Concentration: 0.99t ng/mL 

Calculated Cone: N/A 

Acq. Date: 10/7/2011 

Smoothin g Wid i 

RT Window : 

.34e-0O5 cpa 

4.9 15.0 15.1 15.2 15.3 15.4 15 5 15.6 15.7 15.8 15.9 16.0„I6.1 16.2 16.3 16.4 16.5 

Jisaus& Page?? of 44 

16.6 16.7 16.8 

Data printe d by STW 

Printin g Time: 3:23:59 PM 

Page 2 of 4 
Results Name: kiiioo6a.<]^10-01-01; Interim Report23 

Analysis of PFOA in Groundwater Samples 

Data printe d by STW 

Printin g Time: 3:23:5 9 PM 

Page 3 o f 4 
*ETS-Kirk Result s Name; 

I

SanvUName:'k111006a03S ' Sanfil* ID:"GLPlO-01-01-23-009 ' Fi*:'k111006a.vJ r 

P** k Name: 'PBDA ' Maw{*s) : "413.00tV369.000 Da,413.000/218.000 Da,413.000/169.000 Da ' 

Comment: 'OAL-GW-TRIPOI-O^ Annotation: -

Sampl e Index : 3 5 

Sampl e Type : Unknow n 

Acq. Tims: 3:0^:03 AM 

Modified: Yea 

Pioc. Alqorithm: Specify Paramet 

Noiae Peccentage: 50 

Base. Sub. Window: 1.00 mir 

Psak-Spllt. Factor: A 

Report Largest Peak: Yes 

Min . Peak Height : 0.0 0 cp 

. Pea k 

Use Relativt 

Int. Type: 

0.00 

Valle y 

15.7 

11753 cc 

2.56e+003 

14.7 14.8 14 5 15.0 15.B 16.0 16.1 6.2 16.3 16.4 16.5 16.6 

I

SanvbName:-k111006a04l " San ^ ID:'LCS-111006- r File:'kll1006a.vi( r 

Peak Nam*: 'PFOA ' MtM(e«) : •413.000«e9.00 0 Da.413.000/219.000 Da.413.000/169.000 Da" 

Commen t '0.2ppb LCS ' Annotation: ** 

Sampl . 

kiiioo6a.<5fepio-01-01; Interim Report 23 

Analysis of PFOA in Groundwater Samples 

Sample Type: OC 

Lhm; Spacif y Patome t 

I

Sarr^>leName:"k111006a044 ' Serrpl* ID:'LCS-111006-4 ' Fl*:'klll006a.wi r 

P*ak Name: "PFOA" Mass(es): '413.000/369.000 Da.413.000/219.000 Da ,413.000/169.000 DaComment: '2pf>b LCS ' Annotation:" 

Sample Index: 44 

Sample Type: QC 

Concent rat ion: 1.90 ng/mL 

Calculated Cone: 1.S5 ng/mL 

"0/7/2011 

Acq . 6:1' 

. Algocithr 

. Sub. Wini 

I

SBnvleName:-k111006a04 r Sample ID:'LCS-lHOOe- r File:-klllOOea.intfr 

P*«k Name:'PFOA ' MaM(et):'413.000i'3e9.00 0 Da,413.000/219.0O0Da,413.000/169.000 Di ' 

Commen t '1 0 ppb LCS ' Annotation:'" 

Sample Index: 47 

Specify Pai 

.: 50 

.w: 1.00 

Proc. Algcrl 

Peak-Split. 

Report Largeat I 

Min. Peak Height 

Min. Peak Width 

Int. Type: Manual 

Rstantion Tlm-i : 15.7 

Area: 10753272 i 

14.7 14.8 14 5 15.0 15.1 15.2 15.3 15.4 15.5 15.6 15.7 15.8 

Time , min 

15.9 18.0 18.1 16.2 16.3 16.4 

Data printe d by STW 

Printin g Time: 3:23:59 PM 
GLP10-01-01; Interim Report 23 

Analysis of PFOA in Groundwater Samples 

Off-Site 610 Wells; September 2011 

Result s Name: klll006a.rd b 

Data printe d by STW 

Printin g Time: 3:18:29 PM 

Page 1 o f 1 

Page 30 of 44 
GLP10-01-01; Interim Report 23 

Analysis of PFOA in Groundwater Samples 

Off-Site 610 Wells; September 2011 

ATTACHMENT C: ANALYTICAL METHOD(S) 

Page 31 of 44 
GLP10-01-01; Interim Report 23 

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3IVI Envvmonmental 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 y1 ^ /<3"? 

Approved By: 

William K. Reagen, Laboratory Manager Date 

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1 Scope and Application 

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

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

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

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

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

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

particulate may require preparation by an alternate method such as ETS-8-154 "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 Method Summary 

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

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

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

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

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

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

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

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

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

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

accuracy for analytical results. 

3 Definitions 

3.1 Calibration Standard 

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

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

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

concentration. 

3.2 Laboratory Duplicate Sample (LDS, or Lab Dup) 

A laboratory duplicate sample is a separate aliquot of a sample taken in the analytical laboratory that is 

analyzed separately with identical procedures. Analysis of LDSs compared to that of the first aliquot give 

a measure of the precision associated with laboratory procedures, but not with sample collection, 

preservation, or storage procedures. 

3.3 Field Blank (FB)/Trip Blank 

ASTM Type 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. 

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3.4 Field Duplicate Sample (FDS, Field Dup) 

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

handled under identical circumstances and treated exactly the same throughout field and laboratory 

procedures. Analysis of the FDS.compared to that of the first sample gives a measure of the precision 

associated with sample collection; preservation and storage, as well as with laboratory procedures. 

3.5 Field Matrix Spike (FIVIS) 

A sample to which known quantities of the target analytes are added to the sample bottle in the laboratory 

before the bottles are sent to the field for collection of aqueous samples. A known, specific volume of 

sample must be added to the sample container without rinsing. This may be accomplished by making a 

"fill to this level" line on the outside of the sample container. The FMS should be spiked between 

approximately 50% and 10 times the expected analyte concentration in the sample. If the expected range 

of analyte concentrations is unknown, multiple spikes at varying levels may be prepared to increase the 

likelihood that a spike at an appropriate level is made. The FMS is analyzed to ascertain if any matrix 

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

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

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

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

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

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

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

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

3.7 Laboratory Control Sample (LCS) 

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

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

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

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

each day samples are extracted. 

3.8 Laboratory Matrix Spike (LMS) 

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

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

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

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

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

3.9 Laboratory Sample 

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

3.10 Limit of Quantitation (LOQ) 

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

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

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

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

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

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

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

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3.11 Method Blank 

An aliquot of control matrix that is treated exactly like a laboratory sample including exposure to all 

glassware, equipment, solvents, and reagents that are used with other laboratory samples. The method 

blank is used to determine if test substances or other interferences are present in the laboratory 

environment, the reagents, or the apparatus. 

3.12 Sample 

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

material. 

3.13 Stock Standard Solution (SSS) 

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

compound. 

3.14 Surrogate 

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

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

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

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

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

quality control measure and is NOT required. 

3.15 Working Standard (WS) 

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

calibration standards and other required analyte solutions. 

4 Warnings and Cautions 

4.1 Health and Safety 

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

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

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

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

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

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

4.2 Cautions 

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

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

appropriate equipment procedure or operator manual for additional information and cautions. 

5 Interferences 

During sample preparation and analysis, major potential contaminant sources are reagents and 

glassware. All materials used in the analyses shall be demonstrated to be free from interferences under 

conditions of analysis by running method blanks. 

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Parts and supplies that contain Teflon® should be avoided or minimized due to the possibility of 

interference and/or contamination. These may include, but are not limited to: wash bottles. Teflon® lined 

caps, autovial caps, HPLC parts, etc. 

The use of disposable micropipettes or pipettes to aliquot standard solutions is recommended to make 

calibration standards and matrix spikes. 

6 Instrumentation, Supplies, and Equipment 

6.1 Instrumentation and Equipment 

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

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

(LC/MS/MS). I 

Analytical balance capable of reading to 0.0001 g 

A device to collect raw data for peak integration and quantitation 

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

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

1 mL plastic HPLC autovial. 

Disposable pipettes, polypropylene or glass as appropriate 

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

6.2 Chromatographic System 

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

Analytical Column: Betasil C18,4.6 mm x 100 mm, 5 \^m 

Temperature: 10°C 

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

Mobile Phase (B): Methanol 

Gradient Program: 

Flow Rate 

Time (min) %A % B (mL/min) 

0.0 97 3 1.0 

0.5 97 3 1.0 

11.0 5 95 1.0 

13.5 5 95 1.0 

13.6 97 3 1.0 

17.0 97 3 1.0 

Injection Volume: 100 |JL. 

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

RunTime: ~ 17minutes. 

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

provided that data quality objectives are met. 

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6.3 MS/MS System 

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

Analyte Transition Monitored 

PFBA 213^ 169 

PFPeA 263^219 

PFHA 313^269 and 313^119 

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

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

PFNA 463 419, 463 169 and 463 -> 219 

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

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

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

PFBS 299 ^ 80 and 299 99 

PFHS 399 80 and 399 99 

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

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

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

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

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

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

7 Reagents and Standards 

7.1 Chemicals 

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

Methanol - HPLC grade 

Ammonium Acetate - A.C.S. Reagent Grade 

7.2 Standards 

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

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

PerfluorohexanoicAcid (PFHA-C6 acid); Oakwood Products, Inc 

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

Products, Inc 

Perfluorooctanoic Acid (PF0A-C8 acid); 3M 

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

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

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

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

Perfiuorobutanesulfonate (PFBS - C4 sulfonate); 3M 

Perfluorohexanesulfonate (PFHS - C6 sulfonate); 3M 

Perfluorooctanesulfonate (PFOS - C8 sulfonate); 3M 

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

used. 

7.3 Reagent Preparation 

2 mM Ammonium acetate solution (Analysis)—^Weigh 0.3 g of Ammonium acetate and dissolve in 2.0 L of reagent 

water. 

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

7.4 Stock Standard Solution (SSS) and Working Standard Solution Preparation 

The following standard preparation procedure serves as an example. Weighed amounts and final volumes may be 

changed to suit the needs of a particular study. For example, pL volumes may be spiked into volumetric flasks 

when diluting stock solutions to appropriate levels. 

100 [iglmL target analyte SSSs—^Weigh out 10 mg of analytical standard (corrected for percent salt and 

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

125mL LDPE bottle or other suitable container. Prepare a separate solution for each analyte. Expiration dates 

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

procedure. An example of purity and salt con-ection is given below for PFOS. 

, , molecular weight of anion 

salt correction factor = 

moclecular weight of salt 

499 

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

538 

10 mg CsFiySOa'K" with purity 90% = 8.35mg CsFiySOa" (10 mg*0.90*0.9275=8.35 mg) 

5 pg/mL (5000 ng/mL) mixed working standard—Add 0.5mL each of the 100pg/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 pg/mL -mixed worthing standard solution to a 25mL 

volumetric flask and bring up to volume with solvent. 

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

flask and bring up to volume with solvent. 

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

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

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7.5 Calibration Standards 

Using the 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 wori<ing standards may 

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

than those listed below can be prepared as needed. 

Concentration 

of WS, ng/mL Volume of WS, fd. 

Final Volume of 

Calibration Standard (mL 

of ASTM Type 1 Water, or 

other suitable water) 

Final Concentration of 

Calibration Standard, ng/mL 

(ppb) in ASTM Type 1 Water, 

or other suitable water 

125 10 50 0.025 

125 15 50 0.0375 

125 20 50 0.050 

125 30 50 0.075 

250 20 50 0.100 

250 50 50 0.250 

250 100 50 0.500 

250 200 50 1.00 

5000 25 50 2.50 

5000 50 50 5.00 

5000 100 50 10.0 

8 Sample Handling 

8.1 Water Sample Preparation 

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

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

sample aliquot, or filtered. 

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

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

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

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

Prepare at least five method blanks. 

9 Sample Analysis - LC/MS/MS 

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

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

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

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

thoroughly documented in the raw data. 

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

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

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

The coefficient of 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 

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

points will be used to construct the calibration curve. 

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

curve (if necessary) and reanalyze. 

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

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

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

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

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

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

curve should be further diluted and reanalyzed. 

10 Quality Control 

10.1 Data Quality Objectives 

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

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

the raw data and footnoted in the final report. 

10.2 Method Blanks 

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

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

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

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

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

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

the mean area counts of the method blanks exceed 50% of the LOQ standard, then the LOQ must be raised to the 

first standard level in the curve that meets criteria, or alternatively, the method blanks must be evaluated 

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

10.3 Sample Replicates 

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

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

replicates excludes field blanks. 

10.4 Surrogate Spikes 

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: 

. ,. , ., , ,, (Peak Area-Intercept) __ 

Analyte found (ng/mL) = -^^ — x DF 

Slope 

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

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

percent recovery. 

Recovery - ^"^'^^^ found (ng/mL) - Average analyte found in sarnple (ng/mL) ^ ^ 

Analyte added (ng/mL) 

12 Method Performance 

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

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

If criteria listed in this method performance 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 

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

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

have area counts with an RSD of <5% and a retention time RSD of 22% to be compliant. 

12.2 Quantitation 

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

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

the LLOQ, which may be within ±30%. 

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

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

each curve point must be within 25% of the theoretical value (within 30% for lowest curve point). Samples that are 

bracketed by CCVs not meeting these criteria must be reanalyzed. 

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

standard) and the mass spectral response of unique ions. 

12.3 Sensitivity 

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

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

to Section 10 for additional details. 

12.4 Accuracy 

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

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

spikes and laboratory matrix spikes. 

12.5 Precision 

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

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

requirement for replicates excludes field blanks or rinse blanks. 

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

13 Pollution Prevention and Waste Management 

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

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

14 Records 

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

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

sample and standard prep sheets/records, instmment mn log (instmment batch records, instmment 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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ATTACHMENT D: DEVIATION(S) 

Page 43 of 44 
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Analysis of PFOA In Groundwater Samples 

Off-Site 610 Wells; September 2011 

/. Identification 

study / Project No. 

GLP10-01-01-23 

Date(s) of Occurrence: 

k111006a 

Document Number: 

ETS-8-044.0 

Deviation type • SOP 

(Check one) • Protocol 

• Equipment Procedure 0 

• GPO • 

Method 

Other: 

//. Description (attach extra pages as needed) • 

Method Requirements: 

1. RPD within ±20% (section 10.3). 

2. The targeted fortification level should be at least 50% of the endogenous sample concentration (section 

10.6). 

Actual procedure/process: 

1. Sampling location DAL-GW- 61 OS had an RPD of 26% for PFOA. 

2. The high field matrix spike at 1 ng/mL for sampling location DAL GW610L was less than 50% of the 

PFOA concentration in the sample. However, since the ^^C4-PF0A surrogate (which was added to the 

samples) was inadvertently omitted from the analysis, the field matrix spike recovery was calculated and 

found to be 84.5%. 

/// . Actions Taken 

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

Corrective Action (• Yes 0 No) Reference: 

Acceptability of tine nonconforming work: 

1. The PFOA RPD for sampling location DAL GW 61 OL will be flagged in the final report. 

2. The recovery of the high field matrix spike for sampling location DLA GW 61 OL will be reported and 

flagged to indicate that the spike level was outside the targeted fortification range. 

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

0 Other: Deviations will be noted In final report. 

Project Lead/PAI Approval: Date: 

Study Director (if GLP): 

Sponsor Approval (for GLP protocol deviations): NA 

Technical Reviewer (optional): NA Date: NA 

Laboratory Department Manager Approval: Date: 

IV. Authorization to Resume Work 

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

Laboratory Department Manager Approval: NA Date: NA 

Deviation No. 

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

Page 44 of 44 
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ATTACHMENT 2

VEGETATIVE UPTAKE STUDY

TECHNICAL PROGRESS REPORT

OCTOBER 1, 2011 – DECEMBER 31, 2011
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Att 2-1

VEGETATIVE UPTAKE STUDY

TECHNICAL PROGRESS REPORT

3M AND DYNEON DECATUR, ALABAMA

During the period spanning from October 1, 2011 through December 31, 2011, routine 

monitoring of the watering and ventilation systems and plant growth has been performed 

at the Athens, Alabama nursery site where the vegetative uptake study is being 

conducted. Weeding, thinning, and pest control activities have also continued. Upon the 

observation of caterpillars on some tomato plants and aphids on some turnip green plants 

and sprouting potato shoots, food-grade diatomaceous earth (DE) was applied with a 

duster. Adult ladybird beetles were obtained and introduced into the greenhouse as a 

long-term aphid control measure on November 23, 2011. Additional ladybird beetles 

were released on November 30, 2011 to replenish losses associated with greenhouse 

ventilation and a screen was affixed to the exhaust fan to maximize retention.

On December 7, 2011, turnip greens samples were collected by harvesting individual 

leaves from plants using stainless steel scissors. Leaves were rinsed with de-ionized 

water, allowed to air dry and placed in polyethylene Ziploc® bags. Two composite 

samples were collected at each of the control and the six treatment levels. Sample bags 

and sample labels with recorded sample IDs, date and masses were placed in a second 

Ziploc® bag and frozen prior to shipment on dry ice to the 3M Environmental Laboratory 

for PFOA analysis. Once finalized, the analytical results will be provided in a subsequent 

quarterly status report.

Following the collection of the turnip green samples, the remaining turnip green plants 

were removed and the soil from the containers at each of the control and treatment levels 

was emptied into a polyethylene-lined tub for homogenization. Composite samples of the 

post-harvest soil from each of the control and treatment levels were placed into 

polyethylene bottles. Composite samples representing initial pre-planting conditions for 

all three of the crop species were also prepared from the bulk blended soil stored for use 

in hilling the potato plants. The pre-planting soil (initial) composite samples and the postharvest turnip green soil (final) samples were shipped to the 3M Environmental 
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Att 2-2

Laboratory for PFOA analysis. Once finalized, the analytical results will be provided in a 

subsequent quarterly status report.

During the last week of December 2011, one tomato began ripening. Because fruit 

production will vary with the maturity and condition of each of the plants over the next 

quarter, sequential harvest of vine-ripened fruits will be performed. Tomatoes that are 

ripe will be picked, rinsed with DI water and allowed to air dry before weighing. 

Tomatoes will be placed in doubled polyethylene bags with sample labels identifying the 

treatment level and plant sampled and held in frozen storage. Upon completion of the 

tomato harvest, two composite samples with 12 tomatoes per sample will be prepared 

from each of the control and the six treatment level groups and shipped on dry ice to the 

3M Environmental Laboratory for PFOA analysis. Post-harvest final tomato soil 

composite samples will also be collected and shipped ice to the 3M Environmental 

Laboratory for PFOA analysis. Once finalized, the analytical results will be provided in a 

subsequent quarterly status report.

Potatoes have lagged behind the other crops because of slow sprouting of the second 

sowing of seed potato. Harvest and sampling of potatoes, collection of the post-harvest 

final potato soil samples and completion of vegetative uptake study field activities are

expected to occur late in the first quarter of 2012. Photographs of the test facility and 

crops are shown in Figures 1 through 4.
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Figure 1

Turnip Green Plant

October 13, 2011
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Figure 2

Tomato Section

December 31, 2011
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Figure 3

Large Potato Plant

December 31, 2011
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Figure 4

Late Sprouting Potatoes

December 31, 2011